A method of obtaining a zeolite catalysts, a method of obtaining related zeolites, zeolite catalysts

 

The invention relates to the field of catalysts. Describes a method for zeolite catalysts in the form of microspheres comprising zeolite and oligomeric silica, characterized by high mechanical strength. The method consists in placing a quick drying of the suspension, to which is optionally added tetrachlorosilane obtained by synthesis of the zeolite by hydrothermal treatment at autogenous pressure of the reaction mixture containing tetraalkylammonium as a template agent, and the exposure fired product obtained after drying. The technical result is obtained zeolite catalyst in the form of microspheres with high mechanical strength. 2 N. and 26 C.p. f-crystals, 4 Il.

This invention relates to a new process for the preparation of zeolitic catalysts in the form of microspheres comprising zeolite and oligomeric silica, characterized by high mechanical strength.

It is well known that zeolites, synthetic porous crystalline materials having catalytic activity can be linked using inorganic binders to increase a size that allows IP crystals of zeolite promote intergranular diffusion of the internal particles of the reactants and products of reaction and allow you to achieve high performance, on the other hand, similar sizes make it impossible intergranular diffusion in reactors fixed layer or the separation of the zeolite catalyst from the reaction medium in the reactor mixing. To solve these problems, zeolites connected by means of suitable binders. Methods of obtaining related zeolites must be such as to prevent clogging of zeolite cavities, which usually leads to the decrease of catalytic activity. For reactions in which it is necessary to avoid catalytic contribution of the binder, such as many of the oxidation reaction and the reaction catalyzed by acids, the use of a catalytically inert material such as silica as a binder is of particular interest. However, silica has a weak astringent properties and, therefore, not typically used in extrusion, because it does not provide an extrudable product sufficient hardness. European patent 265018 describes a method of producing catalysts based on zeolite and oligomeric silica. According to this way of zeolite catalysts are linked in the form of microspheres with high mechanical strength, and are best suited for reactions, kotoriii:

a) obtaining a zeolite that will be associated with crystallization under hydrothermal conditions from a suitable mixture of reagents;

b) separating the crystals of the zeolite obtained in stage a);

C) possible washing of the zeolite by re-dispersion in water and a new branch of the crystalline phase;

g) obtaining an aqueous solution of the oligomeric silica and tetraalkylammonium hydrolysis liquid tetrachlorozincate in an aqueous solution of tetraalkylammonium, at a temperature in the range from 2 to 120° C, over time, changing in the range from 0.2 to 24 hours;

d) dispersion of the crystalline zeolite phase obtained after stage b), in the solution described in stage g);

e) quick drying this dispersion is loaded into the spray drying;

g) calcining the microspheres of the product obtained at the stage of drying.

We found a relatively simple way of obtaining catalysts comprising zeolite and oligomeric silica, having a high mechanical strength. This simplified method allows to achieve certain properties of the binding phase, such as pore distribution mainly in the area of mesopores and high surface area, which ensures the absence of the WPPT is a new way at the same time allows you to simultaneously reduce the number of required stages of the working cycle and also reduce the amount of reagents used. In particular, in contrast to known techniques, the method according to the invention no longer requires the Department of zeolite crystalline phase from the suspension obtained at the end of the synthesis; indeed, it has been unexpectedly found that the zeolites, synthesis of which requires the presence of tetraalkylammonium (TAAN) as template agent, i.e. as a connection that allows you to specify a regular and constant porosity in the structure of zeolite suspensions obtained after completion of the synthesis, in which the crystals of the zeolite and tetraalkylammonium remain in solution and can be used without subsequent stages of purification and/or filtration, for the preparation of zeolites related oligomeric silica, in the form of microspheres. To avoid phase separation of the zeolite from the industrial point of view has huge advantages, especially when working with zeolite crystals having a size of less than 0.5 μm, which cannot be separated from the environment in which they were synthesized by conventional means, for example by filtration or continuous centrifugation, and require more costly methods.

The invention therefore relates to a method for polut in fast drying of the suspension, which usually add tetrachlorosilane obtained by synthesis of the zeolite by hydrothermal treatment at autogenous pressure of the reaction mixture containing tetraalkylammonium as a template agent, and calcining the obtained after drying products.

The suspension obtained after completion of the synthesis of the zeolite by hydrothermal treatment in the presence of tetraalkylammonium (TAA-OH) as a template agent, which is a fast drying according to this invention may contain zeolite crystals, the fraction of tetraalkylammonium, which is not located inside the pores of the zeolite, and possibly oxides of silicon and other heteroatoms. Indeed it is known that in the synthesis of zeolites is necessary for completion of the synthesis to use excess tetraalkylammonium and an appropriate share of TAA-HE, being in the form of a solution in the reaction medium. The use of this suspension obtained in the synthesis of zeolite, in addition to the advantages mentioned above, thus, reduces the total number of TAA-IT is used in the method of producing zeolites related oligomeric silica, compared with that required in religating silica and add it to the crystals of the zeolite, separated by means of filtration or centrifugation, before the stage of rapid drying.

When according to this invention tetrachlorosilane is added to the suspension obtained in the synthesis of zeolite to the stage of its rapid drying, it must be added in quantities varying in the range from 0.08 to 0.50 mol per 100 grams of the slurry containing the zeolite. Tetrachlorosilane is selected from compounds having the formula Si(OR)4where the substituents R, which may be the same or different from each other, are alkyl chains containing from 1 to 4 carbon atoms.

Rapid drying of the suspension is preferably loaded into the spray dryer. At the end of treatment quick drying receive microspheres are calcined at a temperature in the range from 400 to 800° C.

Zeolite catalysts obtained according to the method according to this invention, characterized by high mechanical strength, they include oligomeric silica and zeolite weight ratio of from 0.05 to 0.30 and have the form of microspheres having a diameter in the range from 5 to 300 μm, in which the zeolite crystals are framed by Si-O-Si bridges. Zeolites, which can be linked oligomeric silica-based method according to this impetago agent, particularly suitable zeolites may be selected from zeolites with structure of MFI, MEL, MFI/MEL, MOR, FAU, FAU/EMT and WEAH.

The suspension, which can be subjected to rapid drying and subsequent calcination to obtain zeolites related oligomeric silica, according to this invention are those obtained by the synthesis of zeolite under hydrothermal conditions, under autogenous pressure and in the presence of TAA-IT is processed by the methods described above in the preceding technology and well-known experts in this area; in particular according to the preferred aspect of this invention, the zeolites, which are connected, are silicalite related to the MFI group, or a zeolite comprising oxides of silicon and aluminum, having an MFI, MEL, MFI/MEL, BEA, MOR, FAU and FAU/EMT structure. The suspension obtained in this synthesis, contain crystals of zeolite, tetraalkylammonium, silicon and possibly oxides of aluminum; in this case, adding tetrachlorozincate not necessarily; these suspensions are served in the spray drying and the resulting microspheres are fired under the conditions described above.

Therefore, one aspect of the invention, therefore, is a method of obtaining a zeolite catalyst is asisa to the MFI group, or from a zeolite comprising oxides of silicon and aluminum, having an MFI, MEL, MFI/MEL, BEA, MOR, FAU and FAU/EMT structure, which is quick drying of the suspension obtained in the synthesis of the specified zeolite by hydrothermal treatment at autogenous pressure of the reaction mixture containing tetraalkylammonium as a template agent, and calcining the product obtained after drying.

The conditions under which receive the suspension is well-known to specialists in this field and is usually described in the existing technology. For example, silicalite related to the MFI group, called S-1, and its reception is described in U.S. patent 4061724; BEA zeolite containing oxides of silicon and aluminum, called beta-zeolite, and access is described in U.S. patent 3308069; MFI zeolite containing silicon oxide and aluminum called ZSM-5, and its reception is described in U.S. patent 3702886 and reprinted in US 29948; MOR zeolite containing oxides of silicon and aluminum, called mordenite, and access is described in U.S. patent 4052472; FAU zeolite, containing oxides of silicon and aluminum, called N-Y, and access is described in U.S. patent 3306922; FAU/EMT zeolite containing oxides of silicon and aluminum, called ECR-30, and obtain the n in American patent 4289607; MEL zeolite containing oxides of silicon and aluminum, called ZSM-11, described in U.S. patent 3709979.

The product obtained after drying before firing can be optionally treated with air at 200 to 300° C for 2-10 hours or entered into the exchange reaction in acid form according to known methods to remove possibly present alkali metals.

The most suitable zeolite for binding according to the preferred aspect is silicalite S-1. Zeolite material in the form of microspheres having a diameter of 5 to 300 μm, consists of silicalite S-1 and oligomeric silica, the weight ratio of oligomeric silica/silicalite varying from 0.05 to 0.3, with high mechanical strength, used in the field of catalysis is new and the next object of the present invention. When using a zeolite comprising oxides of silicon and aluminum belonging to the MFI, MEL, MFI/MEL, BEA, MOR, FAU and FAU/EMT, small amounts of aluminum are also present in the binding phase of the final catalyst. These latter catalysts obtained according to the method of the present invention, having a high mechanical strength, which are used in processes for the conversion of hydrocarbons in cachaca.

According to a particularly preferred aspect of the present invention, when the zeolite, which should be bound, refers to MFI, MFI/MEL and MEL group and optionally containing other heteroatoms in addition to silicon, the suspension, which is then subjected to rapid drying, is the one that is released during the synthesis of zeolite thus obtained to obtain the output of the zeolite after crystallization as close as possible to 100%, for example from 98 to 100%. In particular, it is preferable to obtain thus to get the output after crystallization of 100%, which corresponds to the total allocation in the zeolite only silica and possible heteroatoms present in the reaction mixture. Zeolites MFI, MFI/MEL and MEL groups that are particularly suitable for exit after crystallization of 100% and therefore preferably be contacted according to this preferred aspect of the present invention, are selected from the

1) MFI zeolite having the formula RNO2·qTiO2·SiO2where M is a metal selected from aluminum, gallium, or iron, p varies in the range from 0 to 0.04 and q has a value varying in the range from 0.0005 to 0.03. In particular, when p is 0, the zeolite is a titanium silicalite TS-1, OPI is the 226257, European patent 266825 and European patent 226258, respectively;

2) MFI zeolite having the formula aAl2O3·(1-a)SIO, SIS2where a has a value varying from 0 to 0.02. In particular, when a is zero, the zeolite is silicalite S-1, is described in U.S. patent 4061724; and when different from 0, the zeolite is ZSM-5 described in U.S. patent 3.702.886 and reissued U.S. patent 29948;

3) MEL or MFI/MEL zeolites having the formula HCO2·(1-x)SIO, SIS2where x has a value varying in the range from 0.0005 to 0.03. These zeolites are described in BE 1001038 and title TS-2 and TS-1/TS-2.

Thus, according to a preferred aspect, the obtaining performed so that the suspension is subjected to rapid drying out from the synthesis of MFI zeolite to yield after crystallization of more than 98%, preferably 100%.

This invention relates to a process for the preparation of zeolitic catalysts in the form of microspheres containing MFI zeolite having the formula RNO2·qTiO1·SiO2and oligomeric silica, where M is a metal selected from aluminum, gallium, or iron, p varies in the range from 0 to 0.04 and q has a value varying in the range from 0.0005 to 0.03, which SOS is, is smenauscheesa in the range from 190 to 230° C and over time, changing in the range from 0.5 to 10 hours, in the absence of alkali metals, a mixture containing a silicon source, a titanium source, optionally a source of metal M and tetrapropylammonium having the following composition expressed as molar relations

Si/Ti=35-2000,

M/Si=0-0,04, where M is selected from Al, Ga and Fe,

TPA-OH/Si=0.2 to 0.5, where TPA-tetrapropylammonium,

H2O/Si=10-35,

b) adding tetrachlorozincate to the suspension obtained after the previous stage (a);

C) rapid drying of the suspension obtained in stage b);

g) calcining the product obtained in stage C).

Sources of silicon, titanium and metal are the same as those described in U.S. patent 4410501, European patent 226257, European patent 266825 and European patent 226258. The source of silicon is preferably tetraethylorthosilicate, the source of titanium is preferably tetraethylorthosilicate, the source of metal is preferably soluble salt of the metal. Zeolite, which preferably communicates according to this method is titanium silicalite TS-1.

According to a preferred aspect, the obtaining performed so that suspenseful 100%, and MFI zeolite, which is associated, is l2About3·(1-a)SiO2, an additional object of the present invention relates to a process for the preparation of zeolitic catalysts in the form of microspheres, consisting of MFI zeolite having the formula l2About3·(1-a)SiO2and oligomeric silica, where a has a value varying in the range from 0 to 0.02, which consists of

a) synthesis of the zeolite by means of hydrothermal treatment at autogenous pressure, at a temperature varying in the range from 190 to 230° C and for a time ranging from 0.5 to 10 hours, in the absence of alkali metals, a mixture containing a source of silica, optionally a source of aluminum and tetrapropylammonium having the following composition expressed as molar relationship:

Al/Si=0-0,04,

TPA-OH/Si=0.2 to 0.5, where TPA-tetrapropylammonium,

H2O/Si=10-35;

b) adding tetrachlorozincate to the suspension obtained after the previous stage (a);

C) rapid drying of the suspension obtained in stage b);

g) calcining the product obtained in stage C).

Sources of silicon and aluminum are the same as those described in U.S. patent 4061724 and U.S. patent 3702886. The source of silicon predpochtite the camping alkyl, containing 3 to 4 carbon atoms.

According to a preferred aspect, the obtaining performed so that the suspension is subjected to rapid drying, is obtained from the synthesis of MFI/MEL or MEL zeolite to yield after crystallization of more than 98%, preferably 100%, and MFI/MEL or MEL zeolite, which is associated, is HCO2·(1-x)SiO2, an additional object of the present invention relates to a process for the preparation of zeolitic catalysts in the form of microspheres, consisting of MFI/MEL or MEL zeolite having the formula HCO2·(1-x)SiO2and oligomeric silica, where x has a value varying in the range from 0.0005 to 0.03, which consists of

a) synthesis of the zeolite by means of hydrothermal treatment at autogenous pressure, at a temperature varying in the range from 190 to 230° C and for a time ranging from 0.5 to 10 hours, in the absence of alkali metals, a mixture containing a silicon source, a titanium source, tetraalkylammonium having the following composition expressed as molar relationship:

Si/Ti=35-2000,

TAA-OH/Si=0.2 to 0.5,

H2O/Si=10-35;

b) adding tetrachlorozincate to the suspension obtained after the previous stage (a);

C) rapid drying of the suspension obtained in the article is nigerose, which can be used in binary and ternary mixtures are the same as described in BE 1001038. The source of silicon is preferably tetraethylorthosilicate, the source of titanium is preferably tetraethylorthosilicate.

The hydrothermal treatment in the previous stages of the synthesis of (a) zeolite preferably is carried out at temperatures varying in the range from 200 to 230° C, and is, for example, at a temperature higher than 200° C and less than and equal to 230° C.

