JPH05500650A - Low Aluminum Boron Beta Zeolite - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Low Aluminum Boron Beta Zeolite Background of the Invention Natural and synthetic zeolite crystalline aluminosilicates are useful as catalysts and adsorbents. be. These aluminosilicates have a well-defined crystal structure as shown by X-ray diffraction. do.

This crystal structure forms cavities and pores that are characteristic of different species. each crystalline alumino The adsorption and catalytic properties of silicates are determined in part by the dimensions of their pores and cavities. . Thus, the use of a particular seolide in a particular application may be, at least in part, Depends on its crystal structure.

Because of their unique molecular sieving properties as well as their catalytic properties, crystalline aluminosilicates are It is particularly useful in applications such as gas drying and separation for hydrocarbon conversion. many different Crystalline aluminosilicates and silicates are disclosed, gas separation and drying, carbon New zeolites with desirable properties for hydrogenation and chemical conversion and other applications Silicic acid is still needed.

Crystalline aluminosilicates are usually alkali or alkaline earth metal oxides, 77 Produced from an aqueous reaction mixture containing noca and alumina. "Nitrogen zeolite" is usually an organic membrane agent, usually a reaction containing a nitrogen-containing organic cation. manufactured from a mixture of By changing the synthesis conditions and the composition of the reaction mixture. Thus, the same templating agent can be used to form different zeolites.

Zeolite 5sz-ts N,N,N-trimethylcyclopene used in the production of molecular sieves The use of antitylammonium iodide is disclosed in U.S. Pat. No. 4,610.854. Re.

I-Azoniaspiro[4,4) was used in the production of a molecular sieve called “Losod”. Use of nylbromide and N,N,N-trimethylneopentylammonium iodide The use is He1v.

Chim, Acta (1974); vol, 57. p, 1533 (W.

5ieber and W. M. Meier): referred to as “NU-3”. A European patent has been published on the use of quinuclidinium compounds to produce heptaolides Disclosed in No. 40016: 1.4 for the production of zeolite 5SZ-16 molecular sieves -Use of di(l-azoniabicyclo(2,2,2)octane) lower alkyl compound The heptaolide 5SZ-13 molecule is disclosed in U.S. Pat. No. 4,508,837. The use of N,N,N-trialkyl-1-adamantamine in the manufacture of sieves is a US patent. No. 4,544.538 and U.S. Pat. No. 4.66 for 5SZ-24. No. 5,110.

Beta zeolite is disclosed in U.S. Patent No. 3.308.069 and Re28.341. This zeolite is a well-known synthetic crystalline aluminosilicate described in Further details are mentioned regarding its preparation and properties.

Synthetically, olide crystalline borosilicates are useful as catalysts. Contains skeleton boron Processes for making high silica content zeolites having the structure are known and described in U.S. Pat. No. 4,269. No. 813. The amount of boron normally contained in heptaolide is in the form of zeolite This can be varied by incorporating different amounts of borate into the formulation solution.

U.S. Pat. No. 4,788,169 describes a method for making beta zeolite containing boron. Describe it. According to the analysis presented therein, this boron beta zeolite has 7000 Contains ppm of aluminum.

European Patent Application No. 188.913 contains aluminum containing up to 0.05% by weight. Claims compositions for various mesoporous boron-containing zeolites having an amount of .

Summary of the invention The applicant has discovered that some "crystalline borosilicate molecular sieves" with unique properties, herein Referred to as “low aluminum boron beta zeolite” or simply “(B)beta” I prepared the following. Thus, according to the present invention, the zeolite composition, (B) Takara is served. Beneficial uses have also been discovered.

(B) Beta is greater than about 10:1; silicon oxide, germanium oxide and the like; oxides selected from mixtures of boron oxide or aluminum oxide, gallium oxide or a mixture of iron oxide and boron oxide; Maybe the amount of aluminum is 0. 0% by weight or less and the following 1(a) It has the X-ray diffraction lines in the table. Also using the novel method disclosed here, aluminum It is possible to produce boron beta zeolite that does not contain Ni. Contained in zeolite The amount of aluminum present in the silica source simply depends on the aluminum impurities present in the silica source. .

Furthermore, this zeolite is synthesized and in anhydrous state, with respect to the molar ratio of oxides: It has the following composition: (1,0 to 5.0)Q20・(0,1 to 2.0) LO: LO3 (] greater than 0) YO2, where M is an alkali metal cation , germanium and mixtures thereof, W is selected from boron and Y is selected from silicon. Q is selected from diquaternary ammonium, germanium and mixtures thereof; ion or diquaternary ammonium cation and tetraethylammonium cation It is a mixture of on.

(B) Beta zeolite preferably typically ranges from 10:1 to about 100:1 with a silica:boria ratio of Zeolite is treated with a chelating agent or acid to produce zeolite. Even higher molar ratios are obtained by extracting boron from the light lattice. Halogen Also silica:bonide using silicon nitride and carbon halide and other similar compounds. The real molar ratio can be increased. Boron in the crystalline network is also aluminium, gallium Or it can be replaced with iron. A method for incorporating aluminum is described in U.S. Pat. No. 4,559. No. 315 and No. 4,550.092, each of which is incorporated herein by reference. Enter.

A method for making boron beta zeolite is described in U.S. Patent No. 4.788.169. . 7000 ppm aluminum using tetraethylammonium template zeolite containing nium is produced. However, U.S. Pat. 1000 ppffl or less using the method described in No. 169 of Boron beta zeolite containing aluminum cannot be produced. Furthermore, synthesized boron Low aluminum by replacing aluminum with boron in the beta zeolite structure Unable to produce nium boron beta zeolite. low aluminum boron betase Successful production of olite is achieved using the novel synthetic method described here. is necessary.

According to one embodiment of the present invention, the source of diquaternary ammonium ions is selected from boron oxide. selected oxides and selected from silicon oxide, germanium oxide and mixtures thereof and which, with respect to the molar ratio of the oxides, fall within the following ranges: YO□/W2O3,10.1 to 100:I, where Y is silicon, selected from germanium and mixtures thereof, W is selected from boron, and and Q is a diquaternary ammonium ion, preparing an aqueous mixture, zeolite Keep this mixture at a temperature of at least 100°C until crystals form. and (B) a method for producing beta zeolite, comprising recovering the crystals. or served.

Among other factors, the present invention uses diquaternary ammonium templates to reduce aluminum It is based on the discovery that it is possible to produce nium boron zeolite. This zeolite The structure of the tetraethylammonium template is disclosed in U.S. Pat. No. 4,788,169. The same boron beta zeolite structure as that synthesized using the rate.

Surprisingly, the amount of aluminum incorporated into this structure is A template different from the tetraethylammonium template used in No. 88.169. It was discovered that this can be reduced by using plates. Also, he has a particularly high talent. This zeolite has an unexpectedly high degree of carbonization, including its resistant reforming properties. It was also discovered to have hydrogen conversion properties.

Detailed description of the invention The synthesized (B) beta zeolite has an X-ray powder diffraction pattern or the characteristic curve below. It has a crystal structure showing in.

18, 40 4.82 8 Very wide 21.44 4.14 18 22.53’3.95 100 Representative (B) beta borosilicate and boroaluminosilicate zeolites are listed below. It has the X-ray recovery patterns shown in Tables 2 and 4. The d-spacing is shown in Table 8. Showing bone replacement. Calcined (B) betas are representative as shown in Table 1(b). Has a pattern.

18, 50 4.80 3 Very wide 21, 83 4.07 15 22.87 3.89 100 wide 27, 38 3.26 10 X-ray powder diffraction patterns were measured by standard techniques. Radiation Alpha/Copper Scintillation counter that is dual and has a stop-chart pen recorder – using a spectrometer. Pi as a function of 2θ, which is θ or the Black angle. The peak height I and position were read from the spectrometer. Relative from these measurements Intensity 1001/(o, where lO is the intensity (peak height) of the strongest peak , and d related to the lattice spacing in Angstroms corresponding to the recorded peaks. /n can be calculated. The X-ray diffraction pattern in Table 1 (a) is (B) beta zeolite It is a characteristic of The metals or other cations present in the zeolite can be replaced with various other cations. Does zeolite made by exchanging with , there is a slight shift in the lattice spacing and a slight variation in the relative intensity. in the diffraction pattern Small variations in It also results from variations in the silica to boria molar ratio. Calcination also causes a slight change in the X-ray diffraction pattern. cause a shift in Despite these variations, the fundamental crystal lattice structure remains unchanged. It remains unchanged.

Suitably the source of alkali metal borate is bis(1-azonia, bicyclo(2,2 ,2) Octane-α,ω-alkane diquaternary ammonium ion and silicon or gel (B) Betase from an aqueous solution containing manium oxide or a mixture of these two. Olite can be prepared. This reaction mixture has a composition that falls within the following range in terms of molar ratios: YO□/W2O310-2003O-10001(/YO20,10 -1,00,25-0,50Q/YO20,05-0,500,25-0,35 M+/YO20,05-0,300,05-0,10H20/YO215-30 025-60Q/Q+M+ 0.30-0.90 0.60-0.80 here Q is mixed with diquaternary ammonium ion or te)-ramethylammonium cation. compound, Y is silicon, germanium or both and W is boron . M is an alkali metal, preferably sodium.

The organic compound that acts as a source of quaternary ammonium ions used is hydroxide. It is possible to provide ions.

When using quaternary ammonium hydroxide compounds as templates, alkaline When an excess of the compound is present compared to the amount of potassium metal hydroxide, a purer form ( It has also been found that B) can be prepared overnight.

Bis(1-abuniabicycloC2,2゜2)octane-α',ω of the crystallization mixture - The alkanedi quaternary ionic component Q is derived from a quaternary ammonium compound. Like In other words, this diquaternary ammonium ion has the formula: derived from the compound.

This quaternary ammonium compound is prepared by methods known to those skilled in the art, examples of which include See US Pat. No. 4,508,837.

Prepare the reaction mixture using standard zeolite preparation techniques. for reaction mixture Sources of boron are borosilicate glasses and most especially other reactive borates and borosilicate glasses. Contains uric acid ester. Typical sources of silicon oxide are silicates and silica hydrogels , silicic acid, colloidal silica, tetraalkyl orthosilicate, and silicate Including Kint.

The reaction mixture is maintained at an elevated temperature until zeolite crystals form. representatively The temperature during this hydrothermal crystallization step is from about 140 to about 200°C, preferably about 150°C. to about 170°C and most preferably from about 135 to about 165°C. crystal The curing time is typically greater than one day and preferably from about 3 to about 7 days.

under pressure and usually in an autoclave so that the reaction mixture is subjected to natural pressure This hydrothermal crystallization is carried out.

Once zeolide crystals are formed, standard mechanical separation techniques such as filtration Separate the solid product from the reaction mixture. The crystals are washed with water and then for 8 to 24 hours. , for example, (B) beta zeola as synthesized by drying at 90 to 150″C. Obtain light crystals. This drying step can be carried out at atmospheric or sub-atmospheric pressure.

During this hydrothermal crystallization step, (B) beta crystals are optionally nucleated from the reaction mixture; I'm coming. This reaction mixture is also inoculated with (B) beta crystals for crystallization. to minimize the formation of undesirable aluminosilicate contaminants. I can do that.

This synthetic (B) beta zeolite can be used as synthesized or can be treated with heat. (calcination). Usually, alkali metal cations are removed by ion exchange and this It may be desirable to replace it with hydrogen, ammonium or any desired metal. this The zeolite can be leached with a chelating agent, e.g. EDTA or dilute acid solution to increase the shear strength. The boria molar ratio can be increased. For applications where hydrogenation-dehydrogenation is desired, water Elements such as tungsten, vanadium, molybdenum, rhenium, nickel metal, cobalt, chromium, manganese or precious metals such as palladium or platinum. This zeolite can be used in close combinations. Typical substitution cations are metal ions. metals, such as rare earths, Group 11A, and Group V metals, and mixtures thereof. Including compounds. Among the substituted metal cations, rare earths, Mn, Ca, Mg.

Zn, Cd, Pt, Pd, Ni, Co, Ti, A1. Sn, Cations of metals such as Fe and Co are particularly suitable.

Hydrogen, ammonium and metal components can be exchanged into the heptaolide. This Zeo again The metal can be impregnated with light, or the metal can be impregnated with zeolite using standard methods known to those skilled in the art. can be completely physically mixed with and the desired gold as ions in the reaction mixture. By allowing metals to exist, metals can be occluded in the crystal lattice, from which (B) beta Prepare zeolite.

Typical ion exchange techniques include solutions containing the desired substituted cations or salts of the cations. and a synthetic zeolite. Although a wide variety of salts can be used, salt Particularly preferred are halides and other halides, nitrates, and sulfates. Typical i On-exchange technology is described in U.S. Pat. No. 3.140.253, disclosed in a wide variety of patents.

Following contact with a salt solution of the desired substituted cation, this heptaolide is typically washed with water. and dried at temperatures ranging from 650°C to about 315°C. After washing, 1 or from about 200 to 820°C for a period ranging from 48 hours or more. Especially in hydrocarbon conversion processes by calcining zeolites in air or inert gas at temperatures ranging from It can produce catalytically active products useful for.

Regardless of the cations present in the synthesized form of the heptaolide, the zeolite group The spatial arrangement of the atoms forming the essential crystal lattice remains essentially unchanged. Click On exchange has little, if any, effect on the zeolite lattice structure.

Beta borosilicate and metallo borosilicate can be formed into a wide variety of physical forms. Can be done. Generally speaking, zeolites are powders, particles or shaped articles, e.g. Enough to pass through Tush (Tyler) and stay in 400 Mesh (Tyler) It is a form of extract with a large particle size.

If the catalyst is formed, e.g. by extrusion, with an organic binder, borosilicate The silicate is extruded before drying, or dried or partially dried and then extruded It will be done.

This zeolite is compatible with other materials that are resistant to the temperatures and other conditions used in organic conversion processes. It can be combined with This substrate consists of active and inactive substances and synthetic or naturally occurring zeola. metal oxides, and inorganic materials such as clays, torsions, and metal oxides. this latter is naturally occurring or in the form of a gelatinous precipitate, sol or gel, and contains silica and gold. Contains a mixture of genus oxides. In conjunction with, i.e. in combination with, synthetic zeolites The use of active materials tends to improve conversion and catalyst selectivity in certain organic conversion steps. direction. Inert substances are preferred as diluents to control the amount of conversion in a given process. and therefore can be used without other means to control the rate of the reaction. The product can be obtained economically. Often zeolite materials are naturally occurring clays, e.g. Incorporated in bentonite and kaolin. These materials, i.e. clay, oxidation The substances act, in part, as binders for the catalyst. Has good crushing strength It is desirable to provide a catalyst that is suitable for use in petroleum refining. This is because they are treated poorly. This shows a tendency to crush the catalyst into powder, which is Cause processing problems.

Naturally occurring clays that can be synthetically composited with the olide of the present invention include montmorillonite and Includes the kaolin family, which includes subbentonite and kaolin, which are commonly Always Dixie, McNamee, Georgia and Florida It is known as clay, etc., and its main mineral components are halloysite, kaolinite, and zinc. It is a kite, a nake light, or an anakisit. sepiolite and attapulge Fibrous clays such as clay can also be used as supports. This clay was initially Can be used in its original state as mined or first subjected to calcination, acid treatment or chemical modification. Can be done.

In addition to the above-mentioned materials, (B) the beta zeolite also contains a porous matrix material and a mixture of matrix materials. compounds, such as silica, alumina, titania, magnesia, silica:alumina, Silica: magnesia, silica-zirconia, silica-thoria, silica-beryria , silica ditania, titania-zirconia, as well as ternary compositions, e.g. Car-alumina-thoria, silica-alumina-zirconia, silica-alumina-ma It is composited with gnesia and silica-magnesia-zirconia. This substrate is koge It can be in the form of a le.

(B) Beta zeolite also includes other zeolites, such as synthetic and natural zeolites. Can be composited with jazzite (e.g. X and Y), erionite and mordenite. Ru.

These are also complexed with purely synthetic zeolites, such as those of the 23M series. can. Combinations of zeolites can also be composited into porous inorganic matrices.

(B) Beta zeolites are useful in hydrocarbon conversion reactions. Hydrocarbon conversion reaction is a chemical and catalytic process in which a carbon-containing compound is transformed into a different carbon-containing compound . Examples of hydrocarbon conversion reactions are catalytic cracking, hydrocracking, and olefin and aromatic conversion reactions. Including reaction. This catalyst can be used in other petroleum refining and hydrocarbon conversion reactions, e.g. isomerization of raffins and naphthenes, olefinic or acetylenic compounds, e.g. , polymerization and oligomerization of isobutylene and butene-1, modification, alkylation, polymerization, Isomerization of realkyl-substituted aromatics (e.g. ortho-xylene) and aromatics (e.g. , toluene) to produce benzene, xylene and higher methylbenzenes. The effect is to obtain a mixture. This (B) beta catalyst has high selectivity and to obtain a high percentage of the desired product relative to the total product under hydrocarbon conversion conditions. Something will happen.

(B) Beta zeolites can be used in processing hydrocarbonaceous feedstocks. Carbonization Hydrogenaceous feedstocks contain carbon compounds and come from many different sources, e.g. natural stone. May be from oil fractions, recycled petroleum fractions, heavy oil, liquefied coal, tar sands oil. and generally any carbon-containing fluid capable of undergoing a zeolite-catalyzed reaction. But that's fine.

Depending on the type of processing, this hydrocarbon feed may be It may or may not contain high or low nitrogen or sulfur impurities. You may. However, the metal, nitrogen, and nitrogen content of the feedstock is lower. Indeed, the process becomes more effective (and the catalyst becomes more active).

(B) Base containing boron and/or aluminum framework replacement and hydrogenation accelerator Temperatures in the range of 175 to 485 °C, ■ to 1 using tazeolite catalyst molar ratio of hydrogen to hydrocarbon charge of 0.00, pressure and pressure in the range from 0.5 to 350 bar. and a liquid hourly space velocity (LH3V) in the range of 0.1 to 30. Under the conditions, heavy oil residual feedstock, recycled feedstock and other hydrocracking charge feedstocks can be hydrocracked. Wear.

This hydrocracking catalyst is a lower effective amount of the types commonly used for hydrocracking catalysts. Both contain one hydrogenation catalyst (component). These hydrogenation catalysts are generally salts, complexes and one or more of Group VIB and Group V[l[ selected from the group of hydrogenation catalysts consisting of metals of the group A. This hydrogenation catalyst is platinum, para Consisting of at least one of dium, rhodium, iridium, and mixtures thereof group or nickel, molybdenum, cobalt, tungsten, titanium, chromium and selected from the group of metals, salts and complexes thereof, consisting of at least one mixture thereof; It is preferable that The elemental state or contains one or more metals in the form of oxides, sulfides, halides, carbonates, etc. shall be included.

The hydrogenation catalyst is present in an amount effective to provide the hydrogenation action of the hydrocracking catalyst and Preferably it is within the range of 0.05 to 25% by weight.

The catalyst is a traditional hydrocracking catalyst, e.g. Can be used with any aluminosilicate. Component parts of hydrocracking catalyst and An example of a previously disclosed zeolite aluminosilicate that can be used as (including, for example, steam stabilized, e.g. ultra-stable Y), zeolite Zeolite ZK-20 (U.S. Patent No. 3.308.069), Zeolite ZK-20 (U.S. Patent No. 3.445.727), Zeolite ZSM-3 (U.S. Pat. No. 3.415.73) No. 6), Faojasite, LZ-10 (UK Patent No. 2.014.970, 1 982.6.9), ZSM-5-type zeolites, e.g. ZSM-5, ZS M-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM -48, crystalline silicates, e.g. silicalite (U.S. Pat. No. 4,061..7 No. 24), erionite, mordenite, offretite, chabazite, FU- ]-type zeolite, NU-type zeolite, LZ-210-type zeolite and mixtures thereof. Conventional products containing Na2O in amounts of about 1% by weight or less Hydrocracking catalysts are generally suitable. (B) Beta zeolite and some However, the relative amounts of conventional hydrocracking catalysts depend, at least in part, on the selected hydrocarbon supply. Depending on the feedstock and the desired product distribution obtained therefrom, in all cases An effective amount of (B) beta is used.

Amorphous catalytic inorganic oxides, e.g. catalytically active silica-alumina, clay, silica Mosquito, alumina, silica-alumina, silica-zirconia, silica-magnesia, Alumina - forms of hydrocracking catalysts including boria, alumina etc. and mixtures thereof Hydrocracking catalysts are typically used with inorganic oxide substrate components that are conventionally used in It will be done. The conventional hydrocracking catalyst component (TC) and (B) beta are separated from the substrate component. (B) Beta is mixed with the TC component and then mixed with formed together with matrix components.

Hydrocarbonaceous feed by selectively removing or converting normal paraffins Can be used for dewaxing.

Catalytic membrane brazing conditions vary greatly depending on the feed used and the desired pour point. one Generally, the temperature is between about 200 and about 475°C, preferably between about 250 and about 450°C. It is between °C. The pressure is typically about 15 to about 3000 psig, preferably is approximately 200 to 3000 psig. LH3V is preferably 0.1 to 2 0, more preferably about 0.2 to about 10.

Hydrogen is preferably in the reaction zone during the catalytic membrane brazing process.

Hydrogen to feed ratios typically range from about 500 to about 30,000 SCF/bbl. standard cubic feet per barrel), preferably from about 1000 to about 20.　OOOSC F/bbl. Generally, hydrogen is separated from the product and recycled to the reaction zone. It will be done.

Typical feedstocks are light gas oil, heavy gas oil, and atmospheric distillation residual oil with a boiling point of approximately 350°F. including.

The (B) beta hydrodewaxing catalyst is optionally of the type commonly used for dewaxing catalysts. Contains hydrogenated components. This hydrogenation component includes metal-containing salts, complexes and solutions. or a group of hydrogenation catalysts consisting of one or more metals of Group V[B and Group Vll[]. You can choose from. Suitable hydrogenation catalysts include platinum, palladium, rhodium, iridium and and at least one of mixtures thereof or nickel, molybdenum, tungste selected from the group consisting of at least one of carbon, titanium, chromium and mixtures thereof. at least one group of selected metals, salts and complexes. catalytically active single-pronged is an elemental state for multiple metals or oxides, sulfides, )) rogides, carbonates, etc. shall include one or more metals in the form of

The hydrogenation component is preferably in the range of about 0.05 to 5% by weight of an effective hydrogenation film. Present in an effective amount to provide a wax catalyst.

(B) Converting straight-run naphtha and similar mixtures to higher aromatic mixtures using Beta. can. Thus, preferably linear and slightly branched hydrocarbon feet from about 400 to about 600° with the heptaolide. C1 temperature preferably in the range 480-55°C, in the range from atmospheric pressure to 10 bar By contacting at a pressure ranging from 0.1 to 15 and a LH3V ranging from 0.1 to 15 This hydrocarbon can be converted into a product with mostly aromatic content. Hydrogen to hydrocarbon ratio ranges from 1 to 10. (B) Beta is fixed bed, fluidized bed or moving bed reformer -Can be used for

The conversion catalyst is preferably a Group Vllll catalyst as it has sufficient activity for commercial use. Contains metal compounds. As used herein, the Group Vllll metal compound refers to the metal itself or means the compound. Group VIII noble metals and their compounds, platinum, palladium and iridium or a combination thereof. The most suitable metal is platinum.

No. V+ present in the conversion catalyst! [Amounts of group metals are within the normal range used in reforming catalysts.] about 0.05 to 2.0% by weight, preferably 0.2 to 0.8% by weight. It's difficult. (B) The performance of noble metals in beta as promoters for aromatization selectivity and is further enhanced by the presence of other metals.

Zeolite/Group Vllll metal conversion catalysts can be used in the binder or matrix. this If used, suitable inorganic substrates are Cab-0-Sil or Ludox. It is a silica-based binder. Using other substrates such as magnesia and titania Can be used. Suitable inorganic substrates are non-acidic.

For example, by poisoning zeolite with basic metals, e.g. alkali metals, compounds (poisouing) It is useful to make the conversion catalyst almost non-acidic. is important for the selective production of aromatics. This zeolite is usually alkaline Prepared from a mixture containing metal hydroxides and thus containing about 1-2% by weight alkali Has metal content. These high levels of alkali metals, usually thorium or Potassium is difficult to accept for most catalytic applications because they are used in cracking reactions. This is because it largely inactivates the catalyst used. Usually hydrogen or ammonium ions ion exchange to remove alkali metals to low levels. use here Alkali metal compounds are elemental or ionic alkali metals or their basic compounds. means.

Surprisingly, if the zeolite itself has virtually no acidity, it is difficult to carry out the synthesis reaction. A basic compound is required in this process to accommodate aromatics production. (B) Be In the case of Not necessary.

For the catalytic crabking of hydrocarbon feedstocks without hydrogen (B ) was also found to be used for raising seedlings. Preferred conditions are 800 to 1500°F Catalyzing hydrocarbon feedstocks in the reaction zone without added hydrogen at average catalyst temperatures over a range of separating the catalyst from the product effluent; into the lapping zone and then into the regeneration zone in the presence of steam and free oxygen-containing gas, where the The reaction coke deposited on the catalyst is subjected to elevated temperatures ranging from 1000 to 1550°F. combustion at high temperature and then recycling the reactivated catalyst to the reaction zone. The fluidized catalytic cracking method consists of

For this purpose, either as combined components or as separate additive particles. (E3) Beta can be used with conventional cracking catalysts.

Contains any aluminosilicate conventionally used as a component in cracking catalysts, This catalyst can be used with conventional cracking catalysts. Conventional cracking catalyst An example of a zeolite aluminosilicate disclosed as being usable as a component is zeolite. Light Y (vapor stabilized Y, rare earth Y, chemically modified Y, ultra-stable Y or this Zeolite X, Zeolite Beta (U.S. Patent No. 3,415) ．． 736), Faojasite, LZ-10 (UK Patent No. 2.014.970) No., June 9, 1982), ZSM-5-type zeolite, e.g. 5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 , ZSM-48, crystalline silicates, e.g. 61.724), erionite, mordenite, zeolite or 24.5 in other dealuminated zeolites or matrix materials of cell size or smaller. Zeolite grown in situ (U.S. Pat. Nos. 3.647.718 and 4.49) 3.902) and mixtures thereof.

The term “zeolite” used here refers not only to aluminosilicates but also to aluminum Substances in which aluminum is replaced with gallium or boron and silicon is replaced with germanium intended for substances that are Other exemplary acids that may also be used as ingredients amorphous silica-alumina catalyst, synthetic mica-montmorillonite catalyst (as defined in U.S. Pat. No. 3,252,889), cross-linked or clay (U.S. Pat. Nos. 4,176.090, 4,248.739, 4. 238.364 and 4.216.188) and acid-activated viscosity. Earth - bentonite, hectorite, sabonite.

Conventional glue 50:1, most preferably incorporating Na2O in an amount generally less than about 1% by weight. from about 1.1 to about 20.1 Alumina, clay, synthetic or acid-activated clay, silica , Aluminum or TC component and (B) Beta are mixed together and then used as substrate or (B) Beta or particles thereof with or without ingredients having a suitable density and particle size distribution; In some cases, it can be added as a discontinuous component to conventional cracking catalysts.

(B) Beta is a straight chain and a branched chain having about 2-21 and preferably 2-5 carbon atoms. It can be used to oligomerize branched olefins. is the product of this process Oligomers are active in fuels, i.e. gasoline or gasoline admixtures and chemicals. Intermediate to heavy olefins, this oligomer method is about 450 to about 1200 ’F temperature, WH3V of about 0.2 to about 50 and carbonization of about 0.1 to about 50 atm. contacting (B) Beta with a vapor phase Refine feedstock at a partial pressure of hydrogen; nothing.

In addition, if the feedstock is in the liquid phase when contacting the zeolite catalyst, Temperatures of up to about 450'F can be used to oligomerize the materials. Thus, When the olefin feedstock is contacted with the heptaolide catalyst in the liquid phase, from about 50 to about Temperatures of 450°F, preferably 80-400°F are used and about 0.05°F. 20, preferably 0.1 to 10 WH3V is used. The pressure used is It will be appreciated that the system must be sufficiently maintained in the liquid phase. To those skilled in the art As is known, pressure is a function of the number of carbon atoms in the feed olefin and the temperature.

Suitable pressures include about 0 to about 3000 psig.

Zeolites can be substituted with a wide variety of other cations by techniques well known to those skilled in the art. has the original cation attached to it. Typical cations are hydrogen, a Contains cations of metals including ammonium and mixtures. Among substituted metal cations, Rare earth metals, manganese, calcium, as well as metals from group ■ of the periodic table, e.g. Zinc and metals of group VNI of the periodic table, such as nickel, are particularly preferred.

The heptaolide has a fairly low aromatization activity, i.e. the aromatization activity produced therein is The main requirement is that the aromatic content should not exceed about 20% by weight. This is n- from about 1 liter to about 120, preferably as measured by its ability to crack hexane. or a hexafluoride having a controlled acid activity [alpha value] of about 0.1 to about 100. This is done by using rides.

The alpha value is, for example, as shown in US Pat. Defined by standard tests known to those skilled in the art, which are incorporated herein by reference in their entirety. It will be done. If necessary, this zeolite can be used in the steaming process, conversion process or as suggested by a person skilled in the art. It can be obtained by any other method.

Light gas C2-C6 paraffins and/or olefins containing aromatic compounds (B) Beta can be used to convert it to a molecular weight hydrocarbon of about 100%. C2-C, Pa 100-700 for converting raffins and/or olefins to aromatics 'C operating temperature, O-1000 psig operating pressure and 0.5-4.0 hr-' WHS V space velocity can be used. Preferably, the zeolite contains a catalytic metal or contains a metal oxide, where the metal is a member of Group IB, Group rIB, or Group V of the Periodic Table. selected from the group consisting of Group LSI and Group 1IIA and most preferably Gari um or zinc and is within the range of about 0.05-5 9 stone by weight.

Aliphatic and aromatic carbons mixed with lower aliphatic alcohols having 1-10 carbon atoms (B) Beta is used for condensation to gasoline-boiling hydrocarbon products, including hydrocarbons. Can be used. This condensation reaction is carried out at a temperature of about 500-1000°F, about 0.5-1000°F. psig pressure and a space velocity of about 0.5-50 WH3V. US Patent No. The method disclosed in No. 3.984.107 further specifically includes the steps used in the method. TERMS AND CONDITIONS, this patent is hereby incorporated by reference in its entirety.

The catalyst is in hydrogen form or preferably in the range of about 0.05 to 5% by weight, base exchanged. or impregnated with ammonium or metal cation complement. can exist The metal cation includes any of the metals of groups r-V[r[ of the periodic table.

However, in the case of Group TA metals, the cation content never really catalyzes the catalyst. 2. Must not be large enough to be inactivated.

The catalyst is highly active and highly selective in isomerizing C4 to 07 hydrocarbons. Made. This activity is thermodynamically favorable to catalysts or highly branched paraffins. This means that it can be operated at relatively low temperatures. As a result, this catalyst is high-octane. It is possible to produce a tan product.

High selectivity means relatively high liquid yields can be obtained when the catalyst is run with high octane. It means to do something.

The method includes contacting an isomerization catalyst with hydrocarbon feet under isomerization conditions.

This foot preferably ranges from 30 to 250°F, preferably from 60 to 200'F. It is a light straight distillate that boils within the range. Preferably, the hydrocarbon feed for this method is contains significant amounts of C4 to C7 straight chain and slightly branched low octane hydrocarbons; preferably contains C6 and C8 hydrocarbons.

The pressure in this method is preferably from 50 to ]000 psig, more preferably 1 00-500 psig.

LH3V is preferably from about 1 to about 10, with a value within the range of about 1 to about 4 or more. preferred. It is also preferable to carry out this isomerization reaction in the presence of hydrogen. preferred preferably 0,5 to 1082/HC1, more preferably 1 to 8H,/HC hydrogen pairs Hydrogen is added to yield a hydrocarbon ratio (H7/HC). The temperature is preferably about 2 00 to about 1000°F, more preferably 400 to 600°F. isomerization As is well known to those skilled in the art, within this wide range temperature selection is primarily a function of This is done as a function of the desired conversion level, taking into account the properties of the catalyst. Afterwards, The inactivation (-compensating) that occurs during the run to obtain a relatively constant value for the As such, the temperature must be raised gradually.

Low sulfur feet are particularly preferred in this method.

This foot (4 preferably loppm or less, more preferably 1 ppm or less, and most preferably 0. Contains less than i ppm of sulfur. Already old If the foot is not low, a preform with a hydrogenation catalyst that is resistant to poisoning is recommended. Acceptable levels are obtained by hydrogenating this feed in the saturation zone. child Examples of suitable catalysts for the hydrogenated membrane incubation process include AnoC Mina co-support and molybdenum oxide. A small catalytic portion of budene, cobalt oxide and/or nickel oxide. Aluminum Platinum on the hydrogenation catalyst also works. In this case, an effective sorbent (5 orbe r) is preferably placed downstream of the hydrogenation catalyst but upstream of the isomerization catalyst of the present application. Ru. Examples of useful sorbents are alkali or alkaline earth on porous refractory inorganic oxides. Metals, zinc, etc. Hydrogenated film aging is typically performed at 315-455°C120 0 to 2000 psig and 1 to 5 LH3V.

It is preferable to limit the nitrogen level and the water content of the feed. suitable for this purpose Catalysts and methods are known to those skilled in the art.

After a certain period of operation, the catalyst is deactivated by coke. L becomes a catalyst when the temperature is increased. Coke can be removed by contacting with oxygen-containing gas.

The isomerization catalyst is preferably prepared from Part V[I] to have sufficient activity for commercial use. Contains Group I metallized compounds. Where are Group VI metal compounds used? It means itself or its compounds. Chapter V1 [[Group noble metals @ and their compounds, platinum , palladium and ilinium, or a combination of these can be used. Together with precious metals Rhenium and tin can be used. Amount of Group VI metal present in the conversion catalyst is about 0.05 to 2.0% by weight, within the range of normal use in isomerization catalysts. Ru.

(B) Beta is used in aromatic hydrocarbon alkylation or transalkylation processes. It can be used as a catalyst for other purposes.

This method produces aromatic aromas in the presence of a catalyst containing (B) beta at least partially in a liquid phase. C2 to C20 olefin alkylating agent or polyalkyl aromatic carbon contacting a hydrotransalkylating agent.

Because of their high catalytic activity, (B) beta zeolites are primarily in the hydrogen ion form. It is a good place to go. Generally, zeolites are prepared by ammonium exchange followed by calcination. Converted to hydrogen form. Zeolite or high sufficient ratio of organic nitrogen cations to sodium When it is synthesized using mu ions, it is sufficient to sinter it. Cation position after calcination preferably at least 80% of the hydrogen ions and/or rare earth ions. Delicious.

Can pure (B) beta zeolite be used as a catalyst? powder with an inorganic oxide binder, such as alumina, silica, silica/alumina, or by mixing with naturally occurring clays and forming this mixture into tablets or extrudates. preferable. The final catalyst contains 1-99% by weight of (B) beta zeolite.

Usually the heptaolide content is between 10 and 90% by weight, and more typically between 60 and 90% by weight. It ranges from 80% by weight. A preferred inorganic binder is alumina. This mixture The desired shape can be formed into tablets or extrudates by methods well known to those skilled in the art.

Suitable aromatic carbonizations that can be alkylated or transalkylated by the method of the invention Examples of hydrogen feedstocks are aromatics such as benzene, toluene and xylene. Ru. A preferred aromatic hydrocarbon is benzene. Mixtures of aromatic hydrocarbons can also be used. Wear.

Olefins suitable for alkylation of aromatic hydrocarbons are those containing 2 to 20 carbon atoms. , for example, ethylene, propylene, butene-1,l-lansbutene-2 and cis -butene-2 and higher olefins or mixtures thereof.

The preferred olefin is propylene. These olefins are derived from the corresponding C2 02゜Can exist in admixture with paraffins to prevent rapid catalyst deactivation Any dienes, acetylenes, nitrogen compounds or nitrogen present in the refine feedstock It is preferable to remove elementary compounds.

When transalkylation is desired, the transalkylating agent may be Polyalkyl containing two or more alkyl groups having about 4 carbon atoms It is an aromatic hydrocarbon. For example, suitable polyalkyl aromatic hydrocarbons include di-,tri-, and tetra-alkyl aromatic hydrocarbons, such as diethylbenzene, triethyl Hensen, diethylmethylbenzene (diethyltoluene), seaisopropyl bene Benzene, di-isopropyltoluene, dibutylbenzene, etc. suitable poria Alkyl aromatic hydrocarbons are dialkylbenzenes. Particularly suitable polyalkyl aromatics The aromatic hydrocarbon is di-isopropylbenzene.

The resulting reaction product is a reaction between benzene and either ethylene or polyethylbenzene. Ethylbenzene, propylene or polyisopropylbenzene and benzene from from the reaction of cumene, from the reaction of ethylene or polyethyltoluene with toluene Reaction of ethyltoluene, propylene or polyisopropyltoluene with toluene? from the reaction of benzene with n-butene or polybutylbenzene. Contains butylbenzene. Alkylation of propylene and benzene or di-isopropylene Particularly suitable for the production of cumene from the transalkylation of pyrubenzene and benzene There is.

When alkylation is the process to be carried out, the reaction conditions are as follows. aromatic The hydrocarbon feed must be present in stoichiometric excess. Rapid catalyst fouling In order to prevent . Reaction temperatures range from 100 to 600°F, preferably from 250 to 4500F. . The reaction pressure is sufficient to keep the catalyst at least partially in the liquid phase to retard catalyst fouling. There must be. This typically ranges from 50 to I00 depending on the feedstock and reaction temperature. It is 0 psig. Contact times can range from 10 seconds to 10 hours, usually from 5 minutes. It is one hour. of aromatic hydrocarbons and olefins per g (bond) of catalyst per hour. The WHSV in terms of grams (pounds) is generally within the range of about 0.5 to 50.

When transalkylation is a process, the molar ratio of aromatic hydrocarbons is constant. Generally ranging from about 1:1 to 25:1, and preferably from about 2:1 to 20:1. Bu.

Reaction temperatures range from about 100 to 600°F, preferably from 250 to 450°F. It is F. The reaction pressure should be sufficient to maintain at least a partial liquid phase and should be in the range of about 500 to I000 psig, preferably 300 to 600 psig. It is within. WHSV ranges from about 0.1-10.

Conversion of the hydrocarbonaceous feed may be carried out in any convenient manner, e.g. Depending on the type, it takes place in fluidized bed, moving bed or fixed bed reactors. The formation of catalyst particles is It varies depending on the method of conversion and operation.

Other reactions that can be carried out using catalysts of the invention that contain metals, such as platinum, include hydrogen This includes hydrogenation-dehydrogenation reactions, denitration and desulfurization reactions.

Several hydrocarbon conversions were carried out in (B) beta zeolite by taking advantage of the large pore shape selection behavior. can be converted. For example, alkylating aromatics using propylene (B) Betazeo substituted when producing cumene or alkylbenzene in the process of Lights can be used.

With active or inert supports, with organic or inorganic binders, and with added metals (B) Heter can be used in conjunction with the hydrocarbon conversion reaction. these reactions are well known to those skilled in the art, and so are the reaction conditions.

As an adsorbent, paper, paint and toothpaste paste-1, as a filler and as a detergent. (B) Beta can also be used as a water softener.

The following examples illustrate the preparation and use of (β)beta.

Synthesis of effective diquaternary ammonium compounds Boron beta crystallization 48 g of DABCO (1,4 diazapinchloro(2,2,2) otane) was added to ethyl acetate. Stir in 800ml of Tate.

42 g of short butane was added dropwise and gradually without stirring the reaction. at room temperature Leaving the reaction to run for several days produces high yields of precipitated diquaternary compounds.

The product is washed with THF, then with ether and then dried under vacuum.

melting point = 255 °C to obtain solutions ranging from 10,25 to 1.5 molar AGI - by stirring overnight in water using an X8 hydroxytoe ion exchange resin. 0.90M solution of template from Example 1 for conveniently converting crystalline salts into hydroxide form Dilute 10.85g with H2 (13.95ml). Add 40t of NaxB to this solution. '181 (200,23g dissolved and then Carbosil M5 Finally, mix 1.95 g. The reaction mixture was heated to 150°C and Parr47 45 reactor and over a period of 9 days on the spit in the Blue, M furnace. Rotate at 43 rpm. The solid components of the reaction were filtered, washed repeatedly and heated to 115°C. dried and analyzed by X-ray diffraction. This product is qualified as (B) beta. Ru.

Example 3 Set up the same experiment as in Example 2, but with the same amount of N4 as in Example 2. of TEAOH. Run the experiment under similar conditions or try crystallization this time6 Completed in a day. The product is ZSM-5 by XRD. This is TEAOH This means that it does not have sufficient selectivity for beta in the borosilicate system. Ru. TEAOH is the template from Example I used in the prior art for beta synthesis. 202g of 0.84M solution of template was added to 8□055g and NaJt07-10. Mix with 4.03 g of LD.

Finally, 35 g of Carbosil M 5 was mixed in and kept at 150°C for 6 days. Run the reaction in a Parr 600 cc stirred autoclave with a liner. Stir at 50 rpm.

The product is fully crystallized boron beta. The patterns are shown in Table 2.

VB = very wide Examples 5-10 are shown in Table 3 and demonstrate the utility of the method of the invention. Examples 5 to 7 are (B) The data is made with very low S+Oz/B2O2 values and higher numbers are It is shown that the result similarly leads to the formation of ZSM-12. Example 8 as a silica source It is shown that the desired product is obtained using Ludox As-30. here The aluminum impurity rose to 530 ppm. Example 9 and Example IO Complement TEA It has been shown that applying N4 as a salt to OH ensures the formation of pure boron beta. show. Example 9 shows the case without inoculation.

Table 4 shows the XRD data for the product of Example 5 and Table 5 shows the XRD data for the product of Example 5. This is the form in which both are combined.

Table 4 7.7 11.5 28 B 18.55 4.78 8 VB 2+, 55 4.12 22 22.60 3.93 110 25, 60 3.48 4 26.00 3.43 3B 27, 58 3.24 8 29.00 3.08 6 B 29, 98 2.98 6 30, 65 2.92 2 31.15 2.87 1 VB 33.67 2.66 4B 35, 27 2.55 2 36.50 2.47 2B VB - very wide 7.7 11.5 27 B 18.45 4.82 5 VB 21, 47 4.14 18 22, 56 3.94 128 25, 53 3.49 6 26.00 3.43 3B 27, 52 3.24 9 28.97 3.09 7B 29, 92 2.99 8 30, 60 2.92 2 31.20 2.83 2 VB 33, 66 2.66 5 35.17 2.55 2 36.35 2.47 2 8 B = wide VB = very wide The XRD patterns for the calcined products of Examples 5 and 6 are shown in Tables 6 and 7, respectively. Show below.

The presence of boron in the beta zeolite framework is indicated by changes in the d-spacing. Ru. Table 8 shows that for some of the sharper peaks of the products of Example 4, Example 5 and Example 6, Compare the d-spacing before and after firing. Also, according to the prior art reference (Re 28.341) Also shown are values for aluminum beta zeolite prepared by boron beta exhibits consistently smaller d-spacing than aluminum beta.

7.7 11.5 34 B 13.58 6.53 3 14.88 5.97 5B 18.60 4.77 2 VB 21.85 4.06 10B 22, 89 3.88 42 25.80 3.45 5 B 27, 38 3.26 5 29.35 3.05 2B 30.10 2.97 3 31.15 2.87] VB 34.00 2.64. 1 VB 36.90 2.44 1 VB B-wide VB = very wide 7.7 11.5 38 B 13, 52 6.55 4 14.85 5.95 5B 18.50 4.82 2 VB 21.80 4.08 5 B 22, 82 3.90 50 25.75 3.46 6B 27, 35 3.26 5 29.27 3.05 2B 30,00 2.98 4 31.00 2.88 2 VB 33.90 2.64 2 VB 36.80 2.44 1 VB VB = very wide AIB 3.97 3.30 3.03 3.97 3.30 3.03 Example 4 0.078-B 3.95 3.24 2.99 3.89.3.26 2.9 7 Example 6 0.10B-B 3.94 3.24 2.99 3.90 3.26 2.98 Example 5 0.13B-B 3.93 3.24 2.98 3.88 3.26 2.97 Note 2 The d/n interval for B-beta is the same as for AI-beta. Consistently smaller than those that do.

Example 11 The product of Example 4 was calcined as follows. room at a constant increasing rate over 7 hours. The samples were heated in a Matsufuru furnace under nitrogen to temperatures ranging from 540°C to 540°C. 4 more hours The sample was held at 540°C and then increased to 600°C for an additional 4 hours.

Nitrogen was passed over the zeolite at a rate of 20 standard cfm during heating. calcined product The material had the X-ray diffraction lines shown in Table 9 below.

13, 58 6.52 6 14.87 5.96 8B 18.50 4.80 2 VB 21.83 4.07 10B 22, 87 3.89 70 25.75 3.46 7 27, 38 3.26 7 29.30 3.05 4B 30, 08 2.97 5 31.00 2.88’3 B 33.95 2.64 2 VB B = wide VB = very wide Example 12 Ion exchange of the calcined material from Example 4 using NH,N03 was converted from Na to NH4. Typically the same amount of NH4N0 as zeolite 3 was slurried in 50:II (ratio of 20 zeolite to N20. 100° for 2 hours. The exchange solution was heated and then filtered. This process was repeated twice. last After the last exchange, the heptaolide was washed several times with water and dried.

0.50 g of the hydrogen form of the zeolite of Example 4 (after treatment according to Example 1 and Example I2) was Backed in 378 inch stainless steel tubing with alundum on both sides of the light floor . A Lindberg furnace was used to heat the reactor tube. Reaction at +Occ/min and atmospheric pressure Helium was introduced into the organ. Place the reactor at 250°F for 40 minutes, then at 80°F. Raised to 0°F.

Once temperature equilibrium is achieved, 50150 of n-hexane and 3-methylpentane W/w feed was introduced into the reactor at a rate of 0.62 CC/hr. soringipo A foot move was made through the pump. Gas chromatograph 10 minutes after introduction of feet. Started zumbling directly to Graph' II.

Calculate the restraint index value from the gas chromatographic data using methods known to those skilled in the art did.

Example 14 After treatment as in Examples 11 and 12, the product of Example 4 was converted to AI(NO=)2.9 Refluxed overnight with H30, the latter having the same mass as the zeolite and Example 12 The same dilution as in the ion exchange was used. Filter and wash this product and calcined at 540°C. pelletized into zeolite powder and 20-4 After remaining in the 0 mesh fraction, the catalyst was tested as in Example 13. other metals Table 10 provides data for the reactions with various catalysts prepared from similar treatments with salts. show.

Examples 15-22 See Table fO and No. 11.

Table 10 Metal processing (B) Restraint index measurement for beta 14 A1. (NOr)z 1.0 35.0 60015 Ga (NO3)3 0.25 83.0 80016 5n (Ac) 2 0.70 1.0 80017 MgCL ・6 N20 2.0 0.2 80018 Co(NO3)2' 6820 1.0 5 ．． 0 800 Table 11 shows various amounts of Zn(Ac)z・2N20 Example 4, Example 1 1 shows data for processing the product of Example 12.

Table 11 Example: Exchange/after calcination No, (B) Beta Zn(Ac)z・2 HzOZn weight% 19 4.5 g 2.20g 3.1.220 4.5g 1.10g 1.9521 4. 5g 0.55g +, 3822 4, 5 g 0.25 g 0.76 Example 20 5% conversion (B) beta borosilicate bar at 800'F for C,I test John was evaluated as a reforming catalyst. This zeolite powder is converted into pt (NHZ )t.2NO1 to yield 0.8 wt% Pt. 55 lever substances in the air Calcined to 0°F and held at this temperature for 3 hours. This powder at ]000psi It was pelletized on a carver press, crushed and sieved 24-40 mm. .

psig = 200 when the catalyst was evaluated at 900'F in hydrogen under the following conditions: 1(,/HC=6.4 WH5V = 6 Temperature = 900'F This foot is made of iC7 mixture (Philips Petrole++ mComp any).

Table 12 shows data at 800 and 900°F and at 50 and 200 psig. show.

Table 12 1) Temperature 800°F 800°F 900°F Pressure (H2) 200 50 200 Conversion % 88.8 77.0 100 Aromatization selectivity % 25.4 54.5 25.3 Product toluene 19i 3 9.3 16.9% by weight 84.9 93.7 67.8 Torr% in C6 aromatics C5 yield weight% 46.9 77.4 30.2 C5~C, RUN 89.5 90.6 104.3 (a) This catalyst is extremely stable and the values are averaged over a period of at least 20 hours.

Example 24 The product of Example 18 now contained a second metal according to the formulation. catalyst was calcined to 1000°F. Next, prepare the reforming catalyst as in Example 23. Manufactured. This catalyst was evaluated under the conditions listed in F. psig = 100, 200 Hx/HC=6.4 WHSV = 12 Temperature = 800’F This feed has a jC7 mixture (Philips Petroleum) Ru. Data for the runs are shown in Table 13.

After a 23 hour oz dream, reduce the pressure to lOOpsig and display this data. Shown below. Compared to Example 23, the incorporation of cobalt into the zeolite has a higher C6+ selectivity. Generates a reforming catalyst. The catalyst has good stability at 800°F.

Table 13 Temperature 800°F800°F Pressure 82200 100 Conversion% 83.3 86 Aromatization selectivity% 2737 Product Toluene Weight % 18.8 27.3 Toluene % in C5 + Aromatics 8 3.3 85.9C6 yield, %; 59.8 63.7C6-C, RUN 85.3 90.3 Example 25 The product was prepared as in Example 12. The catalyst was then dried at 6000F and closed. The chain system is cooled and then vacuum impregnated with an aqueous solution of Pd(N)13)4.2N03 to paralyze the This resulted in a 0.5 wt% loading of dium. Next, gradually raise the catalyst to 9000F in air. Calcined and kept there for 3 hours. Table 14 shows the hydrogenolysis of hexadecane. Run conditions and product data are shown. The catalyst has an extremely low temperature at a given temperature. F 625 637 WH3V +, 55 1.55 psig 1200 1200 Conversion 85.1 97.8 Isomerization selectivity 94.5 69.9 Crack selectivity 5.6 30.1 This data shows that the catalyst has good isomerization selectivity and liquid yield. This indicates that the value is higher than that of

Example 26 The hydrogen form of (B) beta can be used in typical fluid catalytic cracking (FCC). Example 2, AI(NO3) prepared as in Example 11 and Example I2 and as in Example 14 ) Spray-dried FCC catalyst octane-loaded (B) beta refluxed with Z.9H20 It was formulated into additives and tested in a fixed flow circulation reactor. For this example, use this F The CC catalytic octane additive nominally contains 25% (B) beta and 32.5% carbon by weight. It contained ollin and 42.5% silica/alumina matrix.

Fixed flow circulation tests were conducted at a catalyst/oil ratio of 7 with an initial catalyst temperature of 1100°F. . Gas chromatographic analysis of the liquid product was then performed to measure the predicted octane. Established.

(B) Catalyst inventory during fixed flow circulation test of Beta FCC catalyst octane additive is 90% Cooked Rare Earth FCC Catalyst and 10% Calcined (B) Beta FCC Catalyst Octane Contains additives. The feed properties of the gas oil used during the fixed flow circulation test were Shown in the table.

Table 15 API gravity 27.43 Aniline point 187.3 Total nitrogen 1040911m pseudo distillation ST　160　℃ 5 Capacity% 256 °C Table 16 shows calculated research and motor octane numbers from fixed flow cycling tests.

Table 16 25% (B) Beta RON 85.6 87.8 M0N 75.9 76, 8 cs-C4゜ RON 85.3 87.5 M0N 75.6 76, 9 Hand'H! correction book rest area 1-Display of incident 2-Name of the invention Low Aluminum Boron Beta Zeolite Chevron Research & Techno Logy Company 4-Agent 6 - Number of claims increased by amendment 7- Subject of correction Description and claims translation 8- Contents of amendment as attached International search report with engraving of the translation of the description and claims (no change in content)

Claims (36)

[Claims] Silicon oxide, germanium oxide and mixtures thereof greater than 1.10:1 boron oxide, or aluminum oxide, gallium oxide or acid It has a molar ratio of oxides selected from a mixture of iron oxide and boron oxide, and containing less than 0.10% by weight and having the X-ray diffraction lines of Table 1(b). Zeolite. 2. As synthesized and in anhydrous state, the composition in terms of molar ratio of oxides is as follows: has: (1.0 to 5) Q2O: (0.1 to 2.0) M2O: W2O3: ( 10) YO2: where M is an alkali metal cation and W is boron Y is selected from silicon, germanium and mixtures thereof, Q is a diquaternary ammonium ion and has the X-ray diffraction lines of Table 1(a). Zeolite. 3. Molecular weight of an oxide selected from silicon oxide to boron oxide greater than 100:1 zeolite according to claim 1, having a 4. A portion of the boron in the zeolite is a first row transition metal or a group IIIA metal. Zeolite according to claim 1, which is replaced by. 5. Substitute metals are aluminum, gallium, iron, silicon, zinc and mixtures thereof Zeolite according to claim 4. 6. Heat treating the zeolite of claim 3 at a temperature of about 200 to 820°C. Zeolite produced by. 7. The diquaternary ammonium ion has the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Zeolite according to claim 2, derived from a compound of. 8. Hydrogen, ammonium, rare earth metal, Group IIA metal, or Group VIII metal A zeolite according to claim 1 or 2, which has been ion-exchanged with ions. to. 9. Rare earth metal, Group IIA metal, or Group VIII metal occluded in zeolite Zeolite according to claim 1 or 2. 10. A zeolite comprising the zeolite of claim 1 or 2 and an inorganic substrate. composition. 11. (a) source of diquaternary ammonium ions, an oxidation selected from boron oxide; oxide selected from silicon oxide, germanium oxide and mixtures thereof. preparing an aqueous mixture comprising; (b) Bring the mixture to a temperature of at least 140°C until zeolite crystals form. and (c) recovering said crystals. A method for producing a zeolite according to claim 1, comprising: 12. The aqueous mixture has a composition falling within the following ranges with respect to the molar ratio of oxides: YO2/W2O3, greater than 10; Q/YO2, 0.05:1 to 0.50: 1, where Y is selected from silicon, germanium, and mixtures thereof, and W is selected from boron, and Q is bis(1-azoniabicyclo[2,2,2]o 12. Process according to claim 11, wherein the ctane-α'ω-alkane compound. 13. Diquaternary ammonium ion has the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A method according to claims 11 and 12, derived from a compound of. 14. A hydrocarbonaceous feed according to claim 1 or 2 under hydrocarbon conversion conditions. A method of converting hydrocarbons comprising contacting them with a zeolite. 15. Hydrocarbon feedstock under hydrocracking conditions with the zeolite of claim 1. 15. A process according to claim 14, which is a hydrocracking process comprising contacting. 16. The hydrocarbonaceous feedstock of claim 1 under catalytic reforming conditions. Claim 14 is a contact reforming method comprising contacting with a light. The method followed. 17. (a) has a boiling point of about 40°C or more and about 200°C or less under aromatic conversion conditions; Claim 1 provides a hydrocarbonaceous feed comprising straight chain and slightly branched hydrocarbons. zeolite, wherein said zeolite substantially contains acidity. There is no, and (b) collecting the aromatic-containing effluent; A method according to claim 14, which is a method for manufacturing a product. 18. According to claim 17, the zeolite comprises a Group VIII metal component. Method. 19. Hydrocarbon feedstock under hydrocracking conditions with the zeolite of claim 1. 15. A process according to claim 14, which is a hydrocracking process comprising contacting. 20. Charge hydrocarbon feedstock in reaction zone under catalytic cracking conditions without added hydrogen It is a catalytic cracking method that involves contacting with a catalyst containing a zeolite according to the scope of item 1. , a method according to claim 14. 21. A component that is a zeolite according to claim 1 and a large-pore crystalline aluminosilicon. According to claim 20 using a catalyst composition comprising an acid salt cracking component Method. 22. Crystalline aluminosilicate cracking component from 8.0 angstroms 22. The method of claim 21, having a large pore size. 23. According to claim 21, the catalyst composition is a physical mixture of two components. method. 24. One of the components is an inorganic oxide, such as silica, alumina, amorphous silica Lumina, silica-magnesia, silica-zirconia, alumina-boria, aluminum natitanate, synthetic clays, such as synthetic mica-montmorillonite, natural clays, For example, kaolin, halloysite, montmorillonite, attapulgite, sepi olites and saponites, acid activated clays, pyra red or cross-linked clays and Claim 1, which is the zeolite of Claim 1 blended into a mixture thereof. Method according to paragraph 21. 25. The two catalyst components are arranged in an inorganic matrix comprising the inorganic oxide of claim 24. 22. A method according to claim 21. 26. at least one Group VIII metal under isomerization conditions and claim 1. Catalysts containing zeolites with linear and slightly branched C4 to C7 hydrocarbons An isomerization process for isomerizing C4 to C7 hydrocarbons, comprising contacting a C4 to C7 hydrocarbon with a feed containing A method according to claim 14, wherein: 27. After impregnation with Group VIII metal, the catalyst is calcined in steam/air at elevated temperature. 27. A method according to claim 26. 28. 27. A method according to claim 26, wherein the Group VIII metal is platinum. 29. at least partially under liquid phase conditions and the presence of a zeolite according to claim 1; At present, at least a molar excess of aromatic hydrocarbons is combined with a C2 to C20 olefin and an alkyl A method of alkylating aromatic hydrocarbons comprising contacting the aromatic hydrocarbons under alkylation conditions. A method according to Scope No. 14. 30. Aromatic hydrocarbons and olefins each present in a molar ratio of about 4:1 to 20:1 A method according to claim 29, comprising: 31. Aromatic hydrocarbons include benzene, toluene and xylene, or mixtures thereof A method according to claim 29, wherein the method is a selected member of the group consisting of: 32. at least partially under liquid phase conditions and the presence of a zeolite according to claim 1; Transalkylation of aromatic hydrocarbons with polyalkyl aromatic hydrocarbons under The claimed method is a process for transalkylation of aromatic hydrocarbons comprising contacting with A method according to Scope No. 14. 33. The aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon are each about 1:1. 33. The method according to claim 32, wherein the method is present in a molar ratio of about 25:1. 34. Aromatic hydrocarbons include benzene, toluene and xylene, or mixtures thereof 33. A method according to claim 32, wherein the method is a member selected from the group consisting of: 35. Claim No. 1, wherein the polyalkyl aromatic hydrocarbon is dialkylbenzene. Method according to paragraph 32. 36. The olefin feed under oligomerization conditions is added to the zeolite of claim 1. according to claim 14, which is an oligomerization method comprising contacting with Method.