Dealuminated zeolite nu-86, how to obtain it (options), the catalyst based on it and its use in the conversion of hydrocarbons

 

(57) Abstract:

The invention relates to the modified zeolite NU-86, containing silicon and at least one element T selected from the group consisting of aluminum, iron, gallium and boron. The element T is removed from the frame of the source of the crude synthetic zeolite NU-86. The total atomic ratio Si/T greater than about 20. Removing an element T of the zeolite framework (or lattice) is realized by means of at least one heat treatment carried out, if necessary, in the presence of water vapor, followed by at least one acid etching in at least one solution of a mineral or organic acid, or better, by direct acid etching. The invention also relates to a catalyst containing a specified zeolite, located at least partially in acid form, and to the use of this catalyst in the conversion of hydrocarbons, in particular, when the oligomerization of olefins WITH2-C8. The modified zeolite NU-86 of the present invention at its introduction into the catalyst results in improved catalytic properties, in particular, activity, stability and selectivity. 6 C. and 8 silicon and at least one element T, selected from the group consisting of aluminum, iron, gallium and boron, preferably aluminium, characterized in that the element T is removed from the frame, and that he has a total atomic ratio Si/T greater than about 20. The way it is received by deleting the element T of the zeolite framework (or lattice) through at least one heat treatment carried out, if necessary, in the presence of water vapor, followed by at least one acid etching at least one solution of a mineral or organic acid, or preferably by direct etching acid. The invention also relates to a catalyst containing a specified zeolite, at least partially, in the acid form and the method of production and use of the specified catalyst in the conversion of hydrocarbons, in particular, when the oligomerization of olefins WITH2-C8(i.e., containing from 2 to 8 carbon atoms in the molecule).

Synthesis of zeolite NU-86 described in the application for the European patent EP-A2-463768. Zeolite NU-86 synthesize, in General, in the presence of sodium cations and structure-forming organic component, which is dibromomethane or dibromomethane.

Structural type zeolite officially yet to be established by the Commission on the synthesis of IZA (international zeolite Association). However, in some published papers of the 9th International Congress on zeolites J. L. Casci, P. A. Box, and M. D. Shannon ("Proceedings of the 9th International Zeolite Conference, Montreal 1992, Eds R. Von Ballmoos et al., 1993 by Butterworth") shows that:

zeolite NU-86 has three-dimensional microporous system,

this three-dimensional microporous system consists of direct cavities, in which the opening of the pores is limited to 11 atoms T (T is the tetrahedral atom, selected mainly from the group consisting of Si, Al, Ga and Fe), direct cavities, separated alternately by the holes 10 and 12 atoms of T, and sinus cavities, also delimited alternately holes 10 and 12 atoms So

The term "pore openings of 10, 11 or 12 tetrahedral atoms (T)" means pores having a 10, 11 or 12 sides. Determining the diameter of the pores present in the zeolite NU-86, leads to the following values: 4,8x5,8 for pores with 10 sides, 5,g,7 for pores with 12 sides, and 5,5x6,2 for pores with 11 sides. Zeolite NU-86 with similar pore diameters belongs to the class of zeolites with an average diameter of pores.

The authors of the present invention have conducted studies and found that zeolite NU-86, at least partially, preferably practically completely, in acid form, and with a ratio Si/T greater than about 20, at its introduction into the catalyst results in improved catalytic properties, in particular, activity, stability and selectivity in the conversion reactions of hydrocarbons, as compared with catalysts of the prior art, and in particular, in comparison with nadesalingam zeolites NU-86, as described in the application for the European patent EP-A2-0463768 that will be shown hereinafter in the examples.

The invention relates to a zeolite NU-86, containing silicon and IU is aluminum, characterized in that the element T is removed from the frame, and that he has a total atomic ratio Si/T greater than about 20, preferably greater than about 22, and more preferably approximately from 22 to about 300.

The invention also relates to a catalyst containing at least one zeolite NU-86, in which the element T is removed from the frame, and which at least partially and preferably practically completely, is in acid form, containing silicon and at least one element T selected from the group consisting of aluminum, iron, gallium and boron, preferably aluminium, and at least one matrix (or binder). Preferably, the total atomic ratio Si/T in the indicated dealumination zeolite exceeds about 20, preferably greater than about 22, and more preferably is from approximately 22 to about 300. The specified catalyst also contains, if necessary, at least one element selected from the set consisting of elements of groups IB and VIII of the periodic table of elements, preferably selected from the group consisting of Ad, Ni and Pd, Pt, preferably among Ni, Pd or Pt.

The matrix is chosen, t), magnesium oxide, alumina, silicon dioxide, titanium oxide, boron oxide, Zirconia, aluminum phosphate, titanium phosphates, zirconium phosphates and silicates and carbon, preferably among the members of the group consisting of alumina and clays.

In the application for the European patent EP-A2-0463768 are x-rays of zeolite NU-86. So, as is well-known specialist in this field of technology, any zeolite NU-86 has a main line of x-ray diffraction of its structure, but the intensity of these lines is amenable to change, depending on the form in which the zeolite, otherwise there are doubts in the facilities specified zeolite to a certain structure. Thus, zeolite NU-86 according to the invention, in which the element T is removed from the frame, has the main lines of its structure, similar to the lines given in the application for the European patent EP-A2-0463768, with the intensity of the sensing lines, different from the intensity contained in the specified application.

When it is contained in the catalyst according to the invention, the zeolite NU-86 according to the invention, at least partially, preferably practically completely, is in the acid form, i.e. in the form (N+). The atomic ratio Na/T with Aligator according to the invention contains, usually, from 10 to 99%, and preferably from 20 to 95%, zeolite NU-86, in which the element T is removed from the frame, which is, at least partially, in the acid form. When the catalyst of the present invention contains at least one element selected from the set consisting of elements of groups 1B and VIII of the periodic table of the elements, the mass content of the element (elements) is usually 0, 01-10%, preferably 0.05 to 7%, and more preferably 0.10 to 5%. The complement to 100 wt.% usually the matrix is part of the catalyst.

The total atomic ratio Si/T zeolite, and therefore, the chemical composition of the samples, determined by rentgenofluorestsentnyi and atomic absorption.

Based on the radiographs, for each sample, measure the total area of the signal at the range of angles (2) from 6 to 40othen, in the same zone, the area of the strips in the form of pulses at a Desk with an interval of 3 seconds with a step of 0.02o(2). The ratio of these quantities - size strips/total area is characteristic of a number of crystalline substances in the sample. Then compare this ratio or content of peaks for each tested sample with the contents of the peaks of the internal standard, prosth in relation to the standard, which it is important to choose correctly, because the relative intensity of the bands varies depending on the nature, number and position of the various atoms in the unit, and in particular, cations and structure-forming component. In the case of measurements made in the examples in this description, the selected standard is a form of zeolite NU-86, calcined in dry air and subjected to 3 times consecutively, the exchange using a solution of ammonium nitrate.

Micropore volume can also be measured in terms of the amount of nitrogen absorbed at 77 K at a partial pressure P/Po, equal to 0.19 (for reference).

The invention also relates to the production of zeolite NU-86, in which the element T is removed from the frame, and to the specified catalyst.

In order to obtain zeolite NU-86 according to the invention, in which the element T is removed from the frame, in the preferred case, where T is A1, you can use two ways to metaluminous, based on the crude synthesized zeolite NU-86 containing organic structure-forming component. They are described below. But all other methods known to experts in this field of technology is also included in the scope of this invention.

Per the ear, usually, at a temperature of 450-550oWith, in order to remove the organic structure-forming component is present in the micropores of the zeolite, followed by a stage of processing in an aqueous solution of mineral acids such as HNO3or Hcl or organic acids, such as CH3COOH. This last stage can be repeated as many times as necessary to obtain the required level of dealumination. Between these two stages can be performed one or more ion exchange with at least one solution of NH4NO3to remove at least part, and preferably practically completely, the cation of an alkali metal, particularly sodium. Also, at the end of processing for dealumination through direct acid etching can be performed one or more ion exchange with at least one solution of NH4NO3to remove the cations of alkali metals, particularly sodium.

To achieve the desired ratio Si/Al, you need to choose carefully working conditions; from this point of view, the most important parameters are temperature treatment in an aqueous solution of acid, the concentration of the latter, its nature, the CI and the number of implemented treatments.

The second method, called thermal treatment (in particular, water vapor, i.e., "steam treatment") with subsequent etching acid includes, at first, calcining in a stream of dry air, usually at a temperature of about 450-550oWith, in order to remove the organic structure-forming component occluded in the micropores of the zeolite. Then, the thus obtained solid substance is subjected to one or more ion exchange with at least one solution of NH4NO3to remove at least part, and preferably practically completely, the cation of an alkali metal, in particular sodium, present in the zeolite in cationic form. Thus obtained zeolite is subjected to at least one cycle dealumination frame including at least one heat treatment carried out, if necessary, and preferably in the presence of water vapor at a temperature of usually about 550-900oWith, and if necessary, followed by at least one acid etching with an aqueous solution of a mineral or organic acid. Conditions of calcination in the presence of water vapor (temperature, pressure water L etching, the concentration of the acid, the nature of the acid used and the ratio between the amount of acid and weight of zeolite) are selected so as to obtain the desired level of dealumination. With the same purpose can have a number of cycles: heat treatment of acid etching, which is effective.

In the preferred case, where T is A1, the cycle dealumination frame including at least one stage of heat treatment of zeolite NU-86, carried out, if necessary, and preferably in the presence of water vapor, and at least one stage of etching in an acidic environment, can be repeated as many times as necessary to obtain desalinizing NU-86, having desirable properties. Can also be performed after the heat treatment carried out, if necessary, and preferably in the presence of water vapor, several consecutive acid pickling and acid solutions of different concentrations.

One variant of this second method, the calcination may be in the implementation of thermal treatment of the zeolite NU-86 containing organic structure-forming component, at a temperature of usually about 550-850who s organic structure-forming component and metaluminous frame are carried out simultaneously. Then the zeolite, if necessary, treated with at least one aqueous solution of mineral acid (e.g., HNO3or Hcl) or organic acids (for example, CH3COOH). Finally, the thus obtained solid substance can, if necessary, be subjected to at least one operation of ion exchange with at least one solution of NH4NO3so, to remove almost completely the cation of an alkali metal, in particular sodium, present in the zeolite in cationic form.

Obtaining catalyst can be carried out by any method known to the expert in this field of technology. In General, it is obtained by mixing the matrix and the zeolite, followed by molding. Possible element from the set consisting of elements of group 1B or VIII of the periodic table of elements, you can enter or before molding, or during mixing, or in the zeolite even before mixing, or better, preferably, after forming. Molding is usually followed by calcination, generally at a temperature of about varying between 250 and 600oC. Possible element from the set consisting of elements of group 1B or VIII of the periodic table of elements, you can enter after you specified the Cesky fully on the zeolite, or almost entirely on the matrix, or partially on the zeolite and partly on the matrix, and this selection is carried out as known to the expert in this field, using the parameters at the specified deposition, for example, the nature of the selected predecessor, to implement the specified deposition.

The element of group 1B or VIII, selected preferably from the group consisting of Ad, Ni, Pd and Pt, preferably among Ni, Pd and Pt, can, if necessary, uniformly precipitated on the pre-formed mixture of the zeolite matrix by any method known to the expert in this field of technology. This deposition is usually carried out by impregnation in a dry condition, ion exchange (ion exchange) or coprecipitation. In the case of ion exchange on the basis of predecessors on the basis of silver, Nickel or platinum, usually use of silver salts, such as chlorides or nitrates, tetraammineplatinum complex or Nickel salts, such as chlorides, nitrates, acetates, or formate. This method of cation exchange can also be used for direct deposition of metal on the zeolite powder possible before mixing it with the matrix.

With the possible deposition element (elementele - when 350-550oWith, and with a duration of 0.5-10 hours, preferably 1-4 hours.

When the catalyst contains several metals, the latter can either be all the same, or different methods, before or after molding, and in any order. If, when using the method of ion exchange, it is possible to carry out several successive exchanges required to introduce the required quantity of metals.

For example, one of the preferred methods for producing the catalysts according to the invention consists of mixing the zeolite in the wet gel matrix (obtained, usually, by mixing at least one acid and one powder matrix), for example, aluminum oxide, in a period of time necessary to obtain good homogeneity of the thus obtained paste, or, for example, within ten minutes, with subsequent deletion of the specified paste through a die plate to form the extrudate, for example, with a diameter of 0.4 to 4 mm after drying for several minutes at 100oWith in a drying oven and, after annealing, for example, for 2 hours at 400oWith, can be precipitated possible element, such as Nickel, for example, by ion exchange, and for specified is the W catalyst according to the invention usually is the catalyst, preferably, takes the form of pellets, aggregates, extrudates or pellets, with regard to its application.

Obtaining catalyst ends, typically, calcination, the so-called final annealing, typically at a temperature varying between 250 and 600oWith, preferably, with the previous drying, for example, in a drying oven at a temperature of, usually, from ambient temperature to 250oC, preferably from 40 to 200oC. Specified stage of drying is conducted preferably during the temperature increase until necessary to implement the specified ignition.

You can then start to recover in an atmosphere of hydrogen, typically at a temperature of 300-600oWith, preferably 350-550oWith, and when the duration of 1-10 hours, preferably 2-5 hours, to obtain an element from groups 1B and VIII mainly in restored form, which is necessary for the activity of the catalyst. Such recovery may occur ex situ or in situ relative to the location of application of the specified catalyst in this reaction.

The invention also relates to the use of such catalyst in the conversion of hydrocarbons, in particular, when the oligomerization of olefins With
1) energy-dense fuel good quality,

2) combustible component for jet fuel of excellent quality,

3) gasoil diesel very good quality, based on light hydrocarbons WITH2-C8.

Source olefins for this application can be from any suitable source. They can also provide the products of conversion of methanol. So, download that can be used are the following:

a) fresh download, containing mainly methanol and, if necessary, water in all proportions of water and methanol); first of all, it enters the catalytic decomposition zone, where it turns to water and light olefins, representing mainly propylene, then, in the second place, after separation of the water formed, the light olefins come into the oligomerization zone, where they are transformed into a mixture of high-calorie fuel and bases for jet fuel and diesel fuel

b) fresh load consisting only of light olefins C2-C8opening or from a catalytic cracking unit, or installation of a vapor-phase cracking, or from the installation kataliticheskoe in section oligomerization, where it turns into a mixture of high-calorie fuel and bases for jet fuel and diesel fuel

C) a fresh boot, consisting of a mixture of the two previous downloads.

In the so-called zone of the catalytic decomposition of the transformation of methanol into the water and light olefins is usually carried out in the vapor phase in the presence of acidic zeolite catalyst or acidic molecular sieve, the process proceeds or in a fixed bed, or preferably in a fluidized bed catalytic system, at a temperature of about 450-650o(Preferably when 530-590oC) at a pressure of 0.01 to 1 MPa, preferably 0.05 to 0.5 MPa), at a flow rate of the liquid loaded (space velocity) of about 5-100 volumes on the volume of catalyst per hour.

The so-called oligomerization reaction is carried out in the liquid phase, in the supercritical phase or in the gas phase, in the presence of acidic zeolite catalyst according to the invention, precipitated in the form of a fixed layer, at a temperature of about 50-400oWith (preferably 150-350oC) at a pressure of 2 to 10 MPa (preferably 3-7 MPa), at a flow rate of liquid hydrocarbons (space velocity) of about 0.3 to 4 volume volume of catalyst per hour.

Example 1. Obtaining zeolite NU-86/1 according to the invention

The original used the substance is a zeolite NU-86, with a total atomic ratio Si/Al equal to 10.2, and mass sodium corresponding to the atomic ratio Na/Al (%) equal 30,8.

Such zeolite NU-86 is subjected to a first, so-called annealing - drying at 550oWith the flow of dry air for 10 hours. Then the obtained solid substance is subjected to a quadruple ion exchange in a 10 N solution of NH4NO3approximately at 100oC for 4 hours for each exchange. The thus obtained solid substance called NH4-NU-86, and it has a ratio of Si/Al = 10,4, and the ratio Na/Al = 1.3 per cent. Other physico-chemical characteristics are given in table.1.

Such zeolite NH4-NU-86 is subjected to hydrothermal treatment in the presence of 100% steam at 650oC for 4 hours. This zeolite is subjected to acid etching 7 N nitric acid, approximately, 100oC for 4 hours to extract variety aluminum, formed during hydrothermal treatment. The volume of injected solution of nitric acid (V) (in ml) is 10 mass (R) dried wearing Si/Al, equal to 27.5, and the ratio Na/Al below 0.2%. Its crystallographic characteristics and absorption are given in table.2.

Table. 2 shows that after the stages of the steam treatment and acid etching zeolite NU-86 retains good crystallinity and relatively high specific surface area (SBET).

Example 2. Obtaining catalyst C1 according to the invention

Zeolite H-NU-86/1, obtained in example 1 is then formed by extrusion with a gel of aluminum oxide so as to obtain, after drying and calcination in dry air, catalyst C1, containing 70 wt.% zeolite H-NU-86/1 and 30 wt.% aluminum oxide.

Example 3. Obtaining zeolite H-NU-86/2 according to the invention

The original used the substance is the same zeolite NU-86, which is used in example 1. Such zeolite NU-86 is subjected to a first, so-called annealing - drying at 550oWith the flow of dry air for 10 hours. Then, the resulting solid is subjected to ion exchange in a 10 N solution of NH4NO3approximately at 100oC for 4 hours. This operation is sequentially repeated three times. Then the zeolite NU-86 process 0,8 N solution of nitric acid at about 100oWith over 5 hours of the Sabbath.

Obtained as a result of this treatment, the zeolite is referred to as H-NU-86/2. He is in form H and has a total atomic ratio Si/Al equal 20,3, and the ratio Na/Al, equal to 0.7%. Its crystallographic characteristics and absorption are given in table.3.

Example 4. Obtaining catalyst C2 according to the invention

Zeolite H-NU-86/2, obtained in example 3 is then formed by extrusion with a gel of aluminum oxide so as to obtain, after drying and calcination in dry air, catalyst C2, containing 70 wt.% zeolite H-NU-86/2 and 30 wt.% aluminum oxide.

Example 5. Obtaining zeolite H-NU-86/3 according to the invention

The original used the substance is the same zeolite NU-86, which is used in example 1. Such zeolite NU-86 is subjected to a first, so-called annealing - drying at 550oWith the flow of air and nitrogen for 10 hours. Then, the resulting solid is subjected to ion exchange in a 10 N solution of NH4NO3approximately at 100oC for 4 hours. This operation is sequentially repeated three times. Then the zeolite NU-86 treated with 2 N nitric acid solution, approximately, 100oC for 5 hours. The volume of injected solution of nitric acid (V) (in ml) is 10 mass (R) is away in the form of N and has a total atomic ratio Si/Al, equal to 26.2, and the ratio Na/Al, equal to 0.6%. Its crystallographic characteristics and absorption are given in table.4.

Example 6. Obtaining zeolite H-NU-86/4 according to the invention

The original used the substance is the same zeolite NU-86, which is used in example 1. Such zeolite NU-86 is subjected to a first, so-called annealing - drying at 550oWith the flow of air and nitrogen for 10 hours. Then, the resulting solid is subjected to ion exchange in a 10 N solution of NH4NO3approximately at 100oC for 4 hours. This operation is sequentially repeated three times. Then the zeolite NU-86 process 8,5 N solution of nitric acid, about 100oC for 5 hours. The volume of injected solution of nitric acid (V) (in ml) is 10 mass (P) of the dried zeolite NU-86 (V/P=10).

Obtained as a result of this treatment, the zeolite is referred to as H-NU-86/4. He is in form H and has a total atomic ratio Si/Al equal 40,3, and the ratio Na/Al, 0.15%. Its crystallographic characteristics and absorption are given in table. 5.

Example 7. Obtaining catalyst C3 according to the invention

Zeolite H-NU-86/4, obtained in example 6, is then formed by extrusion with gay 70 wt.% zeolite H-NU-86/4 and 30 wt.% aluminum oxide.

Example 8. Obtaining catalyst C4, not relevant to the invention

Used in this example, the zeolite NU-86 zeolite is NH4-NU-86, obtained in example 1 of the present invention. However, in this example, the zeolite NU-86 is not subjected to dealumination.

Zeolite NH4-NU-86, obtained in example 1 is then formed by extrusion with a gel of aluminum oxide so as to obtain, after drying and calcination in dry air, catalyst C4, containing 70 wt.% zeolite H-NU-86 and 30 wt.% aluminum oxide.

Example 9. Evaluation of catalytic properties of catalysts C1, C2, C3, corresponding to the invention, and catalyst C4, not relevant to the invention, when the cracking of methylcyclohexane.

Evaluation of catalytic properties is carried out in a fixed bed at atmospheric pressure. Used the download is methylcyclohexane.

In a series of tests of the catalysts, the results of which are summarized in table. 6, the volumetric loading rate of methylcyclohexane (expressed in grams injected toluene per gram of catalyst per hour) change to get in 4 trials comparable conversion. The reaction temperature remains constant and equal to 500oC.

utilizator C4, not relevant to the invention. In particular, the selectivity to products (toluene + C8+), which is undesirable products, reflecting the tendency of the catalyst to carry out the transfer of hydrogen, which is an undesirable reaction, weaker than in the case of catalyst C4, not relevant to the invention.

Example 10. Evaluation of catalytic properties of catalysts C1, C2, C3, corresponding to the invention, and catalyst C4, not in accordance with the invention, the oligomerization of propylene.

Evaluation of catalytic properties is carried out in a fixed bed at a nitrogen pressure of 5.5 MPa and 300oWhen VVH 1 hour-1(unit/ hour). Used loading represents the fraction3, vapor-phase cracking (5% propane, 95% propylene).

The reaction temperature is high enough (300oC) a change in the ratio Si/Al of active phases NU-86 does not affect the activity of the catalysts C1, C2 and C3 according to the invention and C4, are not relevant to the invention.

The results are shown in table.7, show that the catalysts according to the invention C1, C2 and C3 are more selective in obtaining diesel fraction than the catalyst C4, not relevant to the invention. The increase in selectivity with respect to the ptx2">

Additional examples 11-15

Example 11. Obtaining zeolite H-NU-86/5 according to the invention.

The original used the substance is a zeolite NU-86, with a total atomic ratio of Si/Fe, equal to 15.3, and mass sodium corresponding to the atomic ratio Na/Fe equal to 28.4 per cent.

Such zeolite NU-86 zeolite is initially subjected to calcination at 550oWith the flow of dry air for 10 hours. The obtained solid substance is subjected to a quadruple ion exchange in a 10 N solution of NH4NO3at a temperature of about 100oC for 4 hours for each exchange. The obtained solid is defined as NH4-NU-86 (Fe), and it has a ratio of Si/Fe equal 16,2, and the ratio of Na/Fe, equal to 1.2%. Other physico-chemical characteristics are presented in table.8.

Then NH4-NU-86 (Fe) is subjected to acid etching with use of a 1.5 N nitric acid at a temperature of about 100oC for 5 hours. The volume V of the solution of nitric acid (ml) was 10 times the weight W of the dry zeolite NU-86 (V/W=10).

The result of this processing is zeolite H-NU-86/5 in the form of N, the total atomic ratio of Si/Fe equal to 32.2, and the ratio Na/Fe - below 0.7%. Its crystallographic x is in the shadow

Zeolite H-NU-86/5, obtained in Example 11, is then formed by extrusion with alumoweld and get after drying and calcination in dry air catalyst C5 containing 70 wt.% zeolite H-NU-86/5 and 30 wt.% aluminum oxide.

Example 13. Evaluation of catalytic properties of the catalyst C5, corresponding to the invention by oligomerization of propylene.

Evaluation of catalytic properties, make use of a fixed layer with a nitrogen pressure of 5.5 MPa, a temperature of 300oWith and volumetric flow rate equal to 1 hour-1. As raw materials use fraction C3 vapor cracking (5% propane and 95% propylene).

At a sufficiently high reaction temperature (300o(C) a catalyst C5 (NU-86/5) shows the same activity as any of the catalysts C1, C2 and C3 according to the invention and the catalyst C4, not relevant to this invention.

The data table.10 show that the catalyst C5 according to the invention are more selective in obtaining diesel fraction than the catalyst C4, not relevant to this invention. The increase of selectivity with respect to diesel fraction accompanied by an increase in cetane number of this fraction.

Example 14. Polycentrus aluminosilicate gel and get after drying and calcination in dry air catalyst C6, containing 70 wt.% zeolite H-NU-86/4 and 30 wt.% aluminosilicate.

Example 15. Evaluation of catalytic properties of catalysts C3 and C6, corresponding to the invention when hydroisomerization raw materials containing mainly hydrocarbons having 7 carbon atoms.

An aqueous solution of Pt(NH3)2+42Cl-used for impregnation of catalysts C3 and C6 with the aim of introducing it to 1 wt.% platinum relative to the weight of the catalyst. Then the extrudates calcined in dry air at 500oWith and recover in the reactor hydroisomerization in an atmosphere of pure hydrogen at a temperature of 420oC.

In the reactor hydroisomerization served raw C7, which contains a 15.5% by weight of isoheptane (i-C7) and 84,5% by weight of normal heptane (n-C7).

Reaction conditions are the following:

- total pressure: MPa,

PPH (mass of raw C7 per unit mass of zeolite per hour) = 1,02 h-1,

- the molar ratio of N2/hydrocarbon = 2,

- the temperature is set so as to obtain the conversion of normal heptane about 80%.

The results obtained when using catalysts that are listed in the table.11

The table shows that the use of catalysts C3 and C6, based on the and, that is a significant advantage.

1. The modified zeolite NU-86, containing silicon and at least one element T selected from the group consisting of aluminum, iron, gallium and boron, characterized in that the element T is removed from the frame of the source of the crude synthetic zeolite NU-86, and the total atomic ratio Si/T is from 20 to 300.

2. Zeolite under item 1, where the specified element T represents aluminum.

3. The method of producing zeolite under item 1 or 2, by annealing at a temperature of from 450 to 550oWith and subsequent direct acid etching at least one solution of a mineral or organic acids of the crude synthetic zeolite NU-86 containing structure-forming organic component.

4. The method according to p. 3, which includes the following stages: a) calcination in a stream of dry air untreated synthetic zeolite NU-86 containing structure-forming organic component, at a temperature of from 450 to 550oC, b) acid etching at least one solution of a mineral or organic acid.

5. The method of producing zeolite under item 1 or 2 by heat treatment at a temperature of from 550 to 850o

6. The method according to p. 5, which comprises the following stages: a) heat treatment of the crude synthetic zeolite NU-86 containing structure-forming organic component, at a temperature of from 550 to 850oC, b) acid etching at least one solution of a mineral or organic acid.

7. The method according to p. 5 or 6, in which heat treatment is carried out in the presence of water vapor.

8. The modified zeolite NU-86 received in one of the paragraphs. 3-7.

9. The catalyst for conversion of hydrocarbons containing at least one matrix and at least one zeolite under item 1 or 2, or received one from PP. 3-7, located at least partially in acid form.

10. The catalyst p. 9, additionally containing at least one element from groups 1B and VIII of the Periodic table of elements.

11. The catalyst according to p. 10, wherein said element selected from the group consisting of Ad, Ni and Pt.

12. The catalyst according to any one of paragraphs. 9-11, in which the matrix is chosen among the group consisting of clays, magnesium oxide, alumina, silicon dioxide, titanium oxide, oxide Bo

13. The catalyst according to any one of paragraphs. 9-12 for use in the oligomerization of olefins WITH2-C8in the liquid phase, in the supercritical phase or in the gas phase, with the specified catalyst precipitated in the form of a fixed layer, at a temperature of from 50 to 400oC, at a pressure of from 2 to 10 MPa and the flow rate of liquid hydrocarbons from 0.3 to 4 volumes per volume of catalyst per hour.

14. The method of producing catalyst according to p. 9 by mixing the matrix and the modified zeolite NU-86, followed by molding.

 

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