CS266302B2 - Catalyst for hydrocarbons' cracking, hydrocking and isomerization and method of its production - Google Patents

Abstract

CRYSTALLINE BOROSILICATE (AMS-1B) AND PROCESS USE A new crystalline borosilicate composition of matter and process using it wherein the composition is expressed as mole ratios of oxides as follows: 0.9 ? 0.2 M2/nO : B2O3 : YSiO2 : ZH2O wherein M is at least one cation, n is the valence of the cation, Y is generally a value of from about 4 to about 500 or higher, and Z is a value of from 0 to about 160, and characterized by a specified X-ray powder diffraction pattern as is described herein. Catalytic conversion including processes such as isomerization, disproportionation, or transalkylation are also disclosed.

Description

(57) The catalyst for cracking, hydrocracking and isomerisation of hydrocarbons consists of crystalline borosilicate of a composition expressed in a molar ratio of oxides of (0,9 ± 0,2) ^M 2 / n ^{O: B} 2 ° 3 ^{: Y} SiO 2. a valency c group selected from the group consisting of a tetraalkylammonium cation having from 8 to 12 carbon atoms, an ammonium cation, a hydrogen cation, an alkali metal cation or mixtures of these cations, Y having a value of 4 to 500 and Z having a value of 0 to 160, respectively. of a composition expressed in molar ratio of oxides (0,9 ± 0,2) (W 2 O (1-W) W 2 / nO): 02Оз: У SiO 2 Si H 2 O, where R is a C 8 -C 12 tetraalkylammonium group, preferably tetrapropylammonium group M is an alkali metal ion, W is greater than 0 and less than or equal to 1, and Y and Z have the above values. A process for the preparation of this catalyst consists in mixing, in an aqueous medium, boron, alkali metal and silicon oxides with a tetraalkylammonium compound in weight ratios giving a SiO2 / B2O3 molar ratio value of 5 to 600, R @ 6 N @ + / R @ R @ ^. ) 0.1 to 1, OJr / SiO2 0.01 to 10 and H ₂ O / OH 10 to 500, the reactants are then heated at a temperature of 90 to 250 ° C for a time sufficient to precipitate borosilicate crystals and then isolated from and optionally drying and calcining to obtain calcined crystalline borosilicate.

CS 266 302 B2

The present invention relates to a catalyst for the cracking, hydrocracking and isomerization of hydrocarbons as well as a process for its preparation. The catalyst of the present invention is a crystalline brokerate having the following composition, also useful as a molecular sieve.

It has previously been known that zeolite materials, both natural and synthetic, have been found to possess properties in a variety of hydrocarbon conversion processes. The zeolite materials used to compare the crystalline core flow through the conductors are defined by the structure and the large and small, interconnected cavities. The shapes of the cavities and channels are generally the same throughout the crystalline material in terms of size, thereby allowing selective hydrocarbon separation. Therefore, these materials have been described in various cases in the prior art as molecular sieves and are used in addition to selective adsorption also for their certain catalytic properties. The catalytic properties of these materials are to some extent influenced by the size of the molecules that are selectively permeated by the crystal structure, probably to be brought into contact with the catalytically active sites within the ordered structure of the materials.

The term molecular sieve generally encompasses a large number of crystalline materials containing positive ions, both of natural and synthetic species. They are typically characterized as crystalline aluminosilicates, although this broad definition includes other crystalline materials. The crystalline aluminosilicates are made up of groups sířovím tetrahedra SiO ₄ and AlO ^ in which silicon and aluminum atoms are cross-bridged oxygen atoms. The electrovalence of the aluminum atom is saturated using a positive ion, for example an alkali metal or alkaline earth metal ion.

Further development of the state of the art has led to the formation of numerous synthetic crystalline materials. Among them, crystalline aluminosilicates predominate, which in the patent and journal literature are denoted by letters or other suitable symbols. Examples of such materials are zeolites A (U.S. Pat. No. 2,882,243), zeolites X (U.S. Pat. No. 2,882,244), zeolites Y (U.S. Pat. No. 3,130,007), zeolites ZSM-5 (U.S. Pat. No. 3,702,886), zeolites ZSM-11 (U.S. Patent No. 3,709,979), zeolites ZSM-12 (U.S. Patent No. 3,832,449), and others.

The prior art disclosed in U.S. Pat. No. 3,702,886 discloses crystalline aluminosilicate zeolite ZSM-5 and a process for its preparation. This patent is limited to the formation of zeolite in which the crystalline structure contains aluminum or gallium oxides together with silicon or germanium oxides. The latter are reacted with the latter in a certain ratio to form a class of zeolites, referred to as ZSM-5, which is limited to crystalline aluminosilicate or silicates or germanicates and is characterized by a special X-ray diffractogram. Said patents relating to ZSM-11 and ZSM-12 zeolites are similarly limited to crystalline aluminosilicate or gallo silicates or germanicates and are also characterized by a specific X-ray diffractogram.

In the production of ZSM materials, a mixed alkaline system is used in which sodium aluminate and a silicon-containing material are contacted with sodium hydroxide and an organic base such as tetrapropylammonium hydroxide or tetrapropylammonium bromide under certain reaction conditions to form the desired crystalline aluminosilicate.

U.S. Pat. No. 3,941,871 discloses an organosilicate having a very small amount of aluminum in the crystal structure, which is characterized by an X-ray diffractogram similar to the diffractogram of zeolite ZSM-5. This patent belongs to the prior art closely related to the subject-matter of the invention.

The prior art also discloses US patents describing zirconium silicate or titanic silicates, namely U.S. Patent Nos. 3,329,480 and 3,329,481.

However, the catalyst of the invention is a new group of stable synthetic

CS 266 302 B2 of crystalline materials # which are characterized as borosilicate and referred to as borosilicate and referred to as AMS-1B with a special X-ray diffractogram. These crystalline AMS-1R-borosilicon are formed by the reaction of a boron salt with a silicon-containing substance in a basic condition.

I'i iuIiiiM cm i i, · I <·. ·, (I jr thus к м I л I у z I i io pio kraluivánf, hydroc l lication i I ø øи · г ле I hydrocarbon # which is characterized by # that is composed of crystalline borosilicate with a composition expressed in molar ratio of oxides (0,9 + 0,2) M _{2 / n} O: B ₂ O ₃ : Y SiO ₂ : ZH ₂ O # where

- means at least one valency c of the group consisting of a tetraalkylammonium cation of 8 to 12 carbon atoms # an ammonium cation # a hydrogen cation, an alkali metal cation or a mixture of these cations #

Y has a value of 4 to 500 and

Z is 0 to 160.

This borosilicate is characterized by interplanar distances and associated intensities as shown in Table I below.

In a preferred embodiment, Y is between 40 and 500 and Z is between 0 and 40.

In another broad sense, the present invention provides a catalyst for the cracking, hydrocracking and isomerization of hydrocarbons, consisting of crystalline borosilicate having a composition expressed as a molar ratio of oxides (0.9 + 0.2) (WR „O (1 W) M _n , O): B _n O _{o Y} Si Si _{n n} Z H _o 0,

- 2. 2 / П 2 3 22 where

R is a C8 -C12 tetraalkylammonium group, preferably the tetrapropyl group M is an alkali metal ion,

W is greater than 0 and less than or equal to 1,

Y has a value of 4 to 500 and

Z is 0 to 160.

This borosilicate is characterized by interplanar distances and associated intensities # as shown in Table II below.

In a preferred embodiment, W has a value in the range of 0.6 to 0.9, Y a value in the range of 20 to

500 and Z values between 0 and 40.

The present invention relates to a novel crystalline synthetic AMS-1B borosilicate. The group of crystalline AMS-1B borosilicate materials is characterized by a special X-ray diffractogram as described in the tables below. Crystalline AMS-1B borosilicates can generally be characterized by the molar ratio of oxides as shown in (1):

(0,9 + 0,2) M _{2 / n} O: B ₂ O ₃ : Y SiO _{2 2} H ₂ O (1), where

M is at least one cation, n is the valency of that cation,

Y has a value in the range of 4 to 500 and

Z represents the number of water molecules contained in such material in the range of 0 to 160 or more.

Y otherwise, this crystalline AMS-1B borosilicate, characterized by the molar ratio of oxides, can be described for crystalline, not yet activated or calcined material at higher temperatures by relation (2):

(0.9 ± 0.2) (WR ₂ O + (1 - W) ^M 2 / n ^{0>: B} 2 ° 3 ^{: Y si0} 2 ^{Z H} 2 ° ⁽²⁾ · where

R represents a tetrapropylammonium group,

M means at least one cation,

CS 266 302 B2 n means the valency of this cation,

Y has a value between 4 and 500, Z has a value in the range of 0 W has a value greater than 0 to 160 a and less than 1. r Iti 1k. <1 1 < > n M in you? íf · ιιν »· <hniýrli v /.i> i <· ífh tnužt ' bullfinch / m> л 1 иру, known 1 z rlonnvmln í In

the art _of ion exchange disposed at least partially replaced by other cations. Preferred exchange cations include tetraalkylammonium cations, metal ions, ammonium ions, protons, and mixtures thereof. Particularly preferred cations are those which render the crystalline AMS-1B borosilicate catalytically active, particularly for hydrocarbon conversion. These include hydrogen, rare earth metals, aluminum, Group IB, IIB and VIII metals of the Periodic Table of the Elements, rare metals, manganese, etc. and other catalytic active substances and metals known in the art. The catalytically active ingredients may be present in an amount of about 0.05 to about 25 weight percent based on crystalline AMS-1B borosilicate.

Representatives of the group of crystalline AMS-1B borosilicates have a specified and unambiguous crystalline structure. The X-ray diffractograms of these compounds were obtained by standard procedures using a powdered substance. The X-ray diffractogram used was a Phillips apparatus that operated with K _rf copper radiation along with an AMR-focusing monochrometer and an 0-compensating slit in which its aperture varied at an angle Θ.

The X-ray diffractograph output was processed by a computer with a Canberra data acquisition system with associated programs and captured using a paper strip and tabular expression. The compensating slots and the Canberra data acquisition system tend to increase the ratio of the useful maxima to the disturbing base, with maximum intensities at low 0-angles [high d (R) l decreasing and maximum intensities at high Θ-angles (low d (8)) All of the above X-ray diffractograms were obtained using this analytical technique.

These relative intensities were calculated as (100 Ι / Ιθ), where I means the intensity of the strongest captured maximum and I means the actual value, corresponding to the specific interplanar distance.

For simplicity, relative intensities have been assigned to the following values:

Ι / Ιθ assigned intensity

under 10 = vw 10 to 19 = in 20 May to 39 = M 40 to 70 = MS over 70 vs

A typical X-ray diffraction pattern in which significant lines with relative intensities of 11 or greater for crystalline AMS-1B borosilicate after calcination at 535 ° C is captured is shown in Table I below.

Tabulkal

Interplanar distance d (R) Relative intensity Assigned intensity 11.3 + 0.2 38 M 10.1 + 0.2 30 M 6.01 ± 0.07 14 w 4.35 + 0.05 11 w 4.26 + 0.05 14 w

CS 266 302 B2

T ab U 1 К ^{а 1}

Tnterplanámí gives up 1 transmission 1 · d (Я)

3.84

3.72

3.64

3.44

3.33

4 · 0.05 + 0.05 + 0.05 + 0.05 + 0.05 (continued)

Relative intensity

100 —fc

Assigned intensity

VS

MS

M

W

W w

ω Cu. < * υ φ Φ clay * 4 P’4 3 ’Μ <4 · rtx 0 * H · ♦ · £ 1 i £ i ПХН · № & H * 4 \ V4 3 r * p. ♦ HIM O P h * • o ω 4 ^ c н Ф < UJ <rfM O Н » H and w № CD

&G

H OK

With HQ · * ^

O 440 rt • Ή

O <

(IN

Ox

СГ

O ro

Corrections in printed descriptions of inventions

<О '

4 *

- <3

CS 266 302 B2

T a b u 1 к а III (continued)

Interplanar Handle 1

4.37

4.27

4.00

3.85

3.72

3.64

3.48

3.44

3.30

3.14

3.04

2.98

2.86

2.71

2.60

2.48

2.39

2.32

2.22

2.00

1.99

1/95

1.91

1.86

1.75

1.66 distance d (Я) handle 2

4.62

4.35

4.25

4.00

3.85

3.70

3.64

3.46

3.42

3.30

3.25

3.12

3.04

2.97

2.86

2.71

This shaft ended at 2.71 d (X)

The catalysts of the present invention based on crystalline AMS-1B borosilicate are useful for catalytic cracking and for cracking in the presence of hydrogen or hydrocracking. They also appear to have relatively valuable catalytic properties in other petroleum refining processes, such as isomerization of normal paraffins and naphthenes, in the reforming of certain feedstocks, in isomerization of aromatics, in particular isomerization of polyalkyl-substituted aromatics such as o-xylene, in aromatic disproportionation such as toluene, to form mixtures of other valuable products including benzene, xylene and other methyl-substituted benzenes and hydrodealkylation or dealkylation in the presence of hydrogen. Their use in isomerization processes where cations at ion exchange sites are suitable within crystalline AMS-1B borosilicate results in remarkably high selectivities in the formation of the desired isomers.

The ability of these materials to remain stable at high temperatures or in the presence of other, usually inactivating agents, makes this group of crystalline materials valuable for high temperature processes including cyclic types of fluidized catalytic cracking or other methods.

Crystalline AMS-1B borosilicates can be used as catalysts or as adsorbents, whether in the form of alkali metal, ammonium, hydrogen or some other monovalent or polyvalent cations. Mixtures of cations may be used. Catalysts of the invention consisting of crystalline AMS-1B borosilicates,

CS 266 302 B2 can also be used in close combination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal such as platinum or palladium or rare earth metals, where should achieve a hydrogenation-dehydrogenation effect. Such components may be exchanged, impregnated or physically intimately admixed in the composition at the cationic sites depicted by the M designation in the above formulas. So, for example, the line? ··)> l.il hi.t was 11.111 * n n i i i i i i i i ok ok ok ok ok ok ta ta cf in metal | lal i nu.

The original cation associated with crystalline AMS-1B borosilicate, as described above, can be replaced by a number of other cations by methods known in the art. Ion exchange techniques known in the art are described in numerous patents, including U.S. Patents 3,140,249, 3,140,251 and 3,140,253.

After ion exchange, impregnation, or contact with other material to incorporate or apply catalytically active materials to the borosilicate structure, the treated material may be washed and then dried at temperatures in the range of about 66 to about 316 ° C. It may then be annealed in air or under a nitrogen atmosphere or in a mixture of the two at a precisely controlled temperature in the range of about 260 to about 816 ° C.

