A method of converting hydrocarbons using a bound zeolite zeolite catalyst

 

(57) Abstract:

Usage: in the petrochemical industry. The inventive hydrocarbon feedstock contacts in the conversion of hydrocarbons with the associated zeolite zeolite catalyst comprising (a) first crystals of a first zeolite and (b) a binder containing the second crystals of a second zeolite, the average particle size which is smaller than the first crystal and the second crystal are in the fused state with the first crystals to form on them coverage or partial coverage. Technical result - increase the selectivity of the process. 50 C.p. f-crystals, 8 tab., 4 Il.

The present invention relates to zeolites, which are connected zeolites, which are characterized by high activity, selectivity and/or ability to retain activity when used in the conversion of hydrocarbons.

Both natural and artificial zeolite materials exhibit the presence of a catalytic properties in various processes for the conversion of hydrocarbons. In addition, the zeolite materials used as adsorbents, carriers for catalysts intended for different types of processes for the conversion of hydrocarbons and d is lO4and SiO4tetrahedra connected by a common oxygen atoms. The negativity of these tetrahedra is balanced by the inclusion of cations, such as ions of alkali or alkaline-earth metals. When getting some of zeolites in the synthesis process of the present non-metallic cations such as Tetramethylammonium (TMA) or tetrapropylammonium (TPA). Internodes (distance between nodes) or channels formed by the crystalline lattice, allow the use of zeolites as molecular sieves in separation processes, as catalysts for chemical reactions and as catalyst carriers in a variety of processes for the conversion of hydrocarbons.

The zeolites are materials containing silicon dioxide and optionally aluminum oxide, and materials in which kremmidiotis and aluminiumoxide areas wholly or partly replaced by other oxides. For example, kremmidiotis plot can override the oxide of germanium, tin oxide and mixtures thereof. Aluminiumoxide plot can replace boron oxide, iron oxide, gallium oxide, indium oxide and mixtures thereof. In all cases, unless otherwise stated, used in the description the terms "zeolite" and "zeolite material" oboznacheniya atoms, but also materials which contain acceptable substitute atoms instead of atoms of silicon and aluminum.

Synthetic zeolites are usually obtained by crystallization from supersaturated synthesis mixture. Next, the resulting crystalline product is dried and calicivirus obtaining zeolite powder. Although this zeolite powder has good adsorption properties, its use is strictly limited, because the powder does not show appreciable mechanical strength.

The mechanical strength of the zeolite can be given by the preparation of the zeolite unit, such as granules, pellets or extrudate. The extrudate can be prepared by extrusion of the zeolite in the presence of nazaretova a binder, and drying and calcining the resulting extrudate. Examples of these binders include materials such as aluminum oxide, silicon dioxide, titanium and clay of different types.

Although these related zeolite aggregates and have a much higher mechanical strength in comparison with zeolite powder using a bound zeolite in the catalytic conversion process, however, due to the presence of binders can deteriorate Akti is EP, as the binder, usually contained in an amount up to about 60 wt.% the weight of the zeolite, this binder "dilutes" the adsorption properties of the zeolite. In addition, since the bound zeolite is prepared by extruding the zeolite together with a binder, followed by drying and calcining the extrudate, it is amorphous binder can penetrate into the pores of the zeolite, to block any access to the zeolite pores or reduce the rate of mass transfer to these zeolite pores, which can reduce the effectiveness of the zeolite, when used in the conversion of hydrocarbons and in other applications. Moreover, when the bound zeolite is used in catalytic processes, the binder may influence the course of chemical reactions going on inside the zeolite, and may also catalyze undesirable reactions, which may be the formation of undesirable products.

More close analog of the invention is a method of converting hydrocarbons comprising contacting the hydrocarbons in the conversion of hydrocarbons with zeolite catalyst containing a crystalline zeolite with large pareunia disadvantages.

Thus, there is a need for the development of a method of converting hydrocarbons in the implementation which uses a zeolite catalyst, which can eliminate or at least reduce the above problems.

This object is achieved by a method of converting hydrocarbons by contacting the hydrocarbon feedstock in the conversion of hydrocarbons with the associated zeolite zeolite catalyst, including:

(a) first crystals of a first zeolite and

(b) a binder containing the second crystals of a second zeolite, the average particle size which is smaller than the first crystal and the second crystal are in the fused state with the first crystals to form on them coverage or partial coverage.

It was found that in the case of the use of the zeolite catalyst, which includes the first zeolite particles and wherein the particles of the second zeolite is used as the binder, suddenly get a catalyst, which ensures the prevention of reactions associated with the presence of this binder, and is characterized by improved mass transfer of reagents to this catalyst and increased access Rea is. the AK, for example, the acidity of the particles of this second zeolite can be the same as that of the particles of the first zeolite, or the acidity of the particles of this second zeolite may be higher or lower than the acidity of the particles of the first zeolite, allowing, therefore, further improve the performance of the catalyst. When used in the conversion of hydrocarbons zeolite catalysts of the present invention exhibit improved performance characteristics. The zeolite catalyst of the present invention finds particular application in the conversion of hydrocarbons, where the reaction selectivity is important acidity of the catalyst in combination with a zeolite structure. Examples of such processes include catalytic cracking, alkylation reaction, dealkylation, dehydrogenization, disproportionation and parallelomania. The catalyst of the present invention may also find application in other processes in the conversion of hydrocarbons in which the carbon compounds transform into other carbon compounds. Examples of such processes include processes for hydrocracking, isomerization, dewaxing, oligomerization and reformer.

According to the invention describes a method of converting organic compounds by contacting these organic compounds in the conversion conditions with an associated zeolite zeolite catalyst. This is associated with the zeolite zeolite catalyst comprises particles of the first zeolite, the average size of which in the preferred embodiment, greater than about 0.1 micrometer, and the binder constituting the particles of the second zeolite, the average size of which is smaller than the first particles. To improve the mechanical strength of the zeolite typical zeolite particles, which are used as catalysts in the conversion of hydrocarbons, usually associated with silicon dioxide, aluminum oxide or other commonly used amorphous binders. Related zeolites zeolite catalysts of the present invention in a preferred embodiment, does not contain significant quantities of neoreality binders. Instead, the particles of the first zeolite of the present invention associated with the particles of the second CEO is ne particles of the second zeolite bind the particles of the first zeolite by adhesion to the surface of the first particles, thus formed matrix or bridge structure, which also holds together the first crystalline particles. In a more preferred embodiment, the second zeolite particles bind the first zeolite particles by accretion, resulting in a larger first zeolite crystals formed by coating or partial coating.

Without limiting the scope of the invention by any theory of the process, I believe that the benefits associated with zeolite zeolite catalyst provides a second zeolite, regulating the availability of reagents for acid sites on the external surface of the first zeolite. I believe that the acid sites existing on the external surface of the zeolite catalyst affect the reagents included in the pores of the zeolite, and the products that emerge from the pores of the zeolite. Accordingly, because the acidity of the second zeolite is chosen carefully, the second zeolite has no undesirable influence on the chemicals coming out of the pores of the first zeolite, as it may occur normally associated zeolite catalysts, and can positively vozdeistvovat reagents, coming out of the pores of the first zeolite. In addition, pecoma processes for the conversion of hydrocarbons in the pores of the first zeolite for hydrocarbons are more available. Regardless of the proposed theories such catalysts, when used for carrying out catalytic processes, exhibit improved properties, which are presented in this description.

Used in the description, the term "average particle size" means the average particle diameter, for example, the arithmetic average of the major axis and minor axis.

The meaning of the terms "acidity", "low acidity" and "high acidity" in relation to the zeolite specialists in this field known in the art. The acidic properties of the zeolite is well known. However, regarding the present invention it is necessary to distinguish between the strength of acids and density of acid sites. The acid sites of the zeolite can serve as the acid Bronsted or Lewis acid. The density of acid sites and the number of acid sites are important for determining the acidity of the zeolite. Factors that directly affect the fortress acid, are (I) the chemical composition of the zeolite framework, i.e., the relative concentration and type of atoms of the tetrahedron, (II) the concentration of the extra framework cations and the resulting extra framework materials, (III) the local structure of the zeolite, for example, the dimensions and Ruspoli the presence together of adsorbed molecules. A quantitative parameter acidity is associated with the degree of isomorphous substitution, provided, however, that this acidity is limited to the loss of acid sites for the composition of pure SiO2. Used in the description the terms "acidity", "low acidity" and "high acidity" refers to the concentration of acid sites regardless of the strength of these acid sites, which can be defined by the absorption of ammonia.

Examples of the first and second zeolites suitable for use in the present invention include zeolites with large pores, zeolites with medium pores and zeolites with small pores. Preferably the first and second zeolite is selected from the group consisting of zeolites with large pores, zeolites with medium pores and mixtures thereof. The pore size of zeolites with large pores are usually > 7 and these include zeolites types MAZ, MEI, FAU and EMT. Examples of zeolites with large pores include zeolite L, zeolite Y, zeolite X, offretite, omega zeolite, beta zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20. Typically, the pore size of the catalyst with an average pore size is < 7 , preferably from about 5 to about 6.8% and pore openings usually approximately 10 to 12, preferably use is itov medium pores include ZSM-34, ZSM-38, ZSM-48. The pore size of zeolites with small pores is from about 3 to about 5 Usually pore openings of such structure due to the presence of approximately 8 to 10, preferably about 8-membered cyclic structures, which include types such as CHA, ERI, KFI, LEV, and LTA. Examples of zeolites with small pores include ZK-4, ZK-5, zeolite A, zeolite T, gmelinite, clinoptilolite, habasit and erionite. The zeolites can also be attributed to gallerista and titanosilicates.

Preferably, the acidity of the crystals of a second zeolite either above or below the acidity of the zeolite crystals of the first.

The ratio between silicon oxide and aluminum oxide in the first zeolite usually depends on the specific process for conversion of hydrocarbons, in which the used catalyst. However, usually in the first zeolite ratio between silicon dioxide and aluminum oxide is at least 2:1, the preferred ratio between silicon dioxide and aluminum oxide is in the range from about 10:1 to about 1000:1, more preferably from about 20:1 to about 500:1. When this catalyst is used in the disproportionation of toluene or kikirevenge hydrocarbons, the preferred ratio on the first zeolite is from about 0.1 to about 15 micrometers. In many applications, the preferred average particle size is from about 2 to about 6 micrometers, and more preferably from about 2 to about 4 micrometers. In other applications, such as the cracking of hydrocarbons, the preferred average particle size is from about 0.1 to about 3.0 micrometers.

The size of the second zeolite particles is smaller than the first zeolite particles. Usually, the average size of the second zeolite particles is less than 1 micrometer, preferably from about 0.1 to less than 0.5 micrometer. The ratio between silicon oxide and aluminum oxide in the second zeolite is usually dependent on the specific process for conversion of hydrocarbons, in which the use of such a catalyst. Usually the ratio between silicon dioxide and aluminum oxide is at least 2:1. In those applications where a low acidity, the preferred molar ratio between silicon oxide and aluminum oxide in the second zeolite exceeds the ratio between silicon oxide and aluminum oxide in the first zeolite, and more preferably greater than 200: 1, for example, is 300:1, 500:1, 1000:1 and so on, In some application areas, as watt aluminum. In a preferred embodiment, the pore size of the second zeolite are usually such that an appreciable degree does not limit the access of hydrocarbons in the pores of the first zeolite. For example, when the particle size of the raw material, which is intended for conversion constitute 5-6,8 in the preferred embodiment, as the second zeolite should be used zeolites with large pores or zeolite with medium-sized pores. In the preferred embodiment, this second zeolite is contained in an amount constituting from about 10 to about 60 wt.% the weight of the first zeolite.

The rate of adsorption (PA) related preferred zeolites zeolite catalysts of the present invention exceeds to 1.00, more preferably greater than 1,10 and most preferably greater than 1,20, comprising, for example, of 1.25, 1.30 and so on, the Term "indicator adsorption" refers to the ratio between the weight percent adsorbed hydrocarbon (toluene, when the first zeolite bound zeolite zeolite is a zeolite with large pores or zeolite with an average pore, and n-hexane when the first zeolite bound zeolite zeolite is a zeolite with small pores) the weighted share of ormirovannogo hydrocarbon (toluene for zeolites with large pores and zeolite with medium pores and n-hexane for zeolite with small pores) from the weight amount of the first zeolite bound with silica zeolite catalyst prior to conversion of silicon dioxide (after drying and calcination) in the second zeolite bound zeolite zeolite catalyst. If the bound zeolite zeolite is not prepared by the conversion of amorphous silica to the second zeolite, the rate of adsorption is defined as the ratio between the weight percent adsorbed hydrocarbon (toluene, when the first zeolite bound zeolite zeolite is a zeolite with large pores or zeolite with an average pore, and n-hexane when the first zeolite bound zeolite zeolite is a zeolite with small pores) from the weight amount of the zeolite bound zeolite a zeolite catalyst of the present invention and the weight percent adsorbed hydrocarbon (toluene for zeolites with large pores and zeolite with medium pores and n-hexane for zeolite with small pores) from the weight amount of the first zeolite bound zeolite a zeolite catalyst, when the first zeolite link 30 wt.% amorphous silicon dioxide using the techniques described in example 1, step b, When determining the rate of adsorption of all the variables used in this method to determine the adsorption of the hydrocarbon catalyst, remain unchanged, and only different catalysts. The rate of adsorption finds particular application in the case when veralite used to determine the adsorption of toluene by zeolites with large pores and a zeolite with an average pore and n-hexane for zeolite with small pores to determine the rate of adsorption of the zeolite catalyst, well-known specialists in this field of technology. In the preferred method, which is referred to herein as "method ZHA", provides for the application of thermogravimetric analyzer for measuring the weight of adsorbed hydrocarbon (i.e., n-hexane or toluene), and this method includes a first pre-treatment of the zeolite catalyst, in this example, small amounts of zeolite in a stream of air with a flow rate of 210 ml/min under the following temperature conditions: aging of the catalyst in the 30oC for one minute, then the temperature rise rate of 20oC/min to 150oC; extract catalyst for 10 minutes at 150oC, then the temperature rise rate of 20oC/min to 450oC; exposure of the catalyst at 450oC for 45 minutes and subsequent cooling of the catalyst 30oC. Then measure the weight of the cooled catalyst and in the future, this weight is designated as "W1". Then in a chamber containing a catalyst, at a temperature of 30oC continuously for 60 minutes introducing the gas containing n-hexane (in this example) in nitrogen (P/Po 0,26). In this method, P denotes the partial pressure of the adsorbed hydrocarbon, and Po represents the total pressure. Next, after the filing of the ha Then re-measure the weight of the catalyst, and this weight is further designated as "W2". The amount of adsorbed hydrocarbons (in this case, hexane) in weight percent [(W2 - W1)/WI] 100. If in the case of catalysts containing zeolites with large pores or medium pores, using toluene, the method is identical, except that the preferred value of P/Po for toluene is 0.15. However, in the case of appropriate measures to prevent condensation in the connection lines connecting to the camera for sample, you can use other values of P/Po. The rate of adsorption can be calculated by the following formula

PA = W(ZBZ)/W(SBZ)

where W(ZBZ) denotes the weight percentage of the quantity of adsorbed hydrocarbon (toluene in the case of zeolites with large pores or medium pores or n-hexane for zeolites with small pores) from the weight of the quantity associated with the zeolite zeolite [the total weight of the zeolite (except for the whole not subjected to the conversion of amorphous silicon dioxide or other nucerity material)]; and

W(SBZ) denotes the weight percentage of the quantity of adsorbed hydrocarbon (toluene in the case of zeolites with large pores or medium pores or n-hexane for zeolites with small primitivum on the results of measurements of the total interest amount of absorbed hydrocarbons (zeolite + amorphous silicon dioxide) and dividing the result by (1-x). W(SBZ) is measured using the same associated with the silicon dioxide of the first zeolite unit, which is subjected to a conversion rate associated with the zeolite, the zeolite that is used to measure W(ZBZ), or, if the bound zeolite zeolite is not prepared by the conversion of amorphous silica to the second zeolite is measured using the bound zeolite, which is similar to the first zeolite bound zeolite zeolite and which bind to 30 wt.% amorphous silicon dioxide using the method described in example 1, stage b

The rate of adsorption was calculated for catalysts below. For linked-silica zeolite ZK5, containing 70 wt.% ZK5 and ZK5 associated with ZK5, the method of determining the rate of adsorption was carried out in standard conditions of absorption of n-hexane (P/Po = 0.25 To T = 30oC). The degree of absorption of n-hexane linked silica zeolite was 6,63 wt.%, while the extent of absorption of n-hexane by the zeolite bound zeolite (100% zeolite) was equal 11,10%. These results have been the same amount of zeolite. The degree of absorption of hexane associated silicon dioxide material ZK5 was 9.45 wt.% (6,63/0,70). It was found that the rate dt is 30 wt.% silicon dioxide, were subjected to tests in accordance with the above-described method except that, as the adsorbed substance used toluene. The degree of adsorption of toluene linked silica zeolite KL was equal to 5.4 wt.%, and bound zeolite KL a KL zeolite was 10.0 wt.%. It was found that the rate of adsorption was 1,29.

The catalyst used in the method of conversion according to the invention can be prepared using various methods, but in the preferred embodiment, it is made by three-stage method. The first stage provides a synthesis of the zeolite. Methods for the preparation of zeolites in the art known. So, for example, concerning the preparation of zeolite MFI can be noted that the preferred method comprises preparing a solution containing a hydroxide or bromide of tetrapropylammonium, alkali metal oxide, aluminum oxide, silicon oxide and water; and heating the reaction mixture to a temperature of 80-200oC for from about four hours to eight days. The obtained gel forms a solid crystalline particles that are separated from the reaction medium, washed with water and dried. The final product is then optionally can calcinaro the new one.

