DE2746790A1 - CRYSTALLINE BORSILICATE (AMS-1B) AND THE METHOD OF USING THEREOF - Google Patents

Description

Case US 733 267/836 403

STANDARD 0IL COMPANY, Chicago, Illinois / USA

Crystalline Borosilicate (AMS-IB) and

Procedure using it

The invention relates to new crystalline borosilicates and their use. In particular, the invention relates to novel crystalline ones Borosilicate molecular sieve materials with catalytic Properties and various hydrocarbon conversion processes using such crystalline borosilicates. A relevant prior art from the patent literature can in U.S. Patent Classes 423-326, 252-458 and 260-668.

In the past it has been shown that zeolitic materials, both natural and synthetic, catalytic properties with respect to a wide variety of hydrocarbons fprocedure. The zeolite materials are orderly porous crystalline aluminosilicates with a defined structure with large and small, interconnected by channels Cavities. The cavity and channels are generally through

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the crystalline material through it in terms of its size uniform and thus allow a selective separation of hydrocarbons. As a result, these materials were used in various cases in the prior art classified as molecular sieves and are in addition to adsorptive selective Process used for certain catalytic properties. The catalytic properties of these materials are also affected to some extent by the size of the molecules which one selectively penetrates the crystal structure lets, presumably, in order to deal with the catalytically active sites within the ordered structure of these materials To be brought into contact.

In general, the term "molecular sieve" encompasses a wide variety of positive ion containing crystalline Materials of both natural and synthetic varieties. They are generally called crystalline aluminosilicates although other crystalline materials are encompassed by this broad definition. The crystalline Alumosilicates are made from the network of tetrahedra of SiO, .- and AlO. moieties in which the silicon and aluminum atoms cross-linked by linking the oxygen atoms are. The electrovalence of the aluminum atom is achieved through the use of a positive ion such as alkali metals or alkaline earth metals, balanced.

Developments in the prior art resulted in the formation of numerous synthetic crystalline materials. Crystalline aluminosilicates are the predominant and are used in the patent literature and in the published journals by letters or other suitable symbols. Examples of these materials are Zeolite A (US Pat. No. 2,882,243) and Zeolite X. (U.S. Patent 2,882,244), Zeolite Y (U.S. Patent 3,130,007), Zeolite ZSM-5 (U.S. Patent 3,702,886), Zeolite ZSM-II (U.S. Patent 3,709,979), Zeolite ZSH-12 (U.S. Patent 3,832,449) and others.

A relevant prior art is the above US Pat. No. 3,702,886, which describes the crystalline aluminosilicate Zeolite ZSM-5 and the process

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ren claimed for its production. This patent is limited to the formation of a zeolite in which aluminum or gallium oxides are present in the crystalline structure along with silicon or germanium oxides. The latter are reacted with the former in a specific ratio to form a class of zeolites referred to as ZSH-5 which is limited to crystalline aluminosilicates or germanates and exhibits a special X-ray diffraction pattern. The foregoing ZSM-II and ZSM-12 patents are similarly limited to crystalline aluminosilicate or gallosilicate or germanates and also have specific x-ray diffraction patterns.

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

U.S. Patent 3,941,871 teaches an organosilicate with very little aluminum in its crystal structure, which has an X-ray diffraction pattern analogous to that of the ZSM-5 composition. These Patent specification is considered to be relevant prior art.

Another relevant prior art includes U.S. Patents 3,329,480 and 3,329,481 relating to "zirconosilicates" and "titanosilicates", respectively.

However, the present invention relates to a new family of stable synthetic crystalline materials which are characterized as boron silicate and identified as AMS-IB with a special X-ray diffraction pattern. The present crystalline AMS-IB borosilicates are formed by reacting a boron salt and a silicon-containing material in a basic medium.

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In a broad embodiment, the invention relates to a crystalline borosilicate having a composition expressed by molar ratios of the oxides, v / ie follows:

0.9 ± 0.02 M ₂ / _n 0: B ₃ O ₃ : YSiO ₂ : ZH ₂ O

where M is at least one cation with a valence η, Y is between 5 and about 500 and Z between 0 and about IGO this borosilicate showing the interplanar distances and associated intensities as shown in the following Table I are given.

In a more preferred embodiment, Y is a value between approx. 40 and approx. 500 and Z has a value zv / i see 0 and about 40.

In a further broad embodiment, the invention relates a crystalline borosilicate having a composition expressed through the oxides, v / ie follows:

0.9 ί 0.2 (WR ₂ O) + (1-Vi) ^M ₂ / _n 0: B ₃ O ₃ : YSiO ₂ : ZK ₂ O

where R is tetraalkylammonium, M is an alkali metal cation, W is greater than 0 and less than or equal to 1, Y is between 5 and 500, Z is between 0 and approximately 160, this being the interplanar distances and associated intensities shows as set out in Table II below.

In a more preferred embodiment, W has a value between approximately 0.6 and approximately 0.9, and Y has a value between approximately 20 and approximately approx. 500 and Z a value between 0 and approx. 40.