Features of preparation of the composition of the reaction mixture and the reaction temperature used in the previous stages (a), which provide zeolites with MFI, MFI/MEL and MEL structure, in particular TS-1 and S-1, with high yield after crystallization, preferably 100%, by themselves, are novel and constitute another aspect of the present invention. In the examples relating to the receipt of the zeolites with the MFI, MEL and MFI/MEL structure described in the existing technology, established or calculated yield after crystallization is also significantly lower than 100%.

Using this special preparation of the composition and reaction conditions on stage and receive the microspheres at the end of stage d), consisting of MFI, MEL, MFI/MEL zeolites related Alisa in the range from 0.05 to 0.3, having a large surface area, the pore distribution in the associated phase, mainly in mesoporous area, high mechanical strength, which can be used for catalysis. In particular zeolite material in the form of microspheres having a diameter varying from 5 to 300 μm, consisting of zeolite TS-2 or TS-1/TS-2 and oligomeric silica weight ratio of oligomeric silica/zeolite, changing in the range from 0.05 to 0.3, is a new and additional object of the present invention.

In the previous stages b) tetrachlorozincate (TAOS), preferably tetraethylorthosilicate, is added in amounts varying from 0.08 to 0.50 mol per 100 g of zeolite contained in the suspension obtained at the end of stage a).

Suspension allocated after stage b), is preferably heated to 40 to 100° C for 0.5-10 hours before subjected to the stage of fast drying.

In the previous stages) suspension obtained after stage b), is subjected to rapid drying, preferably spray drying, receive microspheres containing three-dimensional lattice of silicon dioxide, in which by means of a Si-O-Si bridges densely Packed crystallites of zeolite.

The microspheres obtained after stage b), the firing is 14% by weight aqueous solution were loaded into the autoclave. 547 g tetraethylorthosilicate (TEOS) and a solution containing 547 g of TEOS and 30 g tetraethylorthosilicate (TEOT), were then quickly added, the operations were carried out in a closed system. Not thus exposing the mixture to aging, immediately began hydrothermal treatment at autogenous pressure at 200° C for 2 hours. When the crystallization was completed, the autoclave was cooled and molokopodobnye the suspension is unloaded.

100 g of this suspension was centrifuged, re-dispersible in water and centrifuged again; the resulting solid residue was dried, burned and used to identify the crystalline phase. The yield after crystallization was confirmed as 100%, the chemical analysis gave the following results: SiO296,8%, TiO23,19%.

In the analysis of TEM (transmission electron microscopy) was observed crystalline agglomerates with an average diameter of 0.3 microns.

Spectrum in the visible and ultraviolet regions shown in Fig.1, curve A (the wavelength is indicated on the x-axis, the absorption axis of ordinates).

110 g of TEOS was added to the remaining molokopodobnye suspension, and the mixture was heated to 60°C for one hour and then placed into a spray drying ( 1 m). Were obtained compact microspheres having an average diameter of 30 μm, the weight ratio of oligomeric silica/zeolite is 0.1. Microspheres were placed in a sound-absorbing device in nitrogen atmosphere and was heated to 550° C. After 2 hours of storage at this temperature in the nitrogen atmosphere was gradually replaced with nitrogen in the air and the product was left for 2 hours at 550° C in an atmosphere of air. The resulting product had the following composition: SiO297,05%, TiO22,94%.

Spectrum in the visible and ultraviolet regions shown in Fig.1, curve B. by Comparing the spectra shown in Fig.1, you can see that in both samples the entire titanium has a tetrahedral coordination and, consequently, is located in the zeolite structure. In Fig.2 presents the size distribution of the microspheres, determined Granulometre 715 E measured before ultrasonic treatment (curve), and after ultrasonic treatment for 1 hour (curve)(Branson Batch 5200). The average diameter of the microspheres, expressed in microns, is shown on the x-axis, % of microspheres on an axis of ordinates. It is evident from Fig.2 one can see that the distribution of particles is not changed after ultrasonic treatment and sledovatel is HE) in the form of 14% by weight aqueous solution was dissolved in 7 g of aluminum isopropylate and then was added 1094 g tetraethylorthosilicate (TEOS). The resulting mixture was loaded into an autoclave and subjected to hydrothermal treatment at autogenous pressure at 200° C for 2 hours. When the crystallization was completed, the autoclave was cooled and molokopodobnye the suspension is unloaded.