Ion exchange at cation sites within crystalline materials usually has a relatively insignificant effect on the overall X-ray diffraction pattern that characterizes crystalline borosilicate material. There may be small variations at different distances in the diffractogram, but the overall diffractogram remains essentially the same. Small changes in the X-ray diffraction pattern may also be the result of differences in borosilicate preparation. However, the material still falls within the general group of crystalline AMS-1B borosilicates, which are defined by their X-ray diffractogram as shown in Tables I, II and III or in the examples below.

The crystalline borosilicate-forming catalyst of the invention may be used as pure borosilicate or may be mixed with various binders or according to the intended use. In many cases, crystalline borosilicate can be pelletized or extruded. Crystalline borosilicate can be combined with active or inactive materials, synthetic or natural zeolites as well as inorganic or organic materials that are useful for borosilicate binding. Other well known materials include mixtures of silica, silica-alumina, aluminum oxide salts, clays such as bentonite or kaolin, or other binders known in the art. Crystalline borosilicate can also be intimately mixed with porous matrix materials such as silica

- zirconium dioxide, silica-magnesium oxide, silica-alumina, silica-thorium oxide, silica-beryllium oxide, silica-titanium dioxide, and tri-component mixtures which include, but are not limited to, oxide Silica

alumina - thorium oxide, and many other materials known in the art. The content of crystalline borosilicate in the compositions may vary as desired from a few to 100% of the total product.

The invention also provides a method of preparing a catalyst composed of a crystalline borosilicate, a composition in terms of oxide molar ratio of (0.9 + 0, ^{2> Μ} 2 / ^η ΟίΒ 2 ^{Ο 3:} SiO 2 Y ₂ O * .ZH wherein

M represents at least one valence c of the group consisting of a tetraalkylammonium cation of 8 to 12 carbon atoms, an ammonium cation, a hydrogen cation, an alkali metal cation or mixtures of these cations with one another,

Y has a value of 4 to 500 and

Z is 0 to 160,

CS 266 302 B2 which comprises mixing boron, alkali metal and silicon oxides in an aqueous medium with a tetraalkylammonium compound in weight ratios providing molar ratio values.

SiO _? / B ₂ O ₃ IN range 5 to 600 U ₄ (N '') (W _y jN ^F ; i Na *) in range 0, 1 to 1 0 [Г / Б1О ₂ in range 0.01 to 10 H ₂ O / OH ~ in range 10 to 500,

where

R 'represents an alkyl group having 2 or 3 carbon atoms and

Na is a cation of sodium or any other alkali metal of the reactant is heated at a temperature in the range of 90 to 250 ° C for a time sufficient to precipitate the borosilicate crystals, after which the crystals are dried and calcined after isolation of the reaction medium to obtain calcined crystalline borosilicate.

The process according to the invention is similar to the production of a catalyst consisting of crystalline borosilicate having a composition expressed in molar ratio of oxides (0.9 + 0.2) (WR ₂ O + (1 - W) M _{2 / n} O); B ₂ O ₃ : Y SiO ₂ : ZH ₂ O, where

R represents a C 8 -C 12 tetraalkylammonium group, preferably a tetrapropylammonium group,

M is an alkali metal cation,

W is greater than 0 and less than or equal to 1,

Y has a value of 4 to 500 and

Z has a value of 0 to 160, which process consists in mixing the boron, alkali metal and silicon oxides with the tetraalkylammonium compound in an aqueous medium in proportions of molar ratios

Si 2 ° ^{/ B} 2 ° 3 within 5 to 600 R * N ⁺ / (R 'N + Na) in range 0.1 to 1 oh '/ sieve ₂ in range 0.01 to 10 h ₂ o / oh in range 10 to 500

where

R represents an alkyl group having 2 or 3 carbon atoms, preferably a propyl group and

Na * is a cation of sodium or any other alkali metal, the reactants are heated at a temperature in the range of 90 to 250 ° C for a time sufficient to precipitate the borosilicate crystals, whereupon the crystals are isolated from the reaction medium.

Simply by changing the amount of boron (as boron oxide ^B 2 ° 3, ^{in the REA} ^ protrudes mixture can be varied by the molar ratio of silicon к oxide boron SiO ₂ / B ₂ O ₃ in the final product of from about 40 to about 500 or above. In In cases where it is intentional to remove aluminum from the borosilicate crystal structure due to its adverse effect on certain conversions, the molar ratios of silica to SiO ₂ / Al ₂ O _{3 may} easily exceed 2,000 to 3,000. This ratio is generally limited only the availability of aluminum-free raw materials.

CS 266 302 B2

The molar ratios of silica to boron trioxide SiO ₂ / B ₂ O ₃ in the crystalline resulting product may range from about 4 to 500 or above. Current laboratory products under the general conditions described above provide molar ratios of silica to boron oxide SiO ₂ / B ₂ O ₃ starting at about 40 or below. Lower ratios can generally be achieved by the use of manufacturing processes that are still within the scope of the invention.

