MXPA98003994A - Zeolite ssz - Google Patents

Abstract

The present invention relates to a new zeolite crystalline SSZ-44 prepared by processes when preparing crystalline molecular sieves, particularly zeolites with large pores, using a standard agent the cation N, N-diethyl-cis-2,6, dimethyl piperidi

Description

ZEOLITE SSZ-44 The present invention relates to a new crystalline SSZ-44 zeolite, a method for preparing SSZ-44 using a standard agent the cation N, N-diethyl-cis-2, β-dimethyl piperidino, and the process employs SSZ-44 as a catalyst Because of their unique screening characteristics, as well as their catalytic properties, crystalline molecular sieves are especially useful in applications such as hydrocarbon conversion, drying and gas separation. Although several crystalline molecular sieves have been discussed, there is a continuing need for new zeolites with desirable properties for gas separation and drying, chemical and hydrocarbon conversions, and other applications. The new zeolites may contain novel internal porous itectures, which provide improved selectivities in these processes. A variety of patterns have been used to synthesize a variety of molecular sieves, including zeolites from the silicate, aluminosilicate, and borosilicate families. However, the REF: 27397 zeolite specifies that can be obtained when using given pattern is currently unpredictable. The present invention is directed to a family of crystalline molecular sieves with unique properties, referred to herein as "zeolite SSZ-44" or simply "SSZ-44". Preferably SSZ-44 is obtained in its silicate, aluminosilicate, titanosilicate, vanadiosilicate or borosilicate forms. The term "silicate" refers to a zeolite having a high molar ratio of silicon oxide related to aluminum oxide, preferably a molar ratio greater than 100. As used herein the term "aluminosilicate" refers to a zeolite which it contains both alumina and silica and the term "borosilicate" refers to a zeolite containing oxides of boron and silica. In accordance with the present invention, a zeolite having an average pore size of greater than about 6 Angstroms and having the X-ray diffraction lines of Table I is provided. In accordance with this invention, here also provides a zeolite having a molar ratio of an oxide of a first tetravalent element with an oxide of a second trivalent or tetravalent second of said first tetravalent element, said molar ratio is greater than about 20 and has the diffraction lines of the rays. X of Table I. Further in accordance with this invention herein is provided a zeolite having a molar ratio of an oxide selected from silicon oxide, germanium oxide and mixtures thereof with an oxide selected from aluminum oxide , gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures of these greater than about 20 and having lin refraction of the X-rays from Table I below. The present invention also provides a zeolite having a composition, synthesized and in the anhydrous state, in terms of molar ratio as follows: YO2 / WaOb > 20 M7Y02 < 0.05 Q / Y02 0.01-0.10 Wherein Q comprises a cation of N, N-dimethyl-cis-2,6-dimethyl piperidino; M is a cation of a metallic alkali; W is selected from the group of aluminum, gallium, iron, boron, titanium, indium, vanadium and mixtures thereof; a = l or 2, b = 2 when a is 1 (for example, W is tetravalent) and b = 3 when a is 2 (for example, W is trivalent); and Y is selected from the group consisting of silicon, germanium, and mixtures thereof. According to this invention, a zeolite prepared by heat treating a zeolite having a molar ratio of an oxide selected from silicon oxide, germanium oxide, iron oxide, boron oxide, titanium oxide, oxide is provided herein. of indium, vanadium oxide and mixtures of these greater than about 20 and having X-ray diffraction lines of Table I at a temperature from about 200 ° C to about 800 ° C, the zeolite thus prepared having the X-ray diffraction lines of Table II. The present invention also includes this zeolite so prepared that it is predominantly hydrogenated, this hydrogenated form is prepared by ion exchange with an acid or with a solution of an ammonium salt followed by a second calcination. According to the present invention, a catalyst comprising the zeolite of this invention predominantly in the hydrogenated form is also provided herein.

In addition, a catalyst comprising the zeolite of this invention made substantially free of acidity by neutralizing said zeolite with a basic metal is provided according to this invention. Also provided in accordance with the present invention is a method for preparing a crystalline material comprising one or a combination of oxides selected from the group consisting of oxides of one or more tetravalent element (s) and one or more element (s). ) trivalent (s), said method comprises contacting under crystallization conditions the sources of said oxides and a standard agent comprising a cation of N, N-diethyl-cis-2,6,6-dimethyl piperidino. The present invention further provides a process for converting hydrocarbons comprising contacting a hydrocarbonate feed to the hydrocarbon conversion conditions with a catalyst comprising the zeolite of this invention. Furthermore, a thermal hydrofraction process is provided by the present invention, comprising by contacting a feed under conditions of thermal hydrofraction with a catalyst comprising the zeolite of this invention, preferably in the hydrogenated form. This invention also includes a dewaxing process comprising contacting a hydrocarbon feed under the dewaxing conditions with a catalyst comprising the zeolite of this invention, preferably in the predominantly hydrogenated form. Also included in this invention is a process for increasing the octane of a hydrocarbon feed to produce a product having a high aromatics content comprising contacting a hydrocarbonaceous feed comprising normal and slightly branched hydrocarbons having a boiling range above. approximately 40 ° C and less than about 200 ° C, under the conditions of aromatic conversion with a catalyst comprising the zeolite of this invention made substantially free of acidity by neutralizing said zeolite with a basic metal. Also provided in this invention is a process wherein the zeolite contains a metal compound of Group VIII. Also provided by the present invention is a catalytic thermal fractionation process comprising contacting a hydrocarbon feed in a reaction zone under catalytic thermal fractionation conditions in the absence of hydrogen added with a catalyst comprising the zeolite of this invention, preferably in the hydrogenated form predominantly. Also included in this invention is a catalytic thermal fractionation process where the catalyst additionally comprises a crystalline thermal fractionation compound with large pores. The present invention further provides an isomerization process for isomerizing hydrocarbons from C to C7, comprising contacting a catalyst, comprising at least one Group VIII metal and the zeolite of this invention, preferably in predominantly hydrogenated form, with a feed which has normal and slightly branched C4 to C7 hydrocarbons under isomerization conditions. An isomerization process is also provided where the catalyst has been calcined in a vapor / air mixture at an elevated temperature after impregnation of the group VIII metal, preferably platinum. This invention also provides a process for alkylating an aromatic hydrocarbon comprising contacting under alkylation conditions at least one mole in excess of an aromatic hydrocarbon with a C2 to C20 olefin under at least partial liquid phase conditions and in the presence of a catalyst comprising the zeolite of this invention, preferably in the predominantly hydrogenated form. This invention further provides a process for transalkylating an aromatic hydrocarbon comