DK153134B - CRYSTALLIC BORN SILICATE TO USE AS A CATALYST OR CATALYST PRECURSOR FOR CONVERSION OF CARBON HYDROIDS AND PROCEDURE FOR SUCH CONVERSION - Google Patents

Description

DK 153134 B

The invention relates to a crystalline borosilicate for use as a catalyst or catalyst precursor in the conversion of hydrocarbons and a process for the conversion of hydrocarbons using the catalyst or catalyst precursor. In another way, the invention relates to novel crystalline molecular sieves of borosilicates having catalytic properties and various hydrocarbon conversion processes using such crystalline borosilicates. Relevant patents can be found in classes 423-326, 252-458 and 260-668 of the United States Patent Classification.

It is known that both natural and synthetic zeolite materials

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2 has catalytic activity in many hydrocarbon processes. The zeolite materials are ordered porous crystalline aluminosilicates with a specific structure with large and small voids interconnected by channels. The voids and channels through the crystalline material are generally uniform in size, allowing selective separation of hydrocarbons. As a result, these materials are in many cases classified as molecular sieves and used in addition to the adsorptive selective processes due to certain catalytic properties. The catalytic properties of these materials are also affected to a certain extent by the size of the molecules which are selectively allowed to enter the crystal structure which is believed to be brought into contact with active catalytic positions within the ordered structure of these materials.

In general, the term "molecular sieve" encompasses a wide range of crystalline materials containing positive ions, whereby these materials can be both natural and synthetic. They are generally characterized as crystalline aluminosilicates, although other crystalline materials are included in the broad definition. The crystalline aluminosilicates are made from networks of tetrahedrons of SiO₂ and AlO ^ moieties in which the silicon and aluminum atoms are cross-linked by dividing oxygen atoms. The electrovalence of the aluminum atom is balanced by the use of a positive ion, e.g. alkali metals or alkaline earth metals.

Known developments have resulted in the formation of many synthetic crystalline materials. Crystalline aluminosilicates are the most widespread and are denoted by letters or other appropriate symbols in patent literature and in published journals. Examples of these materials are Zeolite A (US Patent 2,882,243), Zeolite X (US Patent 2,882,244), Zeolite Y (US Patent 3,130,007), Zeolite ZSM-5 (US Patent 3-702,886), Zeolite ZSM 11 (US Patent 3,709-979) and Zeolite zsm-12 (US Patent 3,832,449).

Relevant prior art is the above-mentioned United States patent no.

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No. 3,702,886, which relates to the crystalline aluminosilicate zeolite ZSM-5 and the process for its preparation. This patent is limited to the production of a zeolite in which aluminum or gallium oxides are present in the crystalline structure together with silicon or germanium oxides. The latter is reacted with the first stated in a specific relation to the preparation of a class of zeolites designated ZSM-5 which is limited to crystalline alumino or gallo silicates or germates and which exhibits a specified X-ray diffraction pattern. The above-mentioned ZSM-11 and ZSM-12 patents are also limited to crystalline alumino or gallo silicates or germates which also exhibit specified X-ray diffraction patterns.

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

U.S. Patent No. 3,941,871 relates to an organosilicate having very little aluminum in its crystalline structure and having an X-ray diffraction pattern similar to that of the ZSM-5 material. This patent is considered to be relevant prior art.

Other relevant prior art includes United States patents 3-329,480 and 3,329-481 relating to "zirconium silicates" and "titano silicates, respectively."

In relation to the prior art, it may be stated that there is a need for catalysts whose stability at high temperatures or in the presence of other normal inactivating agents makes them more suitable than prior art catalysts for catalytic cracking and hydrocracking.

The crystalline borosilicate of the invention is peculiar

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4 in accordance with the characterizing part of claim 1. Surprisingly, it has been found that the stability of these borosilicates is better than prior art and that the borosilicates according to the invention are therefore more suitable as catalysts or catalyst precursors, especially in catalytic cracking and hydrocracking.

The process of the invention for the conversion of hydrocarbons is characterized by the method of claim 8.

Preferred are the embodiments of the invention where W = 0.