Based on the known properties of mordenite and ferrierite aluminosilicates, the subject crystalline borosilicates contain about 4.5 BO ^-tetrahedron per unit part at a molar ratio of silica to boron oxide of SiO ₂ / B ₂ O _{3 of} about 80. Consequently, at a ratio of silica: boron oxide of SiO ₂ / B ₂ O _{3 of} about 500 is present only BO ₄ ~ tetrahedra. Above this ratio, there would be numerous unit particles that contain no B ^ ^-tetrahedron, and the obtained crystalline structure could not be regarded as borosilicate. There are no fixed criteria to conclude at which molar ratio of silica to boron dioxide SiO ₂ / B ₂ O ₃ crystalline material ceases to be borosilicate. It is sufficient to assume that at high SiO ₂ / B ₂ O ₃ ratios (above 1000 or more), the effect of the BO 4 -stain in the crystalline structure decreases somewhat and the crystalline material is no longer considered a borosilicate.

The crystalline AMS-1B borosilicate-forming catalyst of the invention is formed under carefully controlled conditions using the above data. Typical reaction conditions, as discussed above, include heating the reactants at a temperature of from about 90 to about 250 ° C or above, for any period of time from about a few hours to a few weeks or more. Preferred temperature ranges are from about 150 to about 180 ° C for the time required to precipitate crystalline AMS-1B borosilicate. Particularly preferred conditions include a temperature of about 165 ° C for about Ί days.

The material thus formed can be separated and isolated by known methods, for example by filtration. This material may be slightly dried for a few hours to several days at different temperatures to form a dry cake, which may then be crushed into powder or small particles and extruded, pelletized or rendered in a form suitable for the intended use. Typically, such a mild drying material contains a tetraalkylammonium ion within the solid, and subsequent activation or calcination is required to remove the material from the product.

High temperature calcination is typically conducted at temperatures from about 427 to about 871 ° C or above. Extreme calcination temperatures can have a detrimental effect on the crystal structure or can completely disturb it. In general, calcination at temperatures above 927 ° C does not need to be carried out to remove the tetraalkylammonium cation from the initially formed crystalline material.

When the catalyst of the present invention is used in hydrocracking, the hydrocracking feedstock can be passed through the catalyst at temperatures of from about 260 ° C to about 454 ° C or higher, using known molar ratios of hydrocarbon to hydrogen and various pressures .03 MPa. The hourly liquid flow rate and other operating parameters can be varied as known in the art.

When the catalyst of the invention is used in a fluidized catalytic cracking process, generally known operating conditions include temperatures of from about 260 to about 649 ° C in the reaction zone and temperatures of from about 427 to about 704 ° C in the recovery zone. Contact times of the feedstock and other operating conditions are known in the art.

The specific crystalline AMS-1B borosilicate is also suitable as a reforming catalyst, which is used together with suitable hydrogenation components under known reforming conditions including heat from about 260 to 566 ° C or above, pressures from a few thousandths of MPa to 2.11 to 7 300 MPa and hourly flow rates of liquid components and hydrocarbon molar ratios

CS 266 302 B2 to hydrogen in accordance with known prior art parameters for the reformation process.

The catalyst of the present invention is also suitable for hydrocarbon isomerisation and hydrocarbon disproportionation. It is particularly useful for the xylene disintegration in the liquid or gas phase and in particular for the isomerization of mixed xylenes to products containing predominantly p-xylene. Isomerization conditions include temperatures from about 93 to about 538 ° C, hydrogen to hydrocarbon molar ratios of from about 0 to about 20, and hourly liquid phase flow rates of from about 0.01 to about 90. Catalytically active metals to be deposited on the crystalline The AMS-1B borosilicate may be selected from metals known in the art for this purpose. Nickel appears to be particularly suitable for the isomerization of aromatics.

Crystalline AMS-1B borosilicates can also be used as adsorbents for the selective adsorption of special isomers or generally hydrocarbons from a liquid or gaseous stream.

The following examples illustrate the invention.

Example 1

Crystalline AMS-1B borosilicate was prepared by dissolving 0.25 g of boric acid H 3 BOg and 1.6 g of NaOH in 60 g of distilled water. 9.4 g of tetra-n-propylammonium bromide are then added and allowed to dissolve. Finally, 12.7 g of an aqueous colloidal silicic acid salt (30% dry matter) is added with vigorous stirring. Addition of the silica salt yields a dense, gelatinous, milk solution. This solution is poured into a reaction vessel which is sealed. The reaction vessel was then placed in an oven at 165 ° C for 7 days. After this time, the container is opened and the contents are filtered. The crystalline material obtained is washed with a considerable amount of water and then dried in an air pressure oven at 165 ° C. The dried material was identified by X-ray diffraction as a typical AMS-1B structure with 100% crystallinity. The yield is approximately 2 g.

Example 2

This example describes the crystalline ASM-1B borosilicate of Example 1 and its use to form a catalyst with isomeric properties.

The material of Example 1 was calcined for 4 hours in air at 535 ° C to remove the organic base. The calcined material was first treated with a solution of 20 g of ammonium nitrate NH ₄ NO ₃ in 200 ml of water and then with a solution of 10 g of ammonium acetate CH 2 COONH 4 in 200 ml of water at 87.8 ° C for 2 hours. The resultant ion exchange borosilicate is dried and then calcined in air by heating at 482 ° C for 4 hours; then cooled to 37.8 ° C over a further 4 hours. The calcined material is treated for 2 hours with 100 ml of a 5% solution of nickel nitrate hexahydrate Ni (NO 2) ₂ · 6H ₂ O at 87 ° C. The molecular sieve obtained is washed with water and the nickel-nickel ion Ni is completely removed by washing. The screen is then dried and re-calcined as described above. 2 g borosilicate are dispersed in 16.9 g of PHF-Al ₂ O ₃ hydrosol (8.9% dry matter) and the dispersion is mixed thoroughly. To 1 ml of distilled water, 1 ml of concentrated ammonium hydroxide is added and the mixture is added to the dispersion with vigorous stirring. The AMS-mixture was then dried in an oven at 165 ° C for 4 hours. The dried material is calcined as described above. The calcined catalyst is ground to a particle size in the range of 0.297 to 0.55 nm and soaked with 2 ml of a 5% solution of nickel nitrate hexahydrate Ni (NO ₃ ) ₂ .6H ₂ O in distilled water. The catalyst was dried again and activated again by the fourth calcination.

The calcined catalyst contains 65 wt% borosilicate and 35 wt% amorphous alumina and about 0.5 wt% nickel based on total solids.

CS 266 302 B2 g of the screened and activated catalyst are introduced into the microreactor and treated with hydrogen sulfide at room temperature for 20 minutes. The catalyst was then treated with hydrogen under pressure while heating to 316 ° C. After 1 hour, the microreactor is started to feed under the following conditions:

I <* |>11> 1 л 4 2 7 ° <* • overpressure 1,05 MPa throughput (WHSV) 6,28 h “ ¹ molar H / HC ratio ** (hydrogen / hydrocarbon) 7

The liquid raw material and products obtained by this process are listed below. Due to the limitations imposed by the separating device, only liquid stream analysis was performed. The formation of a light end product on this catalyst is slight according to gas chromatographic analysis of the off-gas stream. It has been found that the amount of off-gas does not appreciably reduce the overall yields of the liquid components obtained using the catalyst.

Folders Liquid raw material weight% Liquid product weight% paraffins and naphthenes 0.03 0.08 benzene - 1.51 toluene 0,077 0.26 ethylbenzene 19.71 17.35 p-xy only - 19.43 m-xylene 79.80 46.40 o-xylene 0.38 14.96 Cg x) - 1,0 x)

(x) approximate values only

Example 3

A solution of 2.5 g of boric acid 1BOH and 7.5 g of sodium hydroxide in 600 g of water is prepared. 94.3 g of tetra-n-propylammonium bromide are then added and allowed to dissolve, followed by the addition of 114.5 g of aqueous colloidal silica sol (30% solids content) with vigorous stirring.

The resulting mixture was placed in a reaction vessel and sealed. The sealed vessel is left in an oven at 165 ° C for 7 days.

After washing and drying the solid obtained as described in Example 1, crystalline borosilicate is identified as AMS-1B; it is characterized by an X-ray diffractogram similar to that of Table II.

Example4

The borosilicate produced by the procedure of Example 1 was calcined at 593 ° C and analyzed to determine its total composition. The results are shown below.

Ingredients (% by weight) SiO2 94.90 boron oxide B2 ° 3 1.06 * sodium oxide Na ₂ O 0.97 aluminum oxide Al ₂ ° 3 0.057 iron oxide ^Fe 2 ° 3 0,029

CS 266 302 B2 volatile components x) __2,984 total 100,000

(x) the assumed value to be 100%

Mr »I / <ΙΊ) í p <> 111 * · 1 γ

I SiO ₂ / B ₂ O ₃ 104.5

Na ₂ O / B ₂ O ₃ 1.0

SiO ₂ / Al ₂ O ₃ 2824.4

A SiO ₂ / Fe ₂ O ₃ 8787.0

SiO ₂ / (Al ₂ O ₃ + ^Fe 2 ° 3 ^{) 2146}

Following the procedure of Example 1, other borosilicates followed, but changing the content of boric acid H ₂ BO _3, thereby к mole ratios of silica к oxide boron Sio ₂ / B ₂ O _3, which are - before calcination borosilicate or before the ion exchange - ranging from 50 to 160 or more. Upon exchange with suitable catalyst materials, the SiO ₂ / B ₂ O ₃ molar ratio generally increases to 80-100 for borosilicate, which as produced had a SiO ₂ / B ₂ O ₃ molar ratio of about 50.

Example 5

Three borosilicate materials were prepared as in Example 1. These materials were calcined at 535 ° C and then analyzed for boron and silicon content; the results are shown below:

borosilicate wt. % of boron SiO ₂ / B ₂ O ₃ molar ratio AND 0.66 4 7,4 В 0.64 49.1 C 0.71 44.5

After ion exchange with ammonium acetate, the borosilicate is calcined at 535 ° C.

After calcination, the values of the observed SiO ₂ / B ₂ O ₃ molar ratio are as follows:

borosilicate molar ratio SiO ₂ / B ₂ O ₃ ⁿ 71.2 ^C 64.2

After calcination at 535 ° C, but prior to ion exchange, samples of the above borosilicates in powder form are subjected to analysis to obtain X-ray diffractograms. The obtained diffractograms are given below at relative intensities (Ι / Ιθ) Ю or higher. In the previous Table III, interplanar distances are shown, as determined on a paper strip for two borosilicate feeds after calcination at 535 ° C, but prior to ion exchange.

Table V (borosilicate A)

Interplanar distance d (Я) Relative intensity (I / I _Q )

11/34 38 10.13 30 6.01 14 4.35 11

CS 266 302 B2

Table V (continued)

Interplanar distance d (R) Relative intensity (I / I) o

4,2614

3,84100

1,7 2 'iλ

3.6531

3.4414

3.3316

3,0416

2.9722

2.4811

1,99 '20

1.6612

Table VI (borosilicate B)

Interplanar distance d (8) Relative intensity (Ι / Ιθ)

11.35 41 10 ^ 14 31 6.02 15 Dec 4.26 15 Dec 3.84 100 ALIGN! 3.72 52 3.65 33 3.44 13 3.32 15 Dec 3.04 16 2.97 12 2.48 11 1.99 20 May 1.66 12 ) u 1 к а VII (borosilicate C) Interplanar distance d (R) Relative intensity (I / l) O 11.40 33 10.17 29 6.03 13 5.62 10 4.27 ¹⁴ 3.84 100 ALIGN! 3.73 51 3.65 30 3.44 13 3.32 16 3.05 ¹⁶ 2.98 21 1.99 19 Dec 1.66 12

Claims (22)