When the preferred MFI, this MFI can be identified in terms of molar ratios of oxides as follows:

0,90,2 M2/nO:Al2O3:5-500SiO2:zH2O

where M is chosen from the group consisting of a mixture of cations of alkali metals, preferably sodium, and organic ions such as tetraalkylammonium cations, preferably alkalemia group contains 2-5 carbon atoms, and z is from 0 to 40. In a more preferred embodiment, the MFI zeolite contains silicon dioxide and aluminum oxide in a molar ratio from about 10:1 to about 300:1.

Further preferred is associated with silica-zeolite is prepared by grinding a mixture containing zeolite crystals, silica gel or Sol, water and optionally an auxiliary agent for extrusion, to form a homogeneous composition in the form of an extrudable paste. Used for cooking is associated with silica zeolite unit kremmidiotis binder in the preferred embodiment, is silicasol, which preferably contains only a very small amount of aluminum oxide, for example less than 2000 ppm million and more prepost and, such that the content of zeolite in the dried extrudate is from about 30 to 90 wt.%, more preferably from about 55 to 85 wt.%, and the rest is mainly silicon dioxide, the content of which is, in particular, from about 15 to 45 wt.%.

Then the resulting paste is formed into, for example ekstragiruyut, and the extrudate is cut into small pieces, for example with a diameter of 2 mm, which are dried at 100-150oC for 4-12 h In a preferred embodiment, the dried extrudates next calicivirus in air at a temperature of from about 400 to 550oC for about 1-10 hours At this stage of calcination destructively also an aid for the extrusion, if it is used.

Associated with silica-optional unit can be obtained in the form of very small particles, which are used in processes carried out in the fluidized bed, such as catalytic cracking. In the preferred embodiment, is provided by mixing the zeolite with a solution containing silicon dioxide matrix, resulting in the formed aqueous solution of zeolite and kremmidiotis binders, which can be dried by spraying with a small p is t well-known specialists in this field of technology. An example of such a method is described in Scherzer (Octaine-Enchancing Zeolitic FCC Catalysts, Julius Scherzer, Marcel Dekker, Inc., New York, 1990). Pseudoryzomys associated with silica aggregate particles are similarly connected by silicon dioxide, the extrudates described above can then be directed to the final stage, described below, for the conversion of kremmidiotis binder in the second zeolite.

The final stage of this three-stage method of preparation of the catalyst is the conversion of silicon dioxide contained in a linked-silica catalyst, the second zeolite, which is used to relate the rest of the zeolite particles. Thus, the first zeolite crystals held together without the use of a significant amount nazaretova binder. In a preferred embodiment, the resulting zeolite catalyst contains less than 10 wt.% (in recalculation on weight of the first and second zeolites) nazaretova binder, more preferably less than 5 wt.% and most preferably less than 3 wt.% nazaretova binder.

Preferably the binder comprises less than 5 wt.% nazaretova binder material by weight of the first zeolite and the second CE is m silicon unit initially subjected to aging in an appropriate aqueous solution at elevated temperature. Then the components of the solution and the temperature at which the unit is subjected to aging, should be selected for the conversion of amorphous kremmidiotis binder in the second zeolite. In some applications, for example when the disproportionation of toluene, it is preferable to use the second zeolite similar to the originally linked zeolite or crystallographically appropriate initially linked zeolite. Freshly prepared zeolite obtained as crystals. These crystals can grow on the source zeolite crystals and/or adhesive to connect with them and can also be obtained in the form of new intergrown crystals, which are usually significantly less than the original crystals, for example, are characterized by submicrometric size. These newly obtained crystals can grow together and interconnected, thereby causing the interconnection of larger crystals.

The nature of the zeolite formed during secondary fusion conversion of silica in the zeolite can vary depending on the secondary structure of synthetic solution and synthesis conditions of aging. This secondary synthesis solution is an aqueous ion restak, for example, upon receipt of the MFI type zeolite is the initial molar ratio between OH-ions and SiO2in the solution reaches the level of approximately 1.2. The MFI type zeolite can be obtained by aging the solution containing the source of tetrapropylammonium (TPA), optional source of aluminum oxide and optionally a source of Na+; type zeolite MEL can be obtained by aging the solution containing the source of tetrabutylammonium and source of Na+. Suitable for preparation of these and other zeolites with medium pore water solutions of well-known specialists in this field of technology. However, it is important that the composition of the solution for aging was the one that usually does not cause dissolution of silicon dioxide, a part associated with the zeolite extrudate, and its leaching from the extrudate. In addition, in some cases, it is preferable that the zeolite formed during the second synthesis was less acidic than the core zeolite.

In a preferred embodiment of the invention the aqueous ionic solution in which aging is associated zeolite contains a source of hydroxide ions (preferably NaOH). In the case of preparation of a zeolite of the MFI type initial preferred is a molar which preferably ranges from about 0.05 to 1.2 and most preferably from about 0.07-0.15. This treatment causes a significant conversion kremmidiotis binder to zeolite of the MFI type, but low acidity, as evidenced by the significantly higher ratio of silicon dioxide and aluminum oxide. This solution also contains a template (for example, the source tetraalkylammonium ions to the zeolite of the MFI type) and optionally may include a source of alumina and a source of Na+-ions. Thus, the ratio between silicon oxide and aluminum oxide in a binder substance after conversion govern the change of the composition of an aqueous solution. If kremmidiotis binder material, which is subjected to the conversion, and the secondary synthesis mixture practically do not contain aluminum oxide obtained by the conversion material is more natural to call silicalite.

It is important that the pH of the solution to aging was so typical for not too alkaline. This can be achieved by obtaining the associated type zeolite MFI using the solution, the initial value of the molar ratio between the HE-and SiO2which is 0.05 to 1.2. Typically, the preferred ratio of 0.07 to 0.15. If the ratio is too large (i.e., alkalinity lastly on zeolite core crystals or education intergrown crystals kremmidiotis binder is dissolved and washed out of the extrudate, crystallizing out of the zeolite core crystals in the surrounding uterine solution. This weakens or breaks the integrity of the extrudate. The higher the alkalinity of a solution for the aging, the more silica is dissolved from the extrudate.

In a preferred embodiment, the aging zeolite extrudate in the solution for the aging is carried out at elevated temperatures, typically in the range of from about 95 to 200oC, more preferably from about 130 to 170oC and most preferably in the range of from about 145 to 155oC. Duration of aging can be from about 20 to 140 hours, more preferably from about 60 to 140 hours, and most preferably from about 70 to 80 hours.

After aging, the zeolite is separated from the solution, washed, dried and calicivirus.

The preferred process of preparation not containing binders of the MFI type zeolite is a mixture of a solution comprising sodium ions, for example aqueous sodium hydroxide solution, with a solution containing ions of TPA, for example, with a solution of halide TPA, such as bromide TPA. Next, you can add a linked by silicon dioxide extrudate from the second phase and composition to heat l is maintained at this temperature for 60-140 hours preferably 70-80 hours. Then, the resulting product can be washed and dried. To remove TPA+materials product after washing calicivirus, preferably at a temperature of 450-550oC.

Acceptable for some applications, for example when the disproportionation of toluene, the preferred bound MFI catalyst can be described as a two-phase catalyst, including the first phase of the particles of the MFI type zeolite, the ratio between silicon dioxide and aluminum oxide is from about 10:1 to about 200:1. The second phase consists of a zeolite of the MFI type or of the crystals, which in crystallographic ratio correspond to the MFI, which is characterized by a higher ratio between silicon oxide and aluminum oxide greater than about 200:1. This second phase consists of small intergrown crystals that cover or partially cover the particles of the first phase, and from small crystalline particles, which are coupled with the surface of the particles of the first phase. In a preferred embodiment, the molar ratio between silicon oxide and aluminum oxide in the particles of the first phase is from about 2:1 to about 150:1, preferably from about 20:1 to 150:1, aluminum oxide greater than about 200:1, more preferably greater than about 300:1. The size of the particles of the first phase can be in the range of conventional particle size zeolite of the MFI type, i.e., in the range of an average particle size of from about 0.1 to 15 micrometers, more preferably about 1-5 micrometers and most preferably from about 2 to 4 micrometers. The average particle size of the second phase, which serve for coupling between the particles of the first phase, much less, i.e., typically the average particle size is less than one micrometer, preferably from about 0.1 to less than 0.5 microns.

In the future, the zeolites of the present invention can be subjected to ion exchange treatment, as is known in the art either to replace at least part of the contained in the zeolite source of an alkali metal other cation, for example, a metal of groups IB to VIII of the Periodic table of elements, such as Nickel, copper, zinc, palladium, platinum, calcium or rare earth metals, or to give the more acidic zeolite shaped by this substitution of the alkali metal with intermediate ammonium, followed by calcination of the ammonium form to give an acidic decationizing form. The material in this acidic form can the eat zeolite can be calcinate at a temperature of 400-550oC for 10-45 hours, removing the ammonium cations. The ion exchange is preferably carried out after the formation of the two-phase bound by zeolite zeolite catalyst. Especially preferred are those cations that give the material a catalytic activity, especially when some of the reactions the conversion of hydrocarbons. These include hydrogen, rare earth metals and metals of groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic table of elements.