Thus, the present invention relates to a new family of stable, synthetic crystalline materials characterized as borosilicates designated as AMS-1B with a specified X-ray diffraction pattern. The required AMS-1B crystalline borosilicates are formed by reacting a borosal with a silicon-containing material in a basic medium.

In another embodiment of the invention, W has a value between ca. 0.6 and approx. 0.9.

Thus, the present invention relates to a novel synthetic AMS-1B crystalline borosilicate. This family of AMS-1B crystalline borosilicates has a specified X-ray diffraction pattern, which is shown in the following tables. The AMS-1B crystalline borosilicates can generally be characterized in terms of the molar ratio of the oxides according to the following formula I: [0.9 + 0.23 M 2 O: B 2: YSiC> 2: ZH 2 O.

In another case, the present AMS-1B crystalline borosilicate as regards the molar ratio of oxides to the crystalline material not yet activated or calcined at high temperatures can be characterized according to the following formula: [0.9 + 0.2]. (WR20 + (lW) M2 ^ n0): B ^: YSi02: ZH20

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5 where W is greater than 0.

The original cation, "M", in the above formulas, can be replaced, at least partially, by other techniques known in the art by ion exchangers. Preferred replacement cations include tetraalkylammonium cations, metal ions, Particularly preferred cations are those which render the AMS-1B crystalline borosilicates catalytically active, especially for hydrocarbon conversion, which include hydrogen, the rare earth metals, aluminum, Group IB metals, IIB and VIII of the Periodic Table, Precious Metals, Manganese, etc., and other catalytically active materials and metals known in the art, The catalytically active components may be present in any concentration between about 0.05 and about 25 % by weight of the AMS-1B crystalline borosilicate.

Members of the family of AMS-1B crystalline borosilicates exhibit a specified and distinctive crystalline structure. The reported X-ray diffraction patterns generated by these materials were obtained using standard technique in connection with powder diffraction patterns. The X-ray LED diffractometer was a Phillips instrument utilizing copper K alpha radiation in conjunction with an AMR focusing mono-chronometer and a theta compensating column, the aperture thereof varying with the theta angle.

The output of the diffractometer was processed through a Canberra-type hardware / software unit and reported using a strip chart and tabulated, printed outlines. The compensating gap and the Canberra unit tend to increase peak / background ratios while reducing peak intensities at low theta angles, / high d {k) J and increasing the intensities of peaks at high theta angles, / Iav d (Å ) /. All of the X-ray patterns reported here made use of the above

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6 given analytical technique.

The relative intensities reported were calculated as (100 I / lQ), where you are the intensity of the strongest reported peak and where you are the value actually read for the particular interplanar distance.

To facilitate reporting, the relative intensities were arbitrarily assigned the following values: I / I Assigned Strength

less than 10 = VW

10-19 = ¥

20-39 = M

40-70 = MS

greater than 70 = VS

A typical X-ray diffraction pattern showing the significant lines having relative intensities of 11 or greater for an AMS-1B crystalline borosilicate after calcination at 535 ° C is shown in the following Table I.

Table I

Interplanar Distance Relative Assigned d (Å) intensity strength

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

3.84 + 0.05 100 US

3.72 + 0.05 52 MS

3.65 ± 0.05 31 M

3.44 + 0.05 14 Vj

3.33 + 0.05 16 W

3.04 + 0.05 16 W

2.97 + 0.02 22 M

2.48 + 0.02 11 w

1.99 ± 0.02 M

1.66 + 0.02 12

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An AMS-1B borosilicate which has only been subjected to mild drying at 165 ° C (as produced material) exhibits an X-ray diffraction pattern having the following significant lines;

Table II

Interplanar Distance Relative Assigned d (Å) intensity strength

11.4 + 0.2 19 W

10.1 + 0.2 17 W

3.84 + 0.05 100 US

3.73 + 0.05 43 MS

3.66 ± 0.05 26 M

3.45 + 0.05 11 W

3.32 + 0.05 13 W

3.05 + 0.05 12 W

2.98 ± 0.02 16 W

1.99 + 0.02 10 - V

1.66 ± 0.02 M

The recordings on the strip map of the calcined borosilicate reported in Table I showed that this material exhibited the following X-ray diffraction lines:

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8

Table III

Interplanar distance d (Å)

Experiment 1 Experiment 2X

11.3 11.2 10.2 10.0 7.49 7.37. 6.70 6.70 6.41 6.36 6.02 5.98 5.71 5.67 5.60 5.57 5.01 5.34 4.62 5.01 4.37 4.62 4.27 4.35 4.00 4.25 3.85 4.00 3.72 3.85 3.64 3.70 3.48 3.64 3.44 3.46 3.30 3.42 3.14 3.30 3.04 3.25 2.98 3.12 2.86 3.04 2.71 2.97 2.60 2.86 2.48 2.71 2.39 2.32 2.32 22 2.00 1.99 1.95 1.91 1.86 1.75 1.66 x This trial ended at 2.71 d (Å)

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The AMS-1B crystalline borosilicates are useful in catalytic cracking and hydrocracking processes. They appear to exhibit relatively useful catalytic properties of other crude oil refining processes, such as the isomerization of normal paraffins and naphthenes, the reforming of certain starting materials, the isomerization of aromatics, in particular the isomerization of polyalkyl substituted aromatics such as orthoxylene, the disproportionation of aromatics such as mixtures of other more valuable products including benzene, xylene and other higher methyl substituted benzenes, and hydrodealkylation. When used as a catalyst in isomerization processes with appropriate cations arranged at the ion-exchangeable positions within the AMS-1B crystalline borosilicate, reasonably high selectivities are obtained to produce desired isomers.

The activity of these materials, which must be stable at high temperatures or in the presence of other deactivating agents, seems to make this class of crystalline materials relatively valuable for high temperature operation, including the cyclic types of fluidized catalytic cracking or other treatments.

The AMS-1B crystalline borosilicates can be used as catalysts or as adsorbents, whether in alkali metal form, in ammonium form, hydrogen form or any other monovalent or multivalent cationic form. Mixtures of cations can be used. The AMS-1B crystalline borosilicates can also be used in thorough combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a precious metal such as platinum or palladium or rare earth metals, where a hydrogenation -dehydrogenation function must be exercised. Such components may be exchanged in the mixture at the cationic positions represented by the term "M" in the above formulas, impregnated therein or thoroughly mixed therewith. In one example, platinum can be introduced onto the borosilicate with an ion containing metallic platinum.

The organic cation associated with the AMS-1B crystalline boric silicate can be replaced, as stated above, with many other other prior art cations.

Known ion exchange technique is described in many patents, including U.S. Pat. U.S. Patent No. 3,140,249, U.S. U.S. Patent No. 3,140,251 and U.S. Pat. Patent No. 3,140,253 ·

After ion exchange, impregnation or contact with another material for introducing catalytically active materials within or on the borosilicate structure, the material can be washed and then dried at temperatures in the range of approx. 66 and 316 ° C. It can then be calcined in air or nitrogen or combinations of both at precisely regulated temperatures in the range of approx.

260 and approx. 816 ° C for various periods.

Ion exchange within the cationic position in the crystalline material will generally have a relatively negligible effect on the overall X-ray pattern produced by the crystalline borosilicate material. Small variations may occur at different distances on the X-ray pattern, but the overall pattern remains essentially the same. However, small changes in the X-ray diffraction pattern may also result from processing differences during the preparation of the borosilicate, as the material will still fall within the generic class comprising AMS-1B crystalline borosilicates defined by their X-ray diffraction pattern as shown in Tables I, II and III or in the following Examples. .

The crystalline borosilicate of the present invention may be incorporated as pure borosilicate in a catalyst or adsorbent or may be mixed with various binders or bases, depending on the intended use. In many cases, the crystalline borosilicate can be combined with active or inactive materials, synthetic or naturally occurring zeolites as well as inorganic or organic materials which would be useful for bonding the borosilicate. Other well-known materials include mixtures of silica, silica-alumina, alumina sols, clays such as bentonite or kaolin or other binders known in the art.