In a further embodiment, the invention relates to a method for converting a hydrocarbon that involves bringing it into contact of this hydrocarbon under transformation conditions with a crystalline borosilicate having a composition, expressed in molar ratios of the oxides, as follows:

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0.9 + 0.2 M ₂ / O: B ₃ O ₃ : YSiO ₂ : ZH ₂ O

possesses, v.'orin M at least one cation with a valence η means Y is in the range from about 5 to about 500 and Z is in the range from 0 to about 160, this borosilicate being the interplanar distances and associated intensities as given in Table I below.

In a further embodiment, the invention relates to a process for the catalytic isomerization of a xylene feed, that of contacting this feed under isomerization conditions with a crystalline borosilicate which has a composition expressed by molar ratios possesses the oxide as follows:

0.9 ί 0.2 W _2/0: B ₂ O _3: YSiO _2: ZH ₂ O

where H is at least one cation with a valence η, Y is in the range from approx. 5 to approx. 500 and Z is in the range from approx. 0 to approx. 40, especially this crystalline borosilicate has the interplanar distances and the associated intensities as never described in Table I below are.

The invention relates to a new synthetic crystalline AMS-IB borosilicate. The family of AMS-1B borosilicate crystalline materials has a unique X-ray diffraction pattern as shown in the tables below. The crystalline AMS-IB borosilicates can generally be expressed by the molar ratio of the oxides, as characterized in Equation 1 below:

0.9 ί 0.2 M _2/0: B ₂ O _3: YSiO _2: ZH ₂ O (1)

where II means at least one cation, η the valency of the cation represents, Y is a value from 5 to about 50O and Z for the water present in such a material indicates a value from 0 up to about 160 or more.

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In another case, the present crystalline AMS-IB borosilicate, expressed by the molar ratios of the oxides, for the crystalline, not yet activated at high temperatures or calcined material represented according to Equation 2 below:

0.9 ί 0.2 (WR ₂ O + (1-W) M ₂ / n ⁰⁾ ■ B ₂ ° 3 ^{: YSi0} 2 ^{: ZH} 2 ° ⁽²⁾

where R is tetrapropylammonium, M is at least one cation is, η indicates the valency of the cation, Y means a value from approx. 5 to 500, Z a value from approx. 0 to approx. 160 and W represents a value greater than 0 and less than 1.

The original cation “M” in the above formulations can at least according to techniques known from the prior art partially replaced by ion exchange with other cations. Preferred exchange cations include Tetraalkylanr-noniuin cations, Metal ions, ammonium ions, protons and their mixtures. Particularly preferred cations are those that the crystalline ATIS-IB borosilicate especially for the hydrocarbons make material conversion catalytically active. These materials include hydrogen, seitone, earth metals, aluminum, metals of groups IB, HB and VIII of the periodic table, precious metals, manganese etc. and others from the prior art known catalytically active materials and metals. The catalytically active components can range from approx. 0.05 to approx. 25% by weight of the crystalline AMS-IB borcilicate are present.

Members of the crystalline AMS-IB borosilicates family have a specified and distinct crystalline structure. The noted X-ray diffraction patterns obtained from these materials were obtained using standard powder diffraction techniques. The X-ray diffraction device was a Phillips instrument that used copper K _a radiation together with an AMR focusing manochrometer and a θ-compensating slit, in which its opening varies with the Θ angle.

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The output from the X-ray diffraction machine was translated into a Canberra abstract developed by data processing system and associated programs and with the help of a paper strip and recorded in a tabular expression. The compensation gap and the Canberra summary tend to be the ratios to increase the usable peaks to the disturbing background, while the Pcak intensities at low G angles [high d (R)] and the peak intensities at high Θ-win

no [low d (A) J can be increased. All of the present X-ray patterns given used the above analytical techniques.

The relative intensities reported were calculated as (100 L / L), where I is the intensity of the strongest recorded Represents peaks and I means the actual value standing for the particular interplanar distance.

For the sake of simplicity, the relative intensities have been made arbitrary assigned to the following values:

i / l Assigned intensity

less than 10 = VW

10-19 = W

20-39 = M

40-70 = MS

higher than 70 = VS

A typical X-ray diffraction pattern showing the significant lines with relative intensities of 11 or higher for a crystalline Al ¹ IS-IB borosilicate after calcination at 535 ° C (1000 F) is given in Table I below.

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(X) Table I. 27 ± 0.2 Relative + 0.2 intensity Assigned + 0.07 38 Intensity. Interplanar distance ί 0.05 30th M. d . + 0.05 14th M. 11.3 ± 0.05 11 W. 10.1 ί 0.05 14th W. 6.01 ± 0.05 100 W. 4.35 ί 0.05 52 VS 4.26 ί 0.05 31 MS 3.84 ± 0.05 14th M. 3.72 ί 0.02 16 W. 3.65 ί 0.02 16 W. 3.44 ± 0.02 22nd W. 3.33 ± 0.02 11 M. 3.04 20th V / 2.97 12th M. 2.48 W. 1.99 1.66

An AMS-IB borosilicate that only undergoes mild drying 165 C (as formed material) has an X-ray diffraction pattern with the following significant lines:

(X) Table II Assigned ± 0.2 Relative intensity Interplanar distance ί 0.2 intensity W. d ί 0.05 19th W. 11.4 ί 0.05 17th VS 10.1 ί 0.05 100 MS 3.84 ί 0.05 43 M. 3.73 ί 0.05 26th W. 3.66 ± 0.05 11 W. 3.45 ί 0.02 13th W. 3.32 ί 0.02 12th W. 3.05 ΐ 0.02 16 W. 2.98 10 M. 1.99 20th 1.66

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The paper strip records given in Table I above of the calcined borosilicate showed that this material had the following X-ray diffraction lines:

Table III

Interplanar distance d (A) approach 1 approach 2 * '

1). 13th 10 , 2 7th , 4 9 6th , 70 6th , 41 6th , 02 5 , 71. 5 , 60 5 , 01 / *. , W. / ;. , 3? / (, , 27 4, , 00 3, , 85 3, , 7 2 3, 3, / i> 3, M. 3, , 30 3, 3, O-'f 2, 9 a 2. 86 2, 71 2. CO 2, / eat 2, 39 2, j 2 2, 22nd 2, 00 1, 99 1, 95 1, 91 1, 86 1,

11.2 10.0 7.37 6.70 6.36 5.98 5.67 5.57 5.34 5.0i. 4.67. /

4.25

«, 00

3.85

3, CA 3, Λ6 3, 1.1

3.12 3.04 2.97 2.86 2.71

1, C6
*) This approach ended at 2.71 d (A)

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The crystalline AMS-IB borosilicates can be used in catalytic * cracking and in hydrogen cracking processes or hydrocracking processes. They seem relatively valuable catalytic properties in other petroleum-Refiningverfahren have yu, as in the isomerization of normal paraffins and naphthenes in reforming processes of certain feedstocks in the isomerization of aromatics, especially the isomerization of polyalkyl aromatics, such as o-xylene in the disproportionation of aromatics such as toluene to form mixtures of other more valuable products including benzene, xylene and other higher methyl substituted benzenes and in hydrodealkylation and hydrogen dealkylation, respectively. When used as a catalyst in isomerization processes, where suitable cations are present at ion-exchangeable sites within the crystalline AMS-1B borosilicate, remarkably high selectivities in the formation of the desired isomers are achieved.

The ability of these materials to undergo high temperatures or in the presence of other normally deactivating agents remaining stable makes this class of crystalline materials suitable for high temperature processes including cyclic ones Types of fluidized catalytic cracking or others Process valuable.

The crystalline AMS-IB borosilicates can be used as catalysts or used as adsorbents, whether they are in the alkali metal forms, the ammonium form, the hydrogen form or any other monovalent or polyvalent cation Form. Mixtures of cations can be used. The crystalline AMS-IB borosilicates can also be used in intimate 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, can be used where hydrogenation-dehydrogenation occurs s-mode of action is to be achieved. Such components can in the composition of the cationic · Stelion, which is caused by the designation "M" in the above formulas

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become visible, exchanged, impregnated therein or physically be intimately mixed. In one example, platinum can be deposited on the borcilicate with a platinum metal containing ion will.

The original one linked to the crystalline AMS-IB borosilicate As described above, the cation can be replaced by a large number of other cations according to those known from the prior art Techniques to be replaced. 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, the disclosure of which is incorporated herein by reference should be.

Following an ion exchange, an impregnation or contact with another material in order to introduce catalytically active materials into the borosilicate structure or to apply to these, the material can be washed and then dried at temperatures ranging from about 66 to about 316 C (150 to 600 F). It can then be in the air or under nitrogen or combinations of the two at precisely regulated temperatures in the range of about 260 to about 816 C. (500 to 1500 F) calcined for various periods of time.

Ion exchange at the cationic sites within the crystalline material generally results in a relatively insignificant one Effect on the total X-ray diffraction cm exhibited by the crystalline boric acid material. It can small changes occur in the diffraction pattern at different distances, but the overall pattern remains essentially the same. Small changes in the X-ray diffraction pattern can also be the result of differences in work during manufacture of borosilicate, but the material is still within the general class of crystalline AMS-IB borosilicates, those based on their X-ray diffraction patterns as shown in Tables I, II and III or in the following examples v / earth, are defined.

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The present crystalline borosilicate can be classified as pure borosilicate placed in a catalyst or adsorbent or it can be with various binders or bases depending on the intended method of use be mixed in. In many cases the crystalline borosilicate can be pelletized or extruded. That crystalline borosilicate can be combined with active or inactive materials, synthetic or naturally occurring zeolites and inorganic or organic materials that are used for the Binding of the borosilicate can be used, be combined. Other Well known materials include mixtures of silicon: - dioxide, silicon dioxide-aluminum oxide, aluminum oxide sols, clays, such as bentonite or kaolin, or other binders well known in the art. The crystalline borosilicate can also intimately with porous matrix materials, such as silicon dioxide: yd-zirconium oxide, Silicon dioxide-magnesium oxide, silicon dioxide-aluminum oxide, Silicon oxide-thorium oxide, silicon dioxide-beryllium oxide, Silicon oxide-titanium oxide and three-component compositions, those, in a non-limiting manner, silica-alumina -Thoriurnoxyd and many other axes state of the art known materials include, mixed. The crystalline borosilicate content can vary arbitrarily from a few few to 100 percent of the total end product.

The crystalline AMS-IB borosilicate can generally be prepared by mixing in an aqueous medium of the oxides of boron, sodium or any other alkali metal and silicon and a tetraalkylammonium compound getting produced. The molar ratios of the various reactants can be varied considerably, to give the crystalline AMS-IB borons. In particular can be the reactant molar ratios expressed by the various oxides used to make the borosilicate vary as indicated in Table IV below.

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Table IV Molar ratios

SxO ₂ / b ₂ O ₃ 5-600 (or higher)

R ₄ NV (R ₄ N ⁺ + Na ⁺ ) 0.1-1 OH ~ / siO ₂ 0.01-10

where R is alkyl and preferably propyl. The above amounts can vary in terms of their concentration in the aqueous Medium can be varied. In general, it is preferred that the molar ratio of water to hydroxyl ion be any of varies from about 10 to about 500 or higher.

By simply regulating the amount of boron (as BpO ₃ ) in the reaction mixture, it is possible to vary the SiOp / Bp0 ₃ molar ratio in the end product in the range from about 40 to about 500 or more. In those cases in which it is consciously sought to eliminate aluminum from the borosilicate crystal structure because of its adverse influence on special conversion processes, the molar ratios of SiO ₀ / Al ₀ O ₃ can easily exceed 2000 to 3000. This ratio is generally limited only by the availability of aluminum-free raw materials.

The molar ratio of SiOp / BpO., In the final crystalline product can vary from about 4 to 500 or higher. Currently laboratory manufactures among those described herein general conditions provide SiOp / ß ^ Oo molar ratios, that start at around 40 or lower. Lower ratios can generally be made using manufacturing methods which are still within the scope of the teachings of the invention.

Based on the known properties of mordenite and ferrite aluminosilicates, the present crystalline borosilicates have approx. 4.5 BO ₄ tetrahedra per unit cell with SiO ₂ / B ₂ O ₃ molar ratios of approx

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It appears that there is a single BO ₄ with SiC ^ / ^ O ^ ratios of approx. 500. Above this ratio, there would be numerous unit _{numbers that did not contain a BO 4} tetrahedron, and the resulting crystalline structure could not be considered to be borosilicate. There are no set criteria for expressing at what SiOp / B ^ O ^ molar ratio the crystalline material ceases to be a borosilicate. There seems to be sufficient to assume that B ₂ O ₃ values / at high SiOP (above 1000 or more), the influence of the BO _- is, tetrahedron is somewhat reduced in the crystalline structure and no longer addressed the crystalline material as borosilicate .

Under carefully controlled conditions using the above indications, the crystalline AMS-IB borosilicate of the present invention is formed. Typical reaction conditions include heating the reactants to a temperature anywhere within the range of about 90 to about 250 ° C or higher for any period of time from about a few hours to a few weeks or more. Preferred temperature ranges are within about 150 to about 180 ° C. for the time required for the crystalline AMS-IB borosilicate to precipitate. Particularly preferred conditions include a gate
7 days,

a temperature of approx. 165 C for a period of approx.

The material so formed can be separated and used according to well known methods Methods such as filtering can be obtained. This material can be mild for a few hours to a few days dried at varying temperatures to form a dry cake which in turn becomes a powder or chopped into small particles and extruded, pelletized, or molded into shapes suitable for the intended use can be. Typically, the material produced by mild drying conditions contains the tetraalkyl anunonium ion within the solid mass, and subsequent activation or calcination is required if it is desirable to have this material out of the formed product

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to remove.

Typically, the high temperature calcination conditions are at temperatures of approx. 427 to approx. 871 C (.800 to IGOO ⁰ F) or higher. Extreme calcination temperatures can prove to be detrimental to the crystal structure or destroy it completely. In general, there is no need to go beyond about 927 ° C (17OO ° F) to remove the tetraalkylammonium cation from the initially formed crystalline material.

Used the crystalline AMS-IB borosilicate as a hydrocracking catalyst used, the hydrocrack stock batches can be used at temperatures of approx. 2G0 to approx. 454 ° C (500 to 850 ° P) or higher are passed over the catalyst, known holing ratios of hydrocarbon to hydrogen and varying Pressures from a multiple of 0.07 at to a multiple of 70.3 at (a few up to many thousands of pounds per square inch) or higher used. The liquid hourly Raung resistance and other process parameters can be set according to the known teachings of the prior art can be varied.

One uses the borosilicate for a fluidized catalytic Cracking processes, well known operating conditions including temperatures of about 260 to about 649 ° C can be used (500 to 1200 F) in the reaction zone and temperatures of about 427 to about 704 ° C (800 to 1300 ° F) in the regeneration zone. Contact times, deliveries and others Procedure conditions are known from the prior art.

The specified crystalline ATIS-1B borosilicate is also available as Reforming catalyst suitable, which skornponen th with the appropriate hydrogenation in well-known reforming conditions including Temperatures from approximately 260 to 566 ° C (500 to 1050 ° F) or higher, pressures from a multiple of 0.07 atmospheres up to 21.1 to 70.3 atu (a few up to 300 to 1000 psig) and liquid hourly space velocities and hydrocarbon-to-

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Hydrogen molar ratios in accordance with those from known in the art for the reforming process be used.

The present composition is also for the hydrocarbon Isomerization and disproportionation suitable. she is especially for the liquid or gas phase isomerization of xylenes and especially for the isomerization of mixed ones Xylenes can be used for predominantly p-xylene products. The isomerization conditions include temperatures of approximately 93 up to about 538 ° C (200 to 1000 ° F), hydrogen to carbon molar ratios from approx. 0 to approx. 20 and liquid hourly space velocities in the range from approx. 0.0.1 to approx. The choice of which to apply to the crystalline AMS-IB borosilicate catalytically active metals can be made from those well known in the art. Nickel seems for the isomerization of aromatics to be particularly suitable.

The present AHS-IB crystalline dorsilicate can also as an adsorbent for the selective adsorption of special Isomers or hydrocarbons are generally used from a liquid or vapor stream.

The following examples illustrate the invention.

example 1

A crystalline AMS-IB borosilicate was produced by adding 0.25 g of H ₃ BO ₃ and 1.6 g of NaOH in GO g of distilled H _? 0 dissolved »Then 9.4 g of tetra-n-propylaminonium bromide (TPABr) were added and dissolved again. Finally, 12.7 g of Ludox-AS (30 % solids) (aqueous colloidal silica sol) were added with vigorous stirring. The addition of Ludox gave a thick, gelatinous, milky solution. This solution was introduced into a reaction boom and this closed. The bomb was placed in a 165 ^° C. oven and left there for 7 days. At the end of this time it was opened and its contents filtered. The crystalline material obtained was ashed with copious amounts of water and then dried at 165 ° C. in a compressed air oven. The GE-

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Dried material was found to be crystalline by X-ray diffraction Material with a typical AHS-1B pattern with 100% crystallinity identified. The yield was approx. 2 g.

Example 2

In this example crystalline ASM-IB borosilicate from Example 1 used to prepare a catalyst with isomerization properties to build.

The material of Example 1 was calcined for 4 hours at 535 ° C (1100 ⁰ F) in air to remove the organic base to. The calcined sieve was once with a solution of 20 g of TJH ₄ KO ₃ in 200 ml of H _? 0 and then exchanged a second time with 20 g of NH ₄ OAc in 200 ml of H ₂ O at 87.8 ⁰ C (190 ° F) for 2 hours. The exchanged borosilicate was dried and left in the air for 4 hours. Heating to 482 ° C (900 ° F) and calcined dried to give the borosilicate held for 4 hours at 482 ° C (900 ° F) and then for 4 hours at 3 7.8 ° C (100 ⁰ F) was cooled. The calcined material was exchanged with 100 ml of a 5% Ni (NO ₃ K-6HpO solution for 2 hours at 87, C ⁰ C (190 ⁰ F). The sieve was gcwa-

see, and the Ni was completely washed out of the sieve. The sieve was dried and calcined again using the above procedure. Disperse 2 grams of borosilicate in 16.9 grams of PHF-Al ^ hydrosol (8.9% solids) and mix thoroughly. 1 ml of distilled water and 1 ml of kona were mixed. NH ₄ OH and added this to the slurry with vigorous mixing. The AMS-IB-AlpO ^ mixture was placed in a drying oven at 165 ° C. for 4 hours. The dried material was recalcined using the above procedure. The calcined catalyst was crushed to give a particle size of 0.297 to 0.55 mm (30 to 50 mesh) and impregnated with 2 ml of a 5% solution of Ni (NO ₃ ) p * 6H ₂ O in distilled H ₃ O. The catalyst was dried again and activated by a fourth calcination.

The calcined catalyst contained 65% by weight borosilicate and 35% by weight amorphous aluminum oxide with about 0.5% by weight

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Total solids as nickel.

1 g of the sieved and activated catalyst was introduced into the microreactor and sulphurised with HS for 20 minutes at room temperature. The catalyst was then brought under H ₂ pressure and heated to 316 ° C (600 ° F). After one hour, the feed was passed through the microreactor under the following flow conditions:

Temperature 427 ° C (800 ° F)

Pressure 10.5 atg (150 psig)

WHSV 6.28 hours " ¹

H / HC molar ratio 7

The liquid feed and effluents for this process are given below. Because of the device limitations at the separation unit only the analysis on liquid streams was carried out and reported. The formation of easy End product over this catalyst was due to the gas chronograph Analysis performed on the exhaust gas stream from the unit, goring. It was found that the volume of the exhaust gas, the liquid volume flows over the catalytic converter not noticeably diminished.

Components Liquid feed Liquid product Weight% Weight S-V, Paraffins and Naphthenes 0.03 0.08 benzene - 1.51 toluene 0.077 0.26 Ethylbenzene 19.71 17.35 p-xylene - 19.43 m-xylene 79.80 46.40 o-xylene O, 38 14.96 C ₉ ⁺ *> - 1.0 *)

Only approximate values

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Example 3

A solution of 600 g of HO, 2.5 g of H ₃ BO ₃ and 7.5 g of NaOH was prepared. 94.3 g of TPABr were added to the original mixture and dissolved. Then 114.5 grams of Ludox-AS (30 wt% solids) was added to the original liquid mixture with vigorous stirring.

The obtained mixture was placed in a reaction bomb and these closed. The bomb was placed in an oven at 165 ° C for 7 days.

After washing and drying the solids obtained as described in Example 1, the crystalline borosilicate was found to be AMS-IB identified and showed an X-ray diffraction pattern similar that of Table II.

at spi. el 4

A borosilicate similar to that prepared in Example was calcined at about 77.3 ° C (HOO ⁰ F) and then analyzed to determine its overall composition. The results are given below.

Components

SiO,% by weight

Al ₂ O ₃
Fe ₂ O ₃

total volatile components

Molar ratios

94.90 1.06 0.97 0.057 O, O29 2.984 100.000

104.5 1.0

2824.4 8787.0 2146.2

Assumed value to give a total of 100%,

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₂₂₃
SiO ₀ Al ₂ O ₃

Other borosilicate were prepared as described in general in Example 1, but the H ₃ BO ₄ -OcI-IaIt varies v.'urdc, v / a :: to SiO _? / B "O_ molar ratios which, before the borosilicate was calcined or exchanged, varied from 50 to IGO or more. After exchanging with appropriate catalytic. Materials, in general, the SiO ^ / ^ O ^ Hol ratio increased to a word of 80 to 100 for a borosilicate as made when it had a SiOp / BpO-j molar ratio of about 50.

Example 5

Three borosilicate materials were produced analogously to the method described in Example 1. The materials obtained were calcined at 535'c (1000 F) and then for the Boron and silicon analyzed as indicated below.

Borosilicate weight% boron molar ratio

47.4 49.1 44.5

A. 0.66 B. 0.64 C. 0.71

After ion exchange with ammonium chloride, the borosilicate became

carried out at 535 ° C for about h:

at 535 C approx. The following provisions were then made

Mole ratio Borosilicate

75 ,1 71 , 2 64 , 2

A B C

The powder X-ray diffraction analysis was performed on samples of the above borosilicates, after they had been calcined at 535 ° C (1000 ⁰ F), but before the ion exchange. The perks are shown below for relative intensities (l / l) of 10 or higher. The vorstohemde Table III shows the intcrplanaren distances, as it were be taken for two borosilicate batches A after calcination at 535 ° C (1000 ⁰ F), but before the ion exchange, a paper strip.

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Table V
(Dorsilicate Λ)
Interplanar / Ojstand d (Λ) Relative intensity (I / I)

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 1.99 20

1.66 12

Table VI

(Borsalient B)
Interplanar distance d (Λ) Relative intensity (l / l)

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 ii

1.99 20

1, G6 12

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Table VII

(Borosilicate C)

Interplanar distance d (Λ) Relative intensity

11.40 33 10.17 29 6.03 13th 5.62 10 4.27 14th 3.84 100 3.73 51 3.65 30th 3.44 13th 3.32 16 3.05 16 2.98 21 1.99 19th 1.66 12th

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Claims (1)

P a t e n t a n languages 1. K.rictallinos borosilicate with a composition expressed by the molar ratio of the oxides as follows: OO "^ Π 0 M / C \ · Ti C) · VCl Π · * 7TI Π where H is at least one cation with a VJertigho '. i; η means that Y. is between 4 and approx. 500 and Z is between 0 and approx. 160, this borosilicate having the following Ron ¹ diffraction lines : Intcrplanar Distance Relative intensity 11.3 ± 0.2 38 10.1 ί 0.2 30 6.01-0.07 14 4.35 ί 0.05 11 4.26 ί 0.05 14 3.84 0.05 100 3.72 + 0.05 52 3.65 + 0.05 31 3.44 ΐ 0.05 14 3.33 ± 0.05 16 3.04 ί Ο, Ο5 16 2.97 ί 0.02 22 2.48 ± 0.02 11 1.99 ± 0.02 20 1.66 ί 0.02 12 2. Composition according to claim 1, characterized in that Y has a value in the range from about 20 to about 500, 3. Composition according to claim 1, characterized in that M is selected from the group consisting of alkylammonium, ammonium, hydrogen, metal cations or their Mixtures. 809816/1001 ORIGINAL INSPECTED 4.: 2η :: - αΐηΓΤΐο: -Γ; · "^. ·" .Υηπ gop.l'ß claim λ, characterized; oil. That Vi includes nickel. 5. ZuTw; :: nr: cn:; ': tr, uricj gc-nut claim 1, characterized in that Κ includes Uasscrstoif, nickel and an alkali metal. G. Composition according to claim 1, characterized in that Vi comprises hydrogen and nickel. 7. Composition according to claim 1, characterized in that that Y is in the range from about 40 to about T> 00. C. The composition of claim 7, characterized in that Z ranges from 0 to about 40. 9. Composition according to claim 1, characterized in that that Z ranges from 0 to about 40. 10. The composition according to claim 9, characterized in that that Y ranges from about 20 to about IGO. 11. The composition of claim 1, characterized in that Y is between about 20 and about 200 and Z is between 0 and around 40. 12. Composition according to claim 1, characterized in that that the borosilicate has the following X-ray diffraction lines having: ο Interplanar distance d (A) 11.3 5.71 4.00 3.30 2.60 1.99 10.2 5.60 3.85 3.14 2.48 1.95 7.49 5.01 3.72 3.04 2.39 1.91 6.70 4.62 3.64 2.98 2.32 1.86 6.41 4.37 3.48 2.86 2.22 1.75 6.02 4.27 3.44 2.71 2.00 1.66 809816/1001 BAD ORIGINAL 2 * - 3 13th Kri. ';. to 11.ines ltorsilicr.t with round assembly -pressed by the molar ratios of the oxides, as follows 0.9 ± 0.2 ^B 2 ° 3 ^YSi0 where M represents at least one cation with a valence η, Y between 4 and approx. 500 and Z between 0 and about 160, v / obei this boron si Ii cat the following X-ray diffraction lines and associated intensities have: Intplanar distance Relative Assigned there) intensity intensity 11.3 ± 0.2 38 M. 10.1 ± 0.2 30th M. 6.01 + 0.07 14th W. 4.35 ± 0.05 11 W. 4.26 + 0.05 14th W. 3.84 ± 0.05 100 VS 3.72 0.05 52 MS 3.65 i 0.05 31 M. 3.44 + 0.05 14th W. 3.33 ± 0.05 16 W. 3.04 + 0.05 16 W. 2.97 t 0.02 22nd M. 2.48 + 0.02 11 W. 1.99 ± 0.02 20th M. 1.66 + 0.02 12th W. 809816/1001 14. Composition according to claim 13, characterized in that that Y has a value in the range from about 4 to about 200. 15. The composition according to claim 13, characterized in that M is selected from the group consisting of alkyl ornmonium, ammonium, hydrogen, metal cations or their! • lisch u ng s. 16. The composition of claim 13, characterized in that M comprises nickel. 17. The composition of claim 13, characterized in that M comprises hydrogen, nickel and an alkali metal. 18. The composition of claim 13, characterized in that M comprises hydrogen and nickel. 19. The composition of claim 13, characterized in that Y ranges from about 4 to about 160. 20. Composition according to claim 19, characterized in that Z is in the range from 0 to about 40. 21. Composition according to claim 13, characterized in that Z is in the range from 0 to about 40. 22. The composition of claim 21, characterized in that Y ranges from about 50 to about 160. 23. The composition of claim 13, characterized in that Y is between about 80 and about 120 and Z is between 0 and approx. 40 lies. 24. The composition of claim 13, characterized in that Y is between about 20 and about 500 and Z is between 0 and about 40. 809816/1001 25. Composition according to claim 24, characterized in that that Y is between about 40 and about 500. 26. Crystalline borosilicate having the following composition, expressed by the oxides: 0.9 ί 0.2 (WR ₂ O + (1-W) M _2/0): B ₂ O _3: YSiO _2: ZH ₂ O where R is tetrapropylammonium, M is an alkali metal cation represents, W is greater than 0 and less than or equal to, Y is between about 4 and about 500, Z is between 0 and 160, this borosilicate essentially having the following X-ray diffraction lines and associated intensities having: Interplanar distance (X) Relative Assigned d + 0.2 intensity intensity 11.4 ί 0.2 19th W. 10.1 ί 0.05 17th W. 3.84 ± 0.05 100 VS 3.73 ± 0.05 43 MS 3.66 ± 0.05 26th M. 3.45 ί 0.05 11 ν; 3.32 ± 0.05 13th W. 3.05 ± 0.02 12th W. 2.98 ί 0.02 16 W. 1.99 ί 0.02 10 W. 1.66 20th M. 27. Composition according to claim 26, characterized in that Y has a value in the range from about 20 to about 500. 28. A composition formed by contacting the composition of claim 26 at a temperature im
Range from approx. 260 to approx. 816 ° C (500 to 1500 ⁰ F ¹ ). 809816/1001 - »v 29. A method for converting a hydrocarbon, thereby characterized in that this hydrocarbon under conversion conditions with a crystalline borosilicate having the following composition expressed in holing conditions of the oxides, has: 0.9 ± 0.2 Vi ^B 2 ° 3 ^YSi0 2 ^ZH 2 ° where M represents at least one cation with a valence η, Y is in the range from approx. 4 to approx. 500 and 2 is in the range from 0 to approx. 160, this borosilicate having the following X-ray diffraction lines and associated intensities: Interplanar distance Relative Assigned there) intensity intensity 11.3 ± 0.2 38 M. 10.1 ± 0.2 30th M. 6.01 + 0.07 14th W. 4.35 0.05 11 W. 4.26 + 0.05 14th W. 3.84 ± 0.05 100 VS 3.72 0.05 52 MS 3.65 ± 0.05 31 M. 3.44 0.05 14th W. 3.33 0.05 16 W. 3.04 ± 0.05 16 W. 2.97 t 0.02 22nd M. 2.48 0.02 11 W. 1.99 ± 0.02 20th M. 1.66 + 0.02 12th W. 30. The method according to claim 29, characterized in that Y is in the range from 20 to about 500. 809816/1001 31. The method according to claim 29, characterized in that Y ranges from about 20 to about 500 and Z ranges from 0 to about 40. 32. The method according to claim 29, characterized in that Y ranges from about 400 to about 500 and Z ranges from 0 to about 40. 33. The method according to claim 29, characterized in that the borosilicate has the following X-ray diffraction lines and has relative intensities: Interplanar distance d (A) 11.3 ± 10.1 ± 6.01 + 4.35 ± 4.26 ± 3.84 ± 3.72 ί 3.65 ± 3.44 ± 3.33 ί 3.04 ± 2.97 ί 2.48 t 1.99 ± 1.66 + 0.2 0.2 0.07 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.02 0.02 0.02 0.02 Relative intensity 38 30 14 11 14 100 52 31 14 16 16 22 11 20 12 34. The method according to claim 29, characterized in that the conversion is a cracking and the conversion conditions temperatures in the range of about 260 ° C to about 593 ° C (500 ° F to HOO ⁰ F), a pressure in the range of about Atmospheric pressure to about 176 atmospheres (2500 psig) and a liquid hourly space velocity in the range of about 0.1 to 609816/1001 include approx. 75. 35. The method according to claim 29, characterized in that the conversion is a hydrocracking process or a hydrogen crack process and that the conversion conditions a temperature in the range of about 232 to about 482 ° C (450 to 900 ° P), a molar ratio of hydrogen to hydrocarbon in the range from approx. 1 to approx. 100, a pressure in the range from approx. 1.41 atmospheres to approx. 176 atmospheres (20 to 2500 psig) and a liquid hourly space velocity in the range of about 0.1 to about 50. 36. The method according to claim 29, characterized in that the conversion is an isomerization and the conversion A temperature in the range of approx. 149 to approx. 538 ° C (300 to 1000 ° F), a pressure in the range of approx. Atmospheric pressure up to approx. 211 atü (3000 psig), a liquid hourly space velocity in the range from about 0.1 to about 50 and a molar ratio of hydrogen to hydrocarbon in the range of about 0.1 to about 35. 37. Process for the catalytic isomerization of a xylene feed; characterized in that the xylene charge brings into contact under isothermalization conditions with a crystalline borosilicate which has a composition expressed by the molar ratios of the oxides as follows: 0.9 ± 0.2 M _2/0: B ₃ O _3: YSiO _3: ZH ₃ O where M is at least one cation with a valence η, Y is in the range from about 5 to about 500 and Z is in the range from 0 to about 160, this being crystalline Borosilicate has the following X-ray diffraction lines and associated intensities: 809816/1001 Interplanar distance d d) 11.3 ± ΙΟ, Ι ± 6, Ol + 4.35 ± 4.26 ± 3.84 ± 3.72 ί 3.65 ± 3.44 ± 3.33 ± 3.04 + 2.97 2.48 1.99 ± 1.66 + O, 2 O, 2 O, 07 0.05 O, O5 O, O5 0.05 0.05 O, O5 0.05 O, O5 O, O2 O, O2 0.02 O, O2 Relative intensity 38 30 14 11 14 IOO 52 31 14 16 16 22 11 20 12 Assigned intensity M.
M. VS HS 38. The method according to claim 37, characterized in that Y is in the range from about 20 to about 500 and Z in the range from 0 to about 40. 39. The method according to claim 37, characterized in that the isomerization conditions have a temperature in the range from about 121 to about 482 ° C (250 to 900 ° F), a pressure in the range of about 0 to about 70.3 atmospheres (0 to about 1000 psig), a molar ratio of hydrogen to hydrocarbon in the range from about 0 to about 20 and an hourly by weight Space velocity in the range of about 1 to 20 include. 40. The method according to claim 39, characterized in that Y is in the range from about 40 to about 500 and Z is in the range from about 0 to about 40. 809816/1001