100 g of this suspension was centrifuged, re-dispersible in water and centrifuged again; the resulting solid residue was dried, burned and used for identitical crystalline phase. The yield after crystallization was confirmed as 100%, the chemical analysis gave the following results: SiO299,440%, TiO20,56%.

110 g of TEOS was added to the remaining molokopodobnye suspension, and the mixture was heated to 60° C for 1 hour and then placed into a spray dryer (Niro Mobile Minor Hi-TEC, the temperature of the incoming air 230° C; the air temperature at the outlet 150° C; a chamber diameter of 1 m). Were obtained compact microspheres having an average diameter of 30 μm, the weight ratio of oligomeric silica/zeolite is 0.1. Microspheres were placed in a sound-absorbing device in nitrogen atmosphere and was heated to 550° C. After 2 hours of storage at this temperature in the nitrogen atmosphere was gradually replaced with nitrogen in the air and the product was left for 2 hours at 550° C atmorrepepina size of the microspheres, defined Granulometre 715 E measured before ultrasonic treatment (curve), and after ultrasonic treatment for 1 hour (curve) (Branson Batch 5200). The average diameter of the microspheres, expressed in microns, is shown on the x-axis, % of microspheres on an axis of ordinates. It is evident from Fig.3 one can see that the distribution of particles is not changed after the ultrasonic treatment, and therefore, the catalyst has good mechanical strength.

Example 3

1102 g of water and 1096 g of TEOS were added to 802 g 40% TPA-HE. The resulting mixture was loaded into an autoclave and subjected to hydrothermal treatment at 180° C for 3 hours. The autoclave is then cooled and molokopodobnye the suspension is unloaded. 100 g of this suspension was centrifuged, re-dispersible in water and centrifuged; the resulting solid residue was dried, burned. The yield after crystallization was confirmed as 84%. The remaining suspension was placed in a spray dryer (Buchi 190, the temperature of the incoming air 200° C; the air temperature at the outlet 140° C).

In Fig.4 presents the size distribution of the microspheres, determined Granulometre 715 E measured before ultrasonic treatment (_data/85/854737.gif" border="0">) (Branson Batch 5200). The average diameter of the microspheres, expressed in microns, is shown on the x-axis, % of microspheres on an axis of ordinates. It is evident from Fig.4 one can see that the distribution of particles is not changed after the ultrasonic treatment, and therefore, the catalyst has good mechanical strength.

Example 4 (comparison)

TS-1 obtained according to U.S. patent 4410501; the solution containing 2844 g TEOS and 153 g TEAT, was added during 1 hour to 4662 g of 15% by weight aqueous solution of TPA-HE. The final solution was slightly heated to accelerate the hydrolysis and evaporation, the resulting ethanol. After about 5 hours at 80° With the added 5850 g of water. The resulting solution was loaded into an autoclave and was heated to 180° C under autogenous pressure for 5 hours. After completion of the crystallization, the autoclave was cooled and molokopodobnye the suspension was unloaded. 1000 g of this suspension was centrifuged, re-dispersible in water and centrifuged; the resulting solid residue was dried, burned and used to identify the crystalline phase. The yield after crystallization was confirmed as 89%, chemical analysis gave the following result: SiO293,97%, TiO23,10%.

leegomery silica, consisting of (a) synthesis of zeolite under hydrothermal treatment at autogenous pressure in the presence of Tetra-alkilammonievymi as template agent to obtain a suspension containing zeolite crystals and Tetra-alkilammoniya; b) rapid drying of the suspension obtained in the result of implementation of stage (a); and C) calcining the product obtained in stage (b).