Related zeolites catalysts, described above, have a mechanical strength which is at least comparable, and often exceeds the mechanical strength of the zeolite unit associated with silicon dioxide. For example, the crushing strength associated with silicon dioxide and related zeolite materials, as a rule, reaches the following values:

the extrudate associated SiO2the crushing strength 0,46 kg/cm2;

associated material type MFI - crushing strength of 1.28 kgf/cm2.

Bound zeolite catalyst also has absorption properties that are comparable to the absorption properties of the zeolite powder.

The most preferred associated zeoli is surrounded by the core crystal particles of the MFI type with the size of the crystals is approximately 2 to 4 micrometers and a ratio of silicon dioxide/aluminium oxide 60:1 to 100:1 and a particle binder of crystals of smaller size, usually from about 0.1 to less than 0.5 micrometer, in which the ratio of silica/alumina of approximately 200:1 or more, for example, 300:1-5000:1 and 750:1 to 5000:1.

The methods of preparation of catalysts which can be used according to the present invention, described in conjunction considering applications for U.S. patents 08/335222, filed November 7, 1994, which is now issued U.S. patent 5460769, and 08/344034, filed November 11, 1994, which is incorporated into this description as references.

Related zeolites zeolites of the present invention can be used in the processing containing hydrocarbon raw materials. Hydrocarbon raw materials include carbon compounds and can be obtained from many different sources, such as fractions of crude oil, recycle petroleum fractions, materials from bituminous sand, and in General they can be any carbon-containing liquid, which is able to join catalyzed by zeolites reaction. Depending on the type of processing, which should be the subject of hydrocarbon raw materials, these raw materials may contain or may not contain metals. In addition, the version of hydrocarbon raw material can be any suitable for this purpose method for example in a fluidized bed reactor, moving bed or fixed bed, which depends on type of the selected processes.

Because related zeolites zeolite catalysts of the present invention are characterized by the regulated acidity and do not contain the usual binders, which can have undesirable impact on the availability of the active sites of the catalyst and/or participation with them, reagents and may also cause leakage of unwanted side reactions associated with the zeolite, the zeolite of the present invention individually or in combination with one or more catalytically active substances, when used as a catalyst for various organic processes, such as processes for the conversion of hydrocarbon compounds may have a high activity, high selectivity, the ability to maintain high activity or combinations of these properties. Non-limiting examples of such processes for the conversion of hydrocarbons include the following.

(A) Catalytic cracking of crude, gasoline, ligroin faction with obtaining light olefins. Typical reaction conditions include temperatures from about 10 atmospheres (gauge pressure) and length of stay (volume of catalyst/feedstock flow rate) from about 10 milliseconds to about 10 seconds).

(B) Catalytic cracking of high molecular weight hydrocarbons to hydrocarbons of lower molecular weight. Typical reaction conditions include temperatures from about 400 to about 700oC, a pressure of from about 0.1 atmosphere (bar) to about 30 atmospheres and average hourly feed rate from about 0.1 to about 100.

(C) Parallelomania aromatic hydrocarbons in the presence of polyallylamine hydrocarbons. Typical reaction conditions include temperatures from about 200 to about 500oC, a pressure from about atmospheric to about 200 atmospheres, average hourly feed rate from about 1 to about 1000, and the molar ratio of aromatic hydrocarbon/polyallylamine hydrocarbon from about 1/1 to about 16/1.

(G) aromatic Isomerization of the starting components (e.g., xylene). Typical reaction conditions include temperatures from about 230 to about 510oC, a pressure of from about 0.5 atmosphere to about 50 atmospheres, average hourly feed rate from preoperational hydrocarbon-selective solvent to remove remotemachine paraffin hydrocarbons. The reaction conditions depend largely on the raw materials used and the target temperature loss of yield of the target product. Typical reaction conditions include temperatures ranging from about 200 to 450oC, pressure up to 3000 pounds per square inch and an average hourly rate of flow of the liquid raw material is 0.1-20.

(E) Alkylation of aromatic hydrocarbons, such as benzene and alkyl benzenes in the presence of an alkylating agent, e.g. olefins, formaldehyde, alkylhalogenide and alcohols containing from 1 to about 20 carbon atoms. Typical reaction conditions include temperatures from about 100 to about 500oC, a pressure from about atmospheric to about 200 atmospheres, average hourly feed rate from about 1 to about 2000 h-1and the molar ratio of aromatic hydrocarbon/alkylating agent of from about 1/1 to about 20/1.

(F) Alkylation of aromatic hydrocarbons, for example benzene, with long chain olefins, e.g.14the olefin. Typical reaction conditions include temperatures from about 50 to about 200oC, a pressure from about atmospheric to about 200 atmospheres, average hourly feed rate of the materials is/1 to about 20/1. Products resulting from this reaction are long chain alkylaromatic compounds, which upon subsequent sulfonation find particular use as synthetic detergents.

(C) Alkylation of aromatic hydrocarbons, light olefins with obtaining short-chain alkylaromatic compounds, such as the alkylation of benzene by propylene to obtain cumene. Typical reaction conditions include temperatures from about 10 to about 200oC, a pressure from about 1 to about 30 atmospheres, average hourly feed rate of aromatic hydrocarbons (JCSS) from 1 to about 50 h-1< / BR>
(I) hydrocracking of heavy original oil recirculating the cracking products and other downloadable for hydrocracking feedstocks. Associated with zeolite zeolite catalyst typically comprises an effective amount of at least one hydrogenation component of the type used in catalysts for hydrocracking.

(C) Alkylation of the product of the reforming process, containing substantial quantities of benzene and toluene with fuel gas containing short-chain olefins (such as ethylene and PR to approximately 250oC, a pressure from about 100 to about 800 psig, JCSS of olefin from about 0.4 to about 0.8 h-1, JCSS product reformer from about 1 to about 2 hours and optional recirculation gas from about 1.5 to about 2.5 volume of/the amount of combustible gas.

(L) Alkylation of aromatic hydrocarbons, for example benzene, toluene, xylene and naphthalene, with long chain olefins, e.g.14-olefin, with the receipt of alkyl aromatic lubricant base oils. Typical reaction conditions include temperatures from about 160 to about 260oC and a pressure from about 350 to 450 pounds per square inch.

(M) Alkylation of phenols with olefins or equivalent alcohols to obtain long-chain ALKYLPHENOLS. Typical reaction conditions include temperatures from about 100 to about 250oC, a pressure from about 1 to about 300 pounds per square inch and the total JCSS from about 2 to about 10 h-1.

(H) Conversion of light paraffin hydrocarbons to olefins and/or aromatics. Typical reaction conditions include temperatures from about 425 to about 760oC and a pressure of from about 10 to 2000 pounds per square inch.

(O) Konum reaction conditions include a temperature of from about 175 to about 375oC and a pressure of from about 100 to 2000 pounds per square inch.

(P) two-Stage hydrocracking for improving the quality of hydrocarbons, the initial boiling point which is greater than approximately 200oC, to obtain the distillate of the highest quality and products with boiling points in the range of the boiling points of the fuel or raw material for other types of fuels or for use in the first stage, various chemical processes, which use associated with zeolite zeolite catalyst comprising one or more catalytically active substances, for example metal of group VIII, and the products discharged from this first stage, the second stage will be to communicate using the second zeolite, for example, beta-zeolite, including as a catalyst one or more catalytically active substances, for example metal of group VIII. Typical reaction conditions include a temperature from about 315 to about 455oC, a pressure from about 400 to about 2500 pounds per square inch, the flow rate of the circulating hydrogen from about 1000 to about 10,000 standard cubic feet per hour and the volumetric rate of fluid (COSI) from about 0.1 to 10.

(B) the Combined process is mponent hydrogenation and beta zeolite. Typical reaction conditions include a temperature of from about 350 to about 400oC, a pressure from about 1400 to about 1500 pounds per square inch, CHOSE from about 0.4 to about 0.6 and a circulating flow of hydrogen from about 3000 to about 5000 standard cubic feet per barrel.

(C) the Interaction of alcohols with olefins to obtain mixed ethers, such as the interaction of methanol with isobutene and/or isopentene obtaining tert-butyl ether (MTBE) and/or tert-mileticova ether (tame). Typical conversion conditions include a temperature of from about 20 to about 200oC, a pressure from about 2 to about 200 ATM, JCSS (grams of olefin per gram of zeolite per hour) from about 0.1 to about 200 h-1and the molar ratio of the starting alcohol and the olefin is from about 0.1/1 to about 5/1.

(T) the Disproportionation of toluene to obtain benzene and para-xylene. Typical reaction conditions include temperatures from about 200 to about 760oC, a pressure from about atmospheric to about 60 atmospheres (bar) and JCSS from about 0.1 to about 30 h-1.

(I) Conversion of gasoline-ligroin fraction (for example, C6-C10products) and analogic is Ogorodov with normal and slightly branched chain, preferably with a boiling point in the range of from more than about 40oC to less than about 200oC, aromatic compounds with a higher octane number by contacting the hydrocarbon feedstock with zeolite at a temperature in the range of from about 400 to 600oC, preferably 480-550oC, under pressure from atmospheric to 40 bar and at hourly volume velocity of the fluid (COSI) in the range of 0.1-15.

(F) the Adsorption of alkylaromatic compounds for the separation of the various isomers of these compounds.

(X) Conversion of oxygen-containing compounds, for example alcohols, such as methanol, or ethers, such as dimethyl ether, or mixtures thereof to hydrocarbons including olefins and aromatics, such reaction conditions that include a temperature of from about 275 to about 600oC, a pressure from about 0.5 to about 50 atmospheres and hour space velocity of the liquid is from about 0.1 to about 100.

(C) Oligomerization of olefins with straight and branched chain, containing from about 2 to about 5 carbon atoms. The oligomers, which are the products of such a process, olefins are medium to heavy, which Mogushkov raw materials. The oligomerization process is usually carried out by contacting olefinic feedstock in a gaseous state phase with a zeolite bound zeolite at a temperature in the range of from about 250 to about 800oC, CHOSE from about 0.2 to about 50 and a partial pressure of hydrocarbon from about 0.1 to about 50 atmospheres. For the oligomerization feedstock when the feedstock is in the liquid state, in the process of introducing into contact with the associated zeolite zeolite catalyst can operate at temperatures below approximately 250oC. Thus, when the olefin feedstock is introduced into contact with the catalyst in the liquid phase, the process can be conducted at a temperature of from about 10 to about 250oC.

(H) Conversion of unsaturated C2-hydrocarbons (ethylene and/or acetylene) in aliphatic C6-C12aldehydes and conversion of these aldehydes into the corresponding C6-C12alcohols, acids or esters.

Normally, therefore, the conditions of catalytic conversion, which is a catalyst comprising a bound zeolite, the zeolite include a temperature of from about 100 to about 760oC, a pressure of from about 0.1 atmosphere (bar) to about 200 atmosfere many processes for the conversion of hydrocarbons, it is preferable to use the second zeolite crystals, which have low acidity, allowing to reduce the flow velocity adverse reactions out of these first zeolite crystals, for some processes it is preferable to use the second zeolite crystals having a high acidity, such as acidity, chosen in such a way as to catalyze the target reaction. Such processes are divided into two types. Regarding the first type can be noted that the acidity and the type of crystallography of the second zeolite are selected so that they match the acidity and the type of crystallography of the first zeolite. This route is usually improve the ratio between the catalytically active material and the weight of the finished catalyst, causing the apparent catalytic activity. This catalyst is usually you can also probably be improved by increasing the adsorption capacity, for example, due to availability and low selective surface acidity. An example of a process that could be improved by using a catalyst of this type is the disproportionation of toluene. In the case of disproportionation of toluene, the target product is non-selective equilibrium mixture of xylenes, selectproduct is more valuable than high selectivity.

The process of the second type, which can be improved by selection of the second acidity of the zeolite phase is a process in which inside the zeolite catalyst are two or more reactions. In this process, the acidity and/or crystallographic structure of the zeolite of the second phase can be chosen so that they differ from the corresponding characteristics of the first zeolite, but essentially were not free from the acid sites. Such a catalyst includes, probably, two different zeolite, each of which could be individually selected in order to accelerate or inhibit different reactions. The process in which use of such a catalyst can be improved not only due to the higher apparent catalytic activity, increase the availability of zeolite and lowering selective surface acidity, it is possible for related zeolites zeolites, but it could also be improved by selection of the obtained product.

A catalyst of this type can be used to improve the combined processes kelloway isomerization/ethylbenzene dealkylation. The catalyst was spent mostly in the first zeolite crystals, and the isomerization of xylenes was mainly the second zeolite crystals. Selection of the catalyst in this way allows you to achieve a balance between the two reactions that otherwise using a catalyst containing only one zeolite, would be impossible.

Preferably the described method of converting hydrocarbons comprises disproportionation of toluene by shielding the flow of hydrocarbons in terms of the disproportionation of toluene with an associated zeolite zeolite catalyst, including:

(a) first crystals of a first zeolite is a medium pore, the average particle size is more than about 0.1 micrometer, and

(b) a binder containing the second crystals of a second zeolite is a medium pore, the average particle size which is smaller than those of the first crystals, and a lower acidity than the first crystals, and these latter crystals are fused state with the first crystals to form on them coverage or partial coverage.

Bound zeolite catalyst of the present invention, in particular, can be used in vapor the disproportionation of toluene. Lakovanym zeolite zeolite catalyst to obtain a mixture of products, which is a mixture of unreacted (not converted) toluene, benzene and xylene. In a more preferred embodiment, before use in the process of disproportionation first regulate the selectivity of the catalyst to promote the conversion of toluene to xylene and to maximize the catalytic selectivity for obtaining para-xylene. Methods to control the selectivity of the catalyst are well-known specialists in this field of technology. For example, the selectivity can be controlled by treatment of the catalyst in the reactor layer thermally destructively organic compound, such as toluene, at a temperature above the temperature of decomposition of the compounds, in particular from about 480 to about 650oC, more preferably 540-650oC, JCSS in the range of from about 0.1 to 20 pounds of raw material per pound of catalyst per hour, a pressure in the range from about 1 to 100 atmospheres, in the presence of from 0 to about 2 moles of hydrogen, more preferably from about 0.1 to about 2 moles of hydrogen per mole of organic compound, and optionally in the presence of 0-10 moles of nitrogen or other inert gas per mole of organic compound. This is th number of coke, usually at least about 2 wt.% and more preferably from about 8 to about 40 weight. % coke. In a preferred embodiment, such regulation selectivity is carried out in the presence of hydrogen to prevent the formation of excessive amounts of catalyst coke. After deposition on the catalytic surface of a significant amount of coke initial molar ratio of gaseous hydrogen and toluene contained in the original stream of toluene, in the implementation of the regulation selectivity can be reduced.

Regulation selectivity of the catalyst can also be accomplished by treatment of the catalyst agent to control the selectivity, such as the organosilicon compound. Organosilicon compounds suitable for use as agents to control the selectivity described in U.S. patent 5365003, which is included in the present description by reference.

If the catalyst is used in the vapor disproportionation of toluene, he is more preferably includes the first phase of the crystalline particles of the MFI type zeolite, an average size of from about 3 to about 4 micrometers, the molar ratio of the RATM structurally coupled with their surfaces of particles of the second MFI or binder type MFI with an average particle size less than about 0.1 micrometer and a ratio between aluminum oxide and silicon dioxide from more than about 300: 1 to about 10,000:1 and most preferably in excess of 900:1.

Options zeolite bound zeolite, with the regulated selectivity when used during vapor-phase disproportionation, exhibit higher selectivity for obtaining para-xylene than conventional MFI catalysts with controlled selectivity.

The catalysts according to the invention is more resistant to coking compared with the known catalysts used for the disproportionation. For example, the regulatory process selectivity, including the disproportionation of toluene, a known catalyst is usually required at least 24 hours, and it lasts as long as the coke will not accumulate in sufficient quantity to achieve the level at which the rate of formation of para-xylene is maximized. Known catalysts MFI less resistant to coking, and their selectivity can be adjusted within a smaller time interval. However, since the known catalyst ZSM-5 is less resistant to coking, when it is used for the disproportionation he usually deactivated faster, which leads to the reduction of operating cycles. Thus, one of the major advantages of using zeolite, cvasinoguide.

After regulation to the extent necessary selectivity of the catalyst, for example after reaching more than 80% selectivity in respect of para-xylene in the environment of oil, reactor conditions selectivity change in terms of disproportionation. These disproportionation conditions include a temperature in the range of from about 400 to 550oC, more preferably in the range from about 425 to 510oC, when the molar ratio between hydrogen and toluene from 0 to about 10, preferably from about 0.1 to 5 and more preferably from about 0.1 to less than 1, a pressure in the range from about 1 to 100 atmospheres and at JCSS in the range from about 0.5 to 50. The hydrocarbon stream further includes hydrogen at a molar ratio of H2/toluene in the range of from 0 to about 10. One of the specific advantages of using this catalyst during the disproportionation is that it provides good selectivity for para-xylene when the values of the molar ratio of H2/toluene less than 1, for example, at about 0.5.

The disproportionation process can be conducted as batch, semi-continuous or continuous, using besieged in re the following coke deactivation by burning coke to the desired degree in oxygen-containing atmosphere at an elevated temperature, as is known in the art.

Associated with the zeolite, the zeolite of the present invention can be particularly effectively used as a catalyst in the isomerization of one or more xylology isomers in the original aromatic C8-products to obtain ortho-, meta - and para-xylene in a ratio approaching the equilibrium value.

Preferably, the method of converting hydrocarbons comprises the isomerization of hydrocarbons containing aromatic stream C8products containing ethylbenzene, xiaowei isomers or mixtures thereof, by contacting the materials in the conversion isomerization with an associated zeolite zeolite catalyst, including:

(a) first crystals of a first zeolite is selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average particle size is greater than 0.1 micrometer, and

(b) a binder containing the second crystals of a second zeolite selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average particle size which is smaller than those of the first crystals, and these second LASS="ptx2">

In particular, kelloway isomerization used in combination with the separation process to obtain a para-xylene. For example, part of para-xylene in the mixed stream aromatic C8products can be distinguished using methods known in the art, for example crystallization, adsorption, and so on, the resulting product stream can be further introduced into the reaction conditions kelloway isomerization in order to restore nearly equilibrium ratio of ortho-, meta - and para-xylenes. Simultaneously, the portion of the ethylbenzene in the feedstock is converted into a xylene or products that are easily distinguished by distillation. The isomerization product is mixed with fresh feedstock and the combined stream is dispersed to remove heavy and light products. Then thread the obtained aromatic C8products returned to the process for re-cycle.

It is important that the catalysts kelloway isomerization produces almost equilibrium mixture of xylenes, and sometimes it is also necessary that these catalysts provided the conversion of ethylbenzene with very little overall loss of xylenes. In this respect, the use of zeolites related zeolites, especially expedient. With the way, to balance kelloway isomerization and ethylbenzene dealkylation, while minimizing undesirable side reactions. Thus, an additional object of the present invention is a method of converting hydrocarbons in the exercise of which in the conditions of the isomerization carry out the contacting of the aromatic stream C8products, includes one or more xylology isomers or ethylbenzene, or their mixture with a zeolite bound zeolite.

Acceptable conditions of isomerization in the vapor phase include a temperature in the range from 250 to 600oC, preferably 300-550oC, absolute pressure in the range from 0.5 to 50 bar, preferably 10-25 ATM, and average hourly feed rate (JCSS) from 0.1 to 100, preferably 0.5 to 50. Isomerization in the vapor phase is not necessary can be carried out in the presence of 3.0-30,0 moles of hydrogen per mole of alkyl benzene. In the case of hydrogen, the catalyst must include 0.1 to 2.0 wt% component hydrogenation/dehydrogenization selected from the group VIII of the Periodic table of elements, especially of platinum, palladium or Nickel. Under component-based metal of group VIII imply metals and their compounds, such rule from 150 to 375oC, absolute pressure in the range from 1 to 200 ATM and JCSS in the range from 0.5 to 50. Isomerization raw materials optionally may include 10-90 wt.% diluent, such as toluene, trimethylbenzene, naphthenic or paraffinic hydrocarbons.

Preferably, the method of converting hydrocarbons includes the cracking of hydrocarbon compounds by contacting the hydrocarbon feedstock under conditions of catalytic cracking with an associated zeolite zeolite catalyst, including:

(a) first crystals of a first zeolite is a medium pore, and

(b) a binder containing the second crystals of a second zeolite is a medium pore, the average particle size which is smaller than the first crystals, and these latter crystals cover at least part of the first crystals.

Zeolites associated with zeolites, the present invention can be particularly effectively used as catalysts in the cracking process, for example, crude, gasoline, ligroin fractions of C4+first of all, crude, gasoline, ligroin C4the fraction with a boiling point of 290oC, obtaining low molecular weight olefins, e.g., C2-C4olefins, especially ethylene and propylene. the tour in the range of from 500 to about 750oC, more preferably 550-675oC, under a pressure of not higher than atmospheric to 10 atmospheres and preferably from about 1 to about 3 atmospheres.

Related zeolites zeolites of the present invention can be particularly effectively used as catalysts in parallelomania polyallylamine hydrocarbons.

Thus, preferably the method of converting hydrocarbons comprises parallelomania aromatic hydrocarbon by contacting the aromatic hydrocarbon in terms of parallelomania with polyallylamine hydrocarbon in the presence of bound zeolite zeolite catalyst, including:

(a) first crystals of a first zeolite is selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average size of the crystalline particles is greater than about 0.1 micrometer, and

(b) a binder containing the second crystals of a second zeolite selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average particle size which is smaller than the first crystals, and these latter crystals are spliced status is dialkylaminoalkyl hydrocarbons include di-, tri - and Tetra-alkylaromatic hydrocarbons, such as diethylbenzene, triethylbenzene, diethylstilbestrol (diethyltoluene), diisopropylbenzene, triisopropylbenzene, diisopropylphenol, dibutylester, etc. or mixtures thereof. Preferred polyallylamine hydrocarbons are dialkylphenol. Especially preferred polyallylamine hydrocarbons are diisopropylphenol and diethylbenzene.

In the process of parallelomania preferred molar ratio between the aromatic hydrocarbon and polyallylamine hydrocarbon is typically from about 0.5: 1 to about 50:1, more preferably from about 2: 1 to about 20:1. The preferred reaction temperature is usually from about 340 to 500oC at least partially maintain the liquid phase, and the preferred excess pressure is usually from about 50 to 1000 psig, more preferably 300-600 pounds per square inch. Average hourly feed rate of the raw material is usually from about 0.1 to 10.

Preferably, the method of converting hydrocarbons involves the conversion of oxygen-containing compounds in the hydrocarbon products containing olefin is containing compounds, under conditions sufficient for the conversion of these oxygen-containing compounds in petroleum products, with the associated zeolite zeolite catalyst, including:

(a) first crystals of a first zeolite, preferably the average particle size in excess of about 0.1 micrometer and

(b) a binder containing the second crystals of a second zeolite, the average particle size which is smaller than the first crystals, and these latter crystals are fused state with the first crystals to form on them coverage or partial coverage.

In addition, preferably, the method of converting hydrocarbons comprises the alkylation of aromatic hydrocarbons by contacting this aromatic hydrocarbon in the alkylation conditions with an alkylating agent containing 2-20 carbon atoms, in the presence of bound zeolite zeolite catalyst, including:

(a) first crystals of a first zeolite is selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average particle size is greater than 0.1 micrometer, and

(b) a binder containing the second crystals of a second zeolite selected from the group, the size of the first crystals, moreover, these latter crystals are fused state with the first crystals to form on them coverage or partial coverage.

The method of preparation of the bound zeolite zeolite catalyst, which can be used according to the present invention, is illustrated in the following example.

Example 1

A. obtaining a ZEOLITE of the MFI TYPE

20,4 kg a synthesis mixture with the following molar composition: 0,45 Na2O; 0,9 TPA Br; 0,125 Al2O3; 10 SiO2; 146 N2Oh, was subjected to aging at 150oC for five days without stirring in 25-liter autoclave made of stainless steel. The obtained product was washed with water to pH 10.2 and dried at 120oC for approximately 16 hours. Part of this product was caliciviral in air at 475oC for 32 hours. Calcined product had the following properties:

radiography: net MFI;

SAM: spherical crystallites with sizes of 3 microns;

elementary analysis: the ratio of SiO2/Al2O3= 80.

(SEM - scanning electron microscopy)

B. OBTAINING PARTICLES ASSOCIATED with SILICON DIOXIDE

Part of the above calcined product (A) joint is PRIGOTOVLENIYA COMPONENTS QUANTITY (grams)

Crystals of MFI (dried at 250oC for 2 hours 200,00

H2O - 49,75

Gel SiO2(product AEROSIL 300) - 18,82

Silicasol (product NALCOAG A) - 197,24

Auxiliary means for extrusion (hypromellose) - 1,07

The above components were mixed in a process plant for the production of food, in that order. After approximately 6 minutes after adding the auxiliary means for the extrusion got a thick and smooth paste. This paste was extrudible with the formation of extrudates with a diameter of 2 mm extrudates were dried overnight at 130oC and then caliciviral at 510oC for 6 h in air.

Composition associated with silicon dioxide calcinatory extrudates:

MFI 69,96 wt.%

SiO2-binder 30,04 wt.%

C. CONVERSION ASSOCIATED with the ZEOLITE ZEOLITE

Preparing a synthesis mixture

USED FOR MAKING COMPONENTS - QUANTITY (grams)

Solution A:

Pellets of NaOH (98,3%) - 1,16

H2O - 24,63

Added wash water - 10,02

Solution B:

Tetrapropylammonium - 8,00

H2O - 25,47

Added wash water which she began.

Solution B was poured together with the added wash water content of the autoclave. Both solutions were mixed. At the end 60,04 g of the extrudates of the MFI type, associated with silica and prepared by the method described above (previously dried for 2 hours at 150oC), were added to the autoclave synthesis mixture.

The mixture in the autoclave had the following composition: 0,48 Na2O; 1,00 TPA Br; 10 SiO2; 147 N2About (at a ratio of OH-:SiO20,1).

The content of the MFI crystals in the mixture amounted to 40.5 wt.% the total weight of the mixture. The autoclave was heated to 150oC and kept at this temperature for 71 hours. After this aging period, the autoclave was opened and the product collected.

The product was washed in a Buechner funnel 4250 ml of water, add 11 portions, and the pH of the last wash water was 10.2. The product was dried for three hours at 150oC. the weight of the product obtained after drying, amounted to 62.5 grams. This product was found to be much more durable than the original associated with silicon dioxide extrudates. The product was caliciviral on the air for 18 hours at 500oC to remove the TPA+-materialia (RGR), scanning electron microscopy (SEM) and absorption hexane to obtain the following results:

RGR: the increase of crystallinity in % in comparison with the original linked silicon dioxide extrudates: 32% (increase the height of the peaks at d values between 3,02 and 2,96 ;

SAM: micrograph with 10,000-fold magnification showed that the composition (A) containing an MFI crystals size 3 micron coated fused newly formed submicrometric crystals. The microphotographs were no appreciable traces of amorphous silicon dioxide source extrudates, which were clearly visible.

The ratio between silicon oxide and aluminum oxide:

The MFI crystals of composition a - 80:1

The newly formed submicrometric crystals - 900:1

Regulation of selectivity and disproportionation processes according to the invention is illustrated in the following examples.

Example 2

The selectivity of calcined bound zeolite catalyst described in example 1, regulate the flow through the catalyst toluene to obtain highly selective catalyst under the following conditions (see table A).

After priblizitelen is the ratio of para-xylene in the normal conditions of disproportionation would reach, probably about 92-94%.

After adjusting the selectivity of such highly selective catalyst used for the selective disproportionation of toluene (SDPT) under the following test conditions:

Test conditions

Temperature (oF) is varied in the interval 805-860o< / BR>
Excessive pressure (pounds/square inch) - 300

JCSS - 3 lb raw/lb catalyst/h

The molar ratio of H2: source toluene - 2:1

Absolute partial pressure of the hydrocarbon - 93.4 pounds/square inch

Operational catalytic characteristics in the environment of petroleum products for this highly selective catalyst is shown in Fig. 1-4.

Upon completion of the probationary experiments described above, the selectivity associated with the zeolite catalyst used during testing, re-regulated under conditions to control the selectivity described above, for an additional 20 hours of obtaining servicecollection catalyst. Next, in a SDPT described above, conducted additional tests with SDPT. Their results are also shown in Fig. 1-4.

During the extra control the selectivity of the catalyst after about the Fig. 1. The temperature that was required to achieve the target conversion of a few degrees higher than the one that used a known catalyst ZSM-5.

However, as shown in Fig. 2, the selectivity associated with the zeolite catalyst in the ratio of para-xylene (PC) was increased up to 94-95%, i.e., ultra-high selectivity for SDPT.

Example 3.

Selectivity known processed by ion exchange disproportionation catalyst HZSM-5, associated with aluminum oxide, regulated feed of toluene through the catalyst. Regulate the selectivity associated with the zeolite of the MFI catalyst of the present invention. This selectivity was regulated in the following conditions (see table B).

After adjusting the selectivity of the known catalyst HZSM-5 and associated with the zeolite MFI catalyst of the present invention used for the disproportionation of toluene in the test conditions given in table 1. Associated with zeolite zeolite catalyst was evaluated in 3 separate test conditions as shown in table 1. Table 2 shows the performance of each catalyst in the medium of oil.

Regulation of the selectivity Isvicre was approximately 34 wt.%. For comparison associated with zeolite catalysts of the present invention typically contains less than 15 wt.% Cox.

It should be noted the fact that the regulation of selectivity associated with the zeolite of the MFI catalyst was much slower than the regulation selectivity known MFI catalyst even when more severe conditions to control the selectivity. Such a long period of time that is required to control the selectivity associated with the zeolite zeolite catalyst, shows that it is very resistant to coking. Since the coking is the main cause of deactivation of the catalyst associated with the zeolite catalyst is deactivated slower famous ZSM-5, which, consequently, leads to a more prolonged duty cycle. The reason for the resistance associated with the zeolite catalyst by coking is that it is characterized by low non-channel, surface acidity MFI and, consequently, low acidity formation of coke precursors. A lower rate of deactivation due to high resistance to coking is one of the advantages of the present sobljudeniem, neither his degree was not the same as the bound zeolite catalyst, as during regulation selectivity was stating the obvious significant loss of activity even though conditions to control the selectivity of the standard catalyst were much less stringent than for bound zeolite catalyst. The selectivity of this catalyst could be brought to a higher degree, but due to the significant decrease in catalytic activity. This regulation selectivity was completed at the level at which the best were balanced catalytic activity and selectivity.

The results clearly indicate that after adjusting the selectivity associated with the zeolite catalyst has a higher activity and selectivity. In addition, more long-term regulation of selectivity even when creating a more stringent regulatory environment selectivity indicate the stability of the bound zeolite catalyst by coking.

To further confirm the stability of the bound zeolite catalyst by coking the catalyst used in the processes in the environment of the oil is :oil of 0.5 for 17 days. Under these conditions, the catalyst had the following initial performance:

Conversion - 31,0%

Selectivity for PC - 94.7% of

The output of the BR - 14,0%

The output of the PC to 13.9%

After 17 days, the catalyst had the following performance characteristics:

Conversion - 31,0%

Selectivity for PC - 95,1%

The output of the BR - 14,2%

Exit PC - 14,1%

This test indicates the absence of losses activity (in fact, some increase) in 17 days. Thus, this catalyst is very resistant to coking.

Associated with zeolite MFI catalyst has high catalytic activity, high selectivity for PC, the ability to provide a higher output of a PC and high resistance to deactivation due to coking in comparison with the known catalyst of the MFI.

Example 4

The present invention regulate the selectivity associated with the zeolite catalyst ZSM-5. Conditions to control the selectivity shown in table 3.

Assessment in four different test conditions are shown in table 4.

Performance characteristics of the catalyst are presented in table 5.

Example 5

Associated with zeolite zeolite catalyst, which was characterized by almost the same composition as the catalyst described in example 1 were evaluated on the ability to cruciality light gasoline, ligroin faction.

The test was performed first by treatment with water vapor associated with the zeolite zeolite catalyst at 704oC for 16 hours to aging of the catalyst. Then over related zeolite zeolite catalyst at 650oC missed the gasoline-ligroin crude fraction with JCSS 1,9-1and the value of the ratio between water vapor and hydrocarbon 0,85. The tests were repeated, except that the catalyst consisted of MFI associated 60 wt.% binder (calculated on the weight of the catalyst), which included silicon dioxide and aluminum oxide.

The results ispy is the associated with the zeolite as a catalyst cracking yield of ethylene and propylene was significantly increased, and the selectivity against unwanted light saturated compounds and aromatic compounds were found to be significantly reduced.

1. A method of converting hydrocarbons comprising contacting the hydrocarbons in the conversion of hydrocarbons with zeolite catalyst, characterized in that the contacting is conducted with the associated zeolite zeolite catalyst comprising (a) first crystals of a first zeolite and (b) a binder containing the second crystals of a second zeolite, the average particle size which is smaller than the first crystal and the second crystal are in the fused state with the first crystals to form on them coverage or partial coverage.

2. The method according to p. 1, characterized in that the average particle size of the first crystals of a first zeolite exceeds 0.1 μm.

3. The method according to p. 1 or 2, characterized in that the conversion of a hydrocarbon selected from the group of processes involving the cracking of hydrocarbons, isomerization of alkylaromatic compounds, disproportionation of toluene, parallelomania aromatic compounds, the conversion of paraffin hydrocarbons and/or olefins to aromatics, conversion of oxygen-containing compounds in petroleum products and cracking of the gasoline-ligroin fraction to light olefins.

4. The method according to PP.1-3, characterized in that the hydrocarbon conversion is conducted at conditions including a temperature of 100 - 760oWith pressure of 0.1 to 100 atmospheres, average hourly feed rate of 0.08 - 200 h-1.

5. The method according to PP. 1-4, characterized in that the second zeolite is selected from the group consisting of zeolites with large pores, zeolites with medium pores and mixtures thereof.

6. The method according to PP. 1-5, characterized in that the first zeolite is selected from the group consisting of zeolites with large pores, zeolites with medium pores and mixtures thereof.

7. The method according to PP.1-6, characterized in that the acidity of the crystals of a second zeolite either above or below the acidity of the zeolite crystals of the first.

8. The method according to PP.1-7, characterized in that the first and second zeolites are selected from the group consisting of zeolite L, X, Y, offretite, omega zeolite, mordenite, zeolite MAZ, MEI, FAU, EMT, ZSM-3, ZSM-4, ZSM-18, ZSM-20, MFI, MEL, MTW, MTT, FER, EUO, HEU, TON, beta-zeolite, ZSM-34, ZSM-38, ZSM-48, galloylated and titanosilicates.

9. Sportliches fact, that hydrocarbons comprises aromatic compounds, gasoline, ligroin faction, paraffin hydrocarbons, olefins, oxygen-containing compounds or mixtures thereof.