SUBJECT OF THE INVENTION Catalyst for the cracking, hydrocracking and isomerisation of hydrocarbons, characterized in that it consists of crystalline borosilicate of a composition expressed in the molar ratio of ox i (ΙΓι (0,9 + 0,2) M _{2 / n} O: B ₂ O ₃ : Y SiO 2 ZH ₂ O, where M represents at least one cation of valency n of the group consisting of a tetraalkylammonium cation of 8 to 12 carbon atoms, an ammonium cation, a hydrogen cation, an alkali metal cation or mixtures of these cations with one another, Y has a value of 4 to 500 and Z has a value of 0 to 160.. 2. Catalyst according to claim 1, characterized in that it consists of crystalline borosilicate having the composition expressed in the ratio of oxides specified in point 1, where Y has a value of 20 to 500 and the other general symbols have the meaning given in point 1. 3. Catalyst according to claim 1, characterized in that it consists of a crystalline borosilicate having the composition expressed in the ratio of oxides referred to in point 1, where M is nickel and the other general symbols have the meaning given in point 1. 4. Catalyst according to claim 1, characterized in that it consists of crystalline borosilicate having the composition in terms of the ratio of oxides specified in claim 1, wherein M comprises hydrogen, nickel and an alkali metal and the other general symbols have the meaning given in claim 1. 5. Catalyst according to claim 1, characterized in that it consists of crystalline borosilicate having the composition expressed in the ratio of oxides specified in point 1, wherein M comprises hydrogen and nickel and the other general symbols have the meaning given in point 1. 6. Catalyst according to claim 1, characterized in that it consists of a crystalline borosilicate having the composition expressed in the ratio of oxide referred to in point 1, wherein Y has a value of 40 to 500 and the other general symbols have the meaning given in point 1. 7. Catalyst according to claim 6, characterized in that it consists of crystalline borosilicate having a composition in terms of the oxides ratio given in point 1, wherein Z has a value of 0 to 40 and the other general symbols have the meaning given in point 1. 8. The catalyst of claim 1, wherein the catalyst is a crystalline borosilicate having a composition in terms of the oxides ratio of 1, wherein Z is from 0 to 40 and the other general symbols are as defined in 1. 9. The catalyst of claim 1, wherein the catalyst is a crystalline borosilicate having a composition in terms of the oxides ratio of point 1, wherein Y is from 20 to 160 and the other general symbols are defined in point 1. 10. The catalyst of claim 1, wherein said catalyst comprises a crystalline borosilicate having a composition expressed as the oxide coating of (1) wherein Y is from 20 to 200; Z has a value of 0 to 40 and the other general symbols have the meaning given in point 1. 11. The catalyst of claim 1, wherein said catalyst is a crystalline borosilicate having a composition in terms of the oxides ratio of (1) wherein Y is from 4 to 200 and the other general symbols are (1). CS 266 302 B2 12. The catalyst of claim 1, wherein the catalyst is a crystalline borosilicate having a composition in terms of the oxides ratio of 1, wherein Y is from 4 to 160 and the other general symbols are defined in 1. 13. Catalyst according to claim 1, characterized in that it consists of crystalline borosilicon having a value of ti 0. other general symbols have the meaning given in point 1. 14. The catalyst of claim 1, wherein the catalyst is a crystalline borosilicate having a composition in terms of the ratio of oxides set forth in point 1, wherein Z is from 0 to 40 and the other general symbols are defined in point 1. 15. The catalyst of claim 14, wherein the catalyst is a crystalline borosilicate having a composition in terms of the oxides ratio of (1) wherein Y is from 50 to 50. 160 and other general symbols have the meaning given in point 1. 16. The catalyst of claim 1, wherein said catalyst comprises a crystalline borosilicate having a composition in terms of the ratio of oxides as defined in claim 1, wherein Y is from 80 to 120, Z has a value of 0 to 40 and the other general symbols have the meaning given in point 1. 17. The catalyst of claim 1, wherein said catalyst is a borosilicate crystalline composition of the oxide pairs described in claim 1, wherein Y is from 20 to 500, Z has a value of 0 to 40 and the other general symbols have the meaning given in point 1. 18. The catalyst of claim 17, wherein the catalyst is a crystalline borosilicate having a composition in terms of the oxides ratio of 1, wherein Y is between 40 and 500 and the other general symbols are as in 1. 19. Catalyst according to claim 1, characterized in that it consists of crystalline borosilicate having a composition expressed in molar ratio of oxides (0,9 + 0,2) [WR ₂ O (1 - W) M _{2 / n} O: B ₂ O ₃ : Y SiO ₂ : ZH ₂ O, where R represents a C 8 -C 12 tetraalkylammonium group, preferably a tetrapropylammonium group, M is an alkali metal ion, W is greater than 0 and less than or equal to 1, Y has a value of 4 to 500 and Z has a value of 0 to 161). 20. Catalyst according to claim 19, characterized in that it consists of crystalline borosilicate having a composition expressed in terms of the oxides ratio given in point 19, wherein Y has a value of 20 to 500 and the other general symbols have the meaning given in point 19. 21. A process for producing a catalyst according to item 1, consisting of crystalline borosilicate having a composition expressed as a molar ratio of oxides of (0.9 ± 0.2) M _{2 / n} O: B ₂ O ₃ : Y SiC> ₂ : ZH ₂ O, M represents at least one valence c of the group consisting of a tetraalkylammonium cation of 8 to 12 carbon atoms, an ammonium cation, a hydrogen cation, an alkali metal cation or mixtures of these cations with one another, CS 266 302 B2 Y has a value of 4 to 500 and 2 has a value of 0 to 160, characterized by SG, in which aqueous boron, alkali metal and silicon oxides are mixed with the tetraalkylammonium compound in weight ratios giving molar values | · <> ^Si ° 2 ^{/ B} 2 ° 3 ₊ within 5 to 600 R'N / (R'N + Na) in range 0.1 to 1 oh ~ / sieve ₂ in range 0.01 to 10 н o / oh ' in range 10 to 500 where R 'represents an alkyl group having 2 or 3 carbon atoms and Na ⁺ is a cation of sodium or any other alkali metal, the reactants are heated at a temperature in the range of 90 to 250 ° C for a time sufficient to precipitate borosilicate crystals, after which the crystals are dried and calcined after isolation from the reaction medium to obtain calcined crystalline borosilicate. 22. A process for producing the catalyst of item 19 consisting of crystalline borosilicate having a composition expressed as a molar ratio of oxides (0.9 + 0.2) [WR _? O (1 - W) ^M ₂ / n ° J ^ϊΒ 2 ^Ο 3 ^{: Υ si0} 2 ^{Z H} 2 ° where R is a C 8 -C 12 tetraalkylammonium group, preferably a tetrapropylammonium group M is an alkali metal cation, W is greater than 0 and less than or equal to 1, Y has a value of 4 to 500 r Z has a value of 0 to 160, characterized in that boron, alkali metal and silicon oxides are mixed in an aqueous medium. with a tetraalkylammonium compound in weight ratios giving molar ratio values sieve ~ / b ₂ o ₃ R'N ^ / (R'N ⁺ + Na ⁺ ) in in range range 5 0.1 to aŽ 600 1 0 oh / sieve ₂ in range 0.01 to 10 h ₂ o / oh ' in range 10 to 500, where R 'denotes a C 2 -C 3 alkyl group, preferably a propylated group and Na ⁺ denotes a cation of sodium or any other alkali metal, the reactants are heated at a temperature in the range of 90 to 250 ° C for a time sufficient to precipitate borosilicate crystals, these crystals are isolated from the reaction medium.