2. A method of obtaining a zeolite catalysts in the form of microspheres comprising zeolite and oligomeric silica under item 1, comprising a) synthesis of zeolite under hydrothermal treatment at autogenous pressure in the presence of Tetra-alkilammonievymi as template agent to obtain a suspension containing zeolite crystals and Tetra-alkilammoniya; b) adding Tetra-alkalitolerant as a source of silicon to the suspension obtained in stage a); C) rapid drying of the suspension obtained in the result of implementation of stage (b); and d) calcining the product obtained in stage (b).

3. The method according to p. 1 or 2, wherein the zeolite is selected from zeolite with structure MFI, MFI/MEL, MEL, BEA, MOR, FAU and FAU/EMT.

4. The method according to p. 2, in which Tetra-alkalitolerant add in the amount of from 0.08 to 0.50 mol per 100 g of zeolite contained in poluchenii the formula Si(OR)4where the substituents R are identical or different, are alkyl chains containing from 1 to 4 carbon atoms.

6. The method according to p. 1 or 2, where fast drying is carried out by spray drying.

7. The method according to p. 1 or 2, in which the firing is carried out at a temperature of from 400 to 800° C.

8. The method according to p. 1 or 2, which is quick drying of the suspension obtained in the synthesis of zeolite under hydrothermal conditions, under autogenous pressure of the reaction mixture containing Tetra-alkilammoniya as a template agent, and calcining the product obtained after drying in which the zeolites are selected from silicalite related to the MFI group, or a zeolite comprising oxides of silicon and aluminum, with MFI, MFI/MEL, MEL, BEA, MOR, FAU and FAU/EMT structure.

9. The method according to p. 2, in which the receipt of zeolite catalysts in the form of microspheres containing MFI zeolite having the formula R CME2·qTi2·SiO2and oligomeric silica, where M is a metal selected from aluminum, gallium or iron; p has a value from 0 to 0.04 and q has a value of from 0.0005 to 0.03, consists of (a) synthesis of the zeolite by means of hydrothermal treatment at autogenous pressure, at a temperature of from 190 to 230° C and in the course of from 0.5 to 10 h, no and Tetra-propylammonium hydroxide, having the following composition expressed as molar relationship:

Si/Ti=35-2000

M/Si=0-0,04, where M is selected from Al, Ga and Fe

TPA-OH/Si=0.2 to 0.5, where TPA = tetrapropylammonium

H2O/Si=10-35

b) adding Tetra-alkalitolerant to the suspension obtained after the previous step a); C) rapid drying of the suspension obtained in stage b); d) calcining the product obtained in stage C).

10. The method according to p. 9, in which the source of silicon is Tetra-utilitarian, the source of titanium is tetraethylorthosilicate and source metal is a water soluble salt of the metal.

11. The method according to p. 9, in which the zeolite is a titanium-silicalite TS-1.

12. The method according to p. 2, in which the receipt of zeolite catalysts in the form of microspheres, consisting of MFI zeolite having the formula and A12About3·(1-a)SiO2and oligomeric silica, where a has a value from 0 to 0.02, consists of (a) synthesis of the zeolite by means of hydrothermal treatment at autogenous pressure, at a temperature of from 190 to 230° C and in the course of from 0.5 to 10 h, in the absence of alkali metals, a mixture containing a source of silicon, optionally, a source of aluminum and Tetra-propylammonium hydroxide having the following composition expressed as molar relationship:

13. The method according to p. 12, in which the source of silicon is Tetra-utilitarian and the source of aluminum is A1(or SIG)3where R is an alkyl containing from 3 to 4 carbon atoms.

14. The method according to p. 12, in which the zeolite is silicalite S-1.

15. The method according to p. 2, in which the receipt of zeolite catalysts in the form of microspheres, consisting of MFI/MEL or MEL zeolite having the formula x TiO2·(l-x)SiO2and oligomeric silica, where x has a value of from 0.0005 to 0.03, consists of (a) synthesis of the zeolite by means of hydrothermal treatment at autogenous pressure, at a temperature of from 190 to 230° C and in the course of from 0.5 to 10 h, in the absence of alkali metals, a mixture containing a source of silicon, a source of titanium, Tetra-alkylammonium hydroxide having the following composition expressed as molar relationship:

Si/Ti=35-2000

TAA-OH/Si =0,2-0,5

H2O/Si= 10-35

b) adding Tetra-alkalitolerant to the suspension obtained after the previous step a); C) rapid drying of the suspension obtained in stage b); d) calcining the product obtained in stage C).

16. The method according to p. 15, in which the Method according to PP.9, 12 and 15, in which the hydrothermal treatment stage (a) is conducted at a temperature of from 200 to 230° C.

18. The method according to PP.9, 12 and 15, in which at the stage b) of Tetra-alkalitolerant add in the amount of from 0.08 to 0.50 mol per 100 g of zeolite contained in the suspension obtained at the end of stage a).

19. The method according to PP.9, 12 and 15, in which at the stage b) of Tetra-alkalitolerant is tetraethylorthosilicate.

20. The method according to PP.9, 12 and 15, in which the firing stage C) is carried out at a temperature of from 400 to 800° C.

21. The method of obtaining MFI zeolite having the formula R CME2·qTi2·SiO2where M is a metal selected from aluminum, gallium and iron, p has a value from 0 to 0.04 and q has a value of from 0.0005 to 0.03, which is in the hydrothermal treatment at autogenous pressure, at a temperature of from 190 to 230° C and in the course of from 0.5 to 10 h, in the absence of alkali metals, a mixture containing a silicon source, a titanium source, optionally, a source of the metal M and tetrapropylammonium hydroxide having the following composition expressed as molar relationship:

Si/Ti=35-2000

M/Si=0-0,04, where M is selected from Al, Ga and Fe

TPA-OH/Si=0.2 to 0.5, where TPA=tetrapropylammonium

H2O/Si=10-35.

22. The method according to p. 21, in which the zeolite is Tito2where a has a value from 0 to 0.02, which is in the hydrothermal treatment at autogenous pressure, at a temperature of from 190 to 230° C and in the course of from 0.5 to 10 h, in the absence of alkali metals, a mixture containing a source of silicon, optionally, a source of aluminum and Tetra-propylaminoethyl having the following composition expressed as molar relationship:

Al/Si=0-0,04

TPA-OH/Si=0.2 to 0.5, where TPA-tetrapropylammonium

H2O/Si=10-35.

24. The method according to p. 23, in which the zeolite is silicalite S-1.

25. The method of obtaining MFI/MEL or MEL zeolite having the formula x TiO2·(l-x)SiO2where x has a value of from 0.0005 to 0.03, which is in the hydrothermal treatment at autogenous pressure, at a temperature of from 190 to 230° C and in the course of from 0.5 to 10 h, in the absence of alkali metals, a mixture containing a source of silicon, a source of titanium, Tetra-alkilammoniya (TAAN) having the following composition expressed as molar relationship:

Si/Ti=35-2000

TAA-OH/Si=0,2-0,5

H2O/Si=10-35.

26. Zeolite catalysts comprising zeolite and oligomeric silica, in the form of microspheres, in which the zeolite is a zeolite comprising oxides of silicon and aluminum related to MFI, MFI/MEL, MEL, BEA, MOR, FAU and FAU/EMT groups, the m consisting of silicalite and oligomeric silica, the weight ratio of oligomeric silica/silicalite from 0.05 to 0.3.

28. Zeolite catalysts in the form of microspheres having a diameter of 5 to 300 μm, consisting of oligomeric silica and zeolite selected from TS-2 or TS-1/TS-2, with the weight ratio of oligomeric silica/zeolite, from 0.05 to 0.3.



 

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