11. The method according to PP.1-10, characterized in that the binder comprises less than 5 weight. % nazaretova binder material by weight of the first zeolite and the second zeolite.

12. The method according to PP.1-11, characterized in that the molar ratio between silicon oxide and aluminum oxide in the second zeolite is 300:1 to 5000:1.

13. A method of converting hydrocarbons under item 1, characterized in that it includes parallelomania aromatic hydrocarbon by contacting the aromatic hydrocarbon in terms of parallelomania with polyallylamine hydrocarbon in the presence of bound zeolite zeolite catalyst comprising (a) first crystals of a first zeolite is selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average size of the crystalline particles is greater than about 0.1 μm, (b) a binder containing the second crystals of a second zeolite selected from the group consisting of zeolites with large pores and zeolites with medium long the hinnon condition with the first crystals to form on them coverage or partial coverage.

14. The method according to p. 13, characterized in that the conditions of parallelomania include the molar ratio between the aromatic hydrocarbon and polyallylamine hydrocarbon of 0.5:1 to 50:1, a temperature of 340 - 500oAnd the excess pressure in the range of 50 to 1000 pounds per square inch.

15. The method according to p. 13 or 14, characterized in that polyallylamine hydrocarbon selected from the group consisting of triethylbenzene, diethylstilbestrol, diethylbenzene, diisopropylbenzene, triisopropylbenzene, Diisopropylamine, debutante and mixtures thereof.

16. A method of converting hydrocarbons under item 1, characterized in that it comprises the alkylation of aromatic hydrocarbons by contacting this aromatic hydrocarbon in the alkylation conditions with an alkylating agent containing 2-20 carbon atoms, in the presence of bound zeolite zeolite catalyst comprising (a) first crystals of a first zeolite is selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average particle size is more than 0.1 ám, (b) a binder containing the second crystals of a second zeolite selected from the group consisting of zeolites with large pores and zeolites with who are in the fused state with the first crystals to form on them coverage or partial coverage.

17. The method according to p. 16, characterized in that the aromatic hydrocarbon is a benzene or alkyl benzenes.

18. The method according to p. 16 or 17, wherein the alkylation conditions include a molar ratio between the aromatic hydrocarbon and the alkylating agent is 1:1 to 20:1 and a reaction temperature of 100 to 500oC.

19. A method of converting hydrocarbons under item 1, characterized in that it comprises the isomerization of hydrocarbons containing aromatic stream C8products containing ethylbenzene, xiaowei isomers or mixtures thereof, by contacting the materials in the conversion isomerization with an associated zeolite zeolite catalyst comprising (a) first crystals of a first zeolite is selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average particle size is more than 0.1 ám, (b) a binder containing the second crystals of a second zeolite selected from the group consisting of zeolites with large pores and zeolites with medium-sized pores, the average particle size which is smaller than those of the first crystals, moreover, these latter crystals are fused state with the first crystals to form on nicklachey cracking hydrocarbons by contacting the hydrocarbon feedstock under conditions of catalytic cracking with an associated zeolite zeolite catalyst, including (a) first crystals of a first zeolite is a medium pore, (b) a binder containing the second crystals of a second zeolite is a medium pore, the average particle size which is smaller than the first crystals, and these latter crystals cover at least part of the first crystals.

21. The method according to p. 20, wherein the hydrocarbon is a crude naphtha fraction WITH4+.

22. The method according to p. 20 or 21, characterized in that the amount of the first crystalline particles is 0.1 - 3 μm.

23. A method of converting hydrocarbons under item 1, characterized in that it includes the disproportionation of toluene by shielding the flow of hydrocarbons in terms of the disproportionation of toluene with an associated zeolite zeolite catalyst comprising (a) first crystals of a first zeolite is a medium pore, the average particle size is more than about 0.1 μm, (b) a binder containing the second crystals of a second zeolite is a medium pore, the average particle size which is smaller than those of the first crystals, and a lower acidity than the first crystals, and these latter crystals are fused 23, characterized in that the selectivity of the catalyst pre-regulate.

25. The method according to p. 24, characterized in that the selectivity of the catalyst pre-regulate by contact of the catalyst with a stream of toluene at a temperature in the range of 480 - 650oWith under a pressure in the range of 1 to 100 atmospheres and at an average hourly feed rate of the feedstock in the range of 0.1 - 20 and this thread toluene additionally contains hydrogen at a molar ratio of N2/toluene 0 - 2.

26. The method according to p. 24 or 25, characterized in that the conditions for the disproportionation of toluene include the contacting of the flow of the hydrocarbon with the catalyst at a temperature in the range of 400 - 550oWith under a pressure in the range of 1 to 100 atmospheres and at an average hourly feed rate of the feedstock in the range of 0.5 - 50 and the hydrocarbon stream further includes hydrogen at a molar ratio of N2/toluene in the range of 0 - 10.

27. The method according to PP.23 to 26, characterized in that the particles of the second zeolite represent the MFI crystals or crystals that crystallographic relation correspond to the MFI and are characterized by a molar ratio between silicon oxide and aluminum oxide, which exceeds nolamp.23-27, characterized in that the molar ratio between silicon oxide and aluminum oxide of the second crystal is 300:1 to 5000:1.

29. The method according to PP.23-28, characterized in that the catalyst is acidic decationizing form.

30. The method according to PP.23-29, characterized in that the molar ratio between silicon oxide and aluminum oxide in the second zeolite is in excess of approximately 300:1.

31. The method according to PP.23-30, characterized in that the molar ratio between silicon oxide and aluminum oxide in the first zeolite is 2:1 to 150: 1.

32. The method according to PP.23-31, wherein the first zeolite and the second zeolite is used zeolite is a medium pore.

33. The method according to PP.23-32, wherein the first and second zeolites are selected from the group consisting of zeolite L, X, Y, offretite, omega zeolite, mordenite, zeolite MAZ, MEI, FAU, EMT, ZSM-3, ZSM-4, ZSM-18, ZSM-20, MFI, MEL, MTW, MTT, FER, EUO, HEU, TON, beta-zeolite, ZSM-34, ZSM-38, ZSM-48, galloylated and titanosilicates.

34. The method according to PP.23-33, wherein the particle size of the first crystals is 2 to 6 μm, and the particle size of the second crystals is 0.1 - 0.5 micron.

35. The method according to PP.23-34, wherein the second zeolite p with respect corresponds to the first zeolite.

36. The method according to PP. 23-35, wherein the average particle size of the first crystals is 3 to 4 μm.

37. The method according to PP.23-36, wherein the first zeolite is MFI.

38. The method according to PP.23-37, wherein the second zeolite is MFI.

39. The method according to PP.23-38, characterized in that the ratio between silicon oxide and aluminum oxide in the second zeolite is in excess of approximately 1000:1.

40. The method according to PP.23-39, characterized in that the rate of adsorption of the zeolite bound zeolite exceeds 1,00.

41. The method according to PP.23-40, characterized in that the ratio between silicon oxide and aluminum oxide in the second zeolite exceeds the ratio between silicon oxide and aluminum oxide in the first zeolite.

42. The method according to PP.23-41, characterized in that the rate of adsorption of the zeolite bound zeolite exceeds 1,10.

43. A method of converting hydrocarbons under item 1, characterized in that it involves the conversion of oxygen-containing compounds in the hydrocarbon products containing olefins, aromatic compounds, or mixtures thereof, by contacting the hydrocarbon feedstock, comprising oxygenated compounds, under conditions sufficient for convesation, including (a) first crystals of a first zeolite and (b) a binder containing the second crystals of a second zeolite, the average particle size which is smaller than the first crystals, and these latter crystals are fused state with the first crystals to form on them coverage or partial coverage.

44. The method according to p. 43, characterized in that the average particle size of the first crystals of a first zeolite is greater than approximately 0.1 microns.

45. The method according to PP.42-44, wherein the oxygen-containing compound is an alcohol or ether.

46. The method according to PP.43-45, wherein the first and second zeolites are selected from the group consisting of zeolite L, X, Y, offretite, omega zeolite, mordenite, zeolite MAZ, MEI, FAU, EMT, ZSM-3, ZSM-4, ZSM-18, ZSM-20, MFI, MEL, MTW, MTT, FER, EUO, HEU, TON, beta-zeolite, ZSM-34, ZSM-38, ZSM-48, galloylated and titanosilicates.

47. The method according to PP.43-46, wherein the conversion conditions include a temperature of about 275 to 600oWith the pressure of about 0.5 to 50 atmospheres and watch the volumetric rate of fluid about 0.1 - 100.

48. The method according to PP.43-47, characterized in that the ratio between silicon oxide and aluminum oxide in the second zeolite p is 43-48, characterized in that the molar ratio between silicon oxide and aluminum oxide in the second zeolite is greater than 500:1.

50. The method according to PP.43-49, characterized in that the oxygen-containing compound selected from the group comprising methanol, dimethyl ether and mixtures thereof.

51. The method according to PP.1-50, characterized in that the rate of adsorption is associated with the zeolite zeolite catalyst exceeds 1,10.

 

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