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11 area. The crystalline borosilicate can also be thoroughly mixed with porous matrix materials such as silica zirconia, silica magnesia, silica-alumina, silica-thoria, silica-beryllia, silica-titania, and mixtures of three components comprising, but not is limited to silica-alumina-thoria, and many other materials known in the art. The content of crystalline borosilicate can range from a few% up to 100% of the total finished product.

The AMS-1B crystalline borosilicate may generally be prepared by mixing in an aqueous medium oxides of boron, sodium or any other alkali metal and silicon, and a tetraalkylammonium compound. The molar ratios of the various reactants can be varied considerably to produce the AMS-1B crystalline borosilicates. In particular, the mole ratios of the reactants expressed as the various oxides for preparing the borosilicate may vary as given in the following Table IV.

Table IV

Mole ratio

SiC ^ / ^O-j 5-600 (or higher) R4N + / (R4N + + Na +) 0.1-1 OH_ / SiO₂ 0.01-10 where R is alkyl and preferably propyl. The amounts indicated above and thus the concentrations in the aqueous medium may be varied. It is generally preferred that the molar ratio of water to the hydroxyl ion varies in the range of from 10 and approx. 500 or more.

By simply controlling the amount of boron (such as B 2 O 3) in the reaction mixture, it is possible to vary the molar ratio of the final product in a range of approx. 40 to approx. 500 or more. In such cases where an intentional effort is made to eliminate aluminum from the crystalline

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12 borosilicate structure due to its deleterious influence on special conversion processes, the molar ratios SiO ^ / AlgO ^ can easily be exceeded 2000-3000. This ratio is generally limited only by the availability of aluminum-free raw materials.

Molecular ratios of SiC2 / l2 and in the final crystalline product can range from about 4 to approx. 500 or more. Actual laboratory preparations under the general conditions described herein produce molar ratios of SiO 2 / B 2 O, beginning about 40 or less. Generally, lower ratios can be obtained using production methods that are still within the scope of the invention as described herein.

On the basis of known properties of killerite and ferrierite alumino silicates, the crystalline borosilicates present will have approx. 4.5 BO 2 tetrahedra per unit cell at molar ratios SiC₂ / I₂O ^ of about 80. Given this, there appears to be a single B00 at a ratio of about 500. Above that ratio, there will be many unit cells that do not contain a BO4 tetrahedron and the resulting crystalline structure need not necessarily be considered a borosilicate. There are no established criteria for assessing at what molar ratio SiO 2 / B 2 O the crystalline material ceases to be a borosilicate. It seems safe to assume that the influence of the B0 ^ tetrahedra in the crystalline structure at high values for SiO2 / B2 O2 (above 1000 or greater) is somewhat reduced and that the crystalline material would no longer be termed a borosilicate.

Under reasonably controlled conditions using the information given above, the required AMS-1B crystalline borosilicate will be prepared. Typical reaction conditions include heating the reactants to a temperature in the range of from 90 and approx. 250 ° C or more for a period of a few hours to a few weeks or more. Preferred temperature ranges are between approx. 150 and approx. 180 ° C, for a period of time necessary to precipitate the AMS-1B crystalline borosilicate. Particularly preferred conditions include

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13 a temperature of about 165 ° G for a period of approx. 7 days.

The material thus prepared can be separated and recovered by known methods such as filtration. This material can be dried under mild conditions for a period of a few hours to a few days, at varying temperatures, to form a dry cake which can be crushed into a powder or into small particles and extruded, tabulated or converted into suitable molds. for the intended use thereof. In a typical case, the material prepared under the mild drying conditions will contain the tetra-alkylammonium ion within the solid mass and a subsequent activation or calcination is required if it is desired to remove this material from the molded product.

In a typical case, the high temperature calcination conditions will comprise temperatures which are within the range of ca. 427 and approx. 871 ° C or above. Extreme Calcination temperatures may prove detrimental to the crystal structure or they can completely destroy it. There is generally no need to exceed approx. 927 ° C to remove the tetraalkylammonium cation from the originally formed crystalline material.

When the AMS-1B crystalline borosilicate is used as a hydrocracking catalyst, portions of starting material to be hydrocracked can pass over the catalyst at temperatures between ca.

260 and approx. 454 ° C or higher using known hydrocarbon-hydrogen molar ratios and using n varying pressures from anything below 1 kg / cm and up to many hundreds of kg / cm 2 or more. The space velocity of the liquid and other process parameters can be varied according to prior art. The space velocity has the dimension hour ^ and may be the volume in liters of liquid or gas per unit volume. passing through a given catalyst volume, divided by the volume of catalyst in liters (VHSV) or the quantity in kg of liquid or gas per liter. hour passes through a given catalyst mass, divided by the catalyst mass in kg (WHSV).

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By using the borosilicate for fluidized catalytic cracking, known operating conditions, including temperatures between ca. 260 and approx. 649 ° C in the reaction zone and temperatures between ca. 427 and approx. 704 ° C in the regeneration zone. Contact times, starting materials and other process conditions are known in the art.

The specified AMS-1B crystalline borosilicate is also suitable as a reforming catalyst which can be used with the appropriate hydrogenation components under well known reforming conditions, including temperatures between 260 and 566 ° C or below, gauge pressures between anything below 1 kg / cm and up to p 21 to 70 kg / cm 2, and fluid velocities and molar ratios of hydrocarbon to hydrogen according to those known in the art of reforming.

The present mixture is also suitable for isomerization and disproportionation of hydrocarbons. It is particularly useful for the isomerization of xylenes, and in particular the isomerization of mixed xylenes into products which are preferably para-xylene products in the liquid or vapor phase. The isomerization conditions include temperatures between ca. 93 to 538 ° C, hydrogen to hydrocarbon molar ratio of about 0 and approx. 20 and space velocities for the liquid in the range of approx. 0.01 and approx. 90 hour-1. The choice of the catalytically active metals which can be introduced into the AMS-1B crystalline borosilicate can be selected from any of the known in the art. Nickel appears to be particularly well suited for the isomerization of aromatics.

The required AMS-1B crystalline borosilicates can also be used as adsorbents for the selective adsorption of specific isomers or hydrocarbons generally from a liquid or vapor stream.

The following examples are specific embodiments of the invention.

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Example 1

An AMS-1B crystalline borosilicate was prepared by dissolving 0.25 g of HgBO ^ and 1.6 g of NaOI in 60 g of distilled E₂O. Then 9.4 g of tetra-n-propylammonium bromide (TPABr) was added, and g dissolved again. Finally, 12.7 g of Ludox-AS (30% solids) was added with vigorous stirring. Ludox-AS is a commercially available solution of 70% water and 30% SiO2 · Ludox is a trademark. Upon the addition of Ludox, a soft gelatinous, milky solution was obtained. This solution was placed in a reaction bomb and sealed. The bomb was placed in a 165 ° C furnace and left there for 7 days. At the end of this time, it was opened and its contents filtered. The recovered crystalline material was washed with copious amounts of H 2 O and then dried at 165 ° C in a forced air oven. The dried material was identified by X-ray diffraction as etched crystalline material with the typical AMS-1B pattern with 100% crystallinity. The yield was approx. 2 g.

Example II

In this example, the ASM-1B crystalline borosilicate of Example 1 was used to prepare a catalyst with isomerization capacity.

The material of Example I was calcined at 535 ° C in air for 4 hours to remove the organic base. The calcined molecular sieve was exchanged once with a solution of 20 g of NH 2 NO 2 in 200 ml of H2 O and then again with 20 g of NH 2 OAc (ammonium acetate) in 200 ml of H 2 <j at 88 ° C for 2 hours. . The exchanged borosilicate was dried and calcined in air by heating it to 482 ° C for 4 hours by holding the borosilicate at 482 ° C for 4 hours and then cooling to 38 ° C for 4 hours. The calcined material was exchanged with 100 ml of a solution of 5%

Ni (NO 2) 2.6 H 2 O for 2 hours at 88 ° C. The molecular sieve was washed with H2 O and Ni + completely washed out of the molecular sieve. The molecular sieve was then dried and calcined again using the above method. Ca. 2 g of the borosilicate was dispersed.

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16 dish in 16.9 g of PHF-A ^ O ^ hydrosol ($ 8.9 dry solids) and mix thoroughly.'1 milliliters of distilled E ^ O and 1 ml of wife. NH 2 OH was mixed and added to the slurry under intense stirring. The AMS-1B-ΑΙ ^ Ο ^ mixture was placed in a drying oven at 165 ° C for 4 hours. The dried material was again calcined using the aforementioned method. The calcined catalyst was crushed to 30-50 mesh and impregnated with 2 ml of 5% NiiNO 4 · 6H2 ° C e. Stilled H2 O. The catalyst was again dried and activated by a fourth programmed calcination.

The calcined catalyst contained 65% by weight borosilicate and 35% by weight amorphous alumina with approx. 0.5% by weight of the total dry matter as nickel.

1 g of the sieved and activated catalyst was introduced into the micro-reactor and sulfided with H 2 S for 20 minutes at room temperature. The catalyst was then placed under H2 pressure and heated to 316 ° C. After 1 hour, starting material was passed through the microreactor under the following conditions corresponding to a single pass;

Temperature 427 ° C

Pressure 10.5 kg / cm2

HtfHSV 6.28 h-1 H / HC, molar ratio 7

The liquid starting material and the outflows associated with this operation are shown below. Due to the equipment limitations on the sieve unit, only fluid flow analyzes were performed and reported. The light end production over this catalyst was low on the basis of the gas chromatographic analysis performed on the stream of exhaust gas from the unit. The volume of the exhaust gas was determined not to significantly reduce the total liquid yields over the catalyst.

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Liquid Starting Material, Liquid Product, Component Weight - ^ _ Weight - ^ _ Paraffins and Naphthen o, 03 0 and Benzene - 1.51 Toluene, 0.1i / 077 0.26 Ethyl Benzene 19, 71 17.35 Paraxylene - 19.43 Methaxylene 79.80 46.40 Orthoxylene 0.38 14.96 "* V * - 1 *

only approximate values Example III

A solution of 600 g of 1 O, 2.5 g of H 94.3 g of TPABr were added to the original mixture and dissolved. Then, 114.5 g of Ludox-AS (30% by weight of solids) was added to the original liquid mixture with vigorous stirring.

The resulting mixture was introduced into a closed reaction bomb. The bomb was introduced into an oven at 165 ° C for 7 days.

After washing and drying the recovered solids as described in Example I, the crystalline borosilicate was identified as AMS-1B and exhibited an X-ray diffraction pattern similar to that of Table II.

Example IV

A borosilicate of a kind similar to that prepared in Example I was calcined at ca. 593 ° C and then analyzed to determine the total composition. The results are shown below.

18

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Component

SiO 2, weight-9é 94.90 B 2 O 3 1.06

Na2 0.97 Al2 O3 0.057

Fe2 O3 0.029

Volatile materialsx 2,984

Total 100,000

Mole ratio S102 / B203 104.5

Na 2 O / B 2 O 3 1.0

Si02 / A1203 2824, 4

SiO2 / Fe2 O3 8787.0

SiO 2 / (Al 2 O 3 + Fe 2 O 3) 2146, 2 assumed value to produce a total value of 10090.

Other borosilicates were prepared as generally set forth in Example I, except that the content of H3B03 was varied, resulting in the molar ratios of SiO2. After exchange with suitable catalytic materials, the molar ratio SiO 2 / B 2 O 3 generally increased to a value of 80-100 for a borosilicate as prepared, exhibiting a molar ratio SiO 50th

Example V

Three borosilicate materials were prepared in a similar manner to the method described in Example I. The recovered materials were calcined at 535 ° C and then analyzed for boron and silicon as set forth below.

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Molar relationship

Borosilicate Weight% boron SiO 2 B 2 A 0.66 47.4 B 0.64 49.1 C 0.71 44.5

After ion exchange with ammonium acetate, the borosilicate was calcined at 535 ° C. The following was then determined:

Molar relationship

Borosilicate SiO 2 / B 2 O 3 A 75.1 B 71.2 C 64.2

X-ray diffraction analyzes were performed on powder in conjunction with samples of the above borosilicates after being calcined at 538 ° C but before ion exchange. The indicated patterns are shown below for relative intensities (I / IQ) of 10 or greater. The above Table ~ III shows the interplanar distances shown by a strip map for two trials of borosilicate A after calcination at 535 ° C but before ion exchange.

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Table V

(Borosilicate A)

Interplanar distance d (Å) Relative intensity (I / I0). 11.34 38 10.13 30 6.01 14 4.35 11 4.26 14 3.84 100 3.72 52 3.65 31 3.44 14 3.33 16 3.04 16 2.97 22 2.48 11 1.9S 20 1.66 12

Table VI

(Borosilicate 3)

Interplanar distance d (Å) Relative intensity tt / i0) 11.35 41 10.14 31 6.02 15 4 · 26 15 3.84 100 3.72 52 3.65 33 3.44 13 3.32 15 3.04 16 2.97 22 2.48 n 1.99 20 1.66 12

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Table YII

(Borosilicate C)

Interplanar distance d (Å) Relative intensity a / i0> 11.40 33 10.17 29 6.03 13 5.62 10 4.27 14 3.84 100 3.73 51 3.65 30 3.44 13 3.32 16 3.05 16 2.98 21 1.99 19 1.66 12

Claims (12)

Crystalline borosilicate for use as catalyst or catalyst precursor in hydrocarbon conversion, characterized in that it has the following composition in terms of oxide molar ratio: [0.9 + 0.2] (WR2O + (1W) M2 / n0), B2 0 and where 0 <Z <160, which borosilicate exhibits the X-ray diffraction lines listed in Tables I or II of the specification. Crystalline borosilicate according to claim 1, characterized in that M is selected from alkyl ammonium, ammonium, hydrogen, metal cations or mixtures thereof. Crystalline borosilicate according to claim 1, characterized in that M comprises nickel. Crystalline borosilicate according to claim 1, characterized in that M comprises hydrogen, nickel and an alkali metal. Crystalline borosilicate according to claim 1, characterized in that M comprises hydrogen and nickel. Crystalline borosilicate according to claims 1-5, characterized in that Y is in the range of approx. 20 to approx. 500, preferably from ca. 20 to approx. 160th Crystalline borosilicate according to claims 1-6, characterized in that Z is in the range of 0 to approx. 40th Process for the conversion of hydrocarbons, characterized in that, under conversion conditions, this hydrocarbon is contacted with crystalline borosilicate according to claims 1-7, if necessary after the borosilicate has been calcined. A method according to claim 8, characterized in that the conversion is a cracking and that the conversion conditions comprise a temperature in the range of from approx. 260 ° C to approx. 593 ° C, a pressure gauge ranging from about atmospheric pressure to approx. 174 kg / cm and a space velocity for liquid in the range of approx. 0.1 to approx. 75 hours ^. The method according to claim 8, characterized in that the conversion is a hydrocracking and that the conversion conditions comprise a temperature in the range of from approx. 232 ° C to approx. 482 ° C, a hydrogen to hydrocarbon molar ratio in the range of about 1 to approx. 100, a pressure gauge in the range of approx. 1.4 kg / cm to approx. 176 kg / cm and a space velocity for liquid in the range of approx. 0.1 to approx. 50 hours A process according to claim 8, characterized in that the conversion is an isomerization and that the conversion conditions comprise a temperature in the range of from approx. 149 ° C to approx. 538 ° C, a pressure gauge ranging from about atmospheric pressure to approx. 211 kg / cm, a space velocity of liquid in the range of approx. 0.1 to approx. 50 hours 1 and a molar ratio of hydrogen to hydrocarbon in the range of about 0.1 to approx. 35th Process according to Claim 8 for catalytic isomerization of a xylene starting material, characterized in that under isomerization conditions, a temperature in the range of from approx. 121 ° C to approx. 482 ° C, a pressure gauge in the range of approx. 0 kg / cm to approx. 1000 kg / cm, a molar ratio of hydrogen to hydrocarbon in the range of approx. 0 and approx. 20 and a space velocity of liquid in the range of about 1 to approx. 20 hours, this starting material contacts the crystalline borosilicate of claims 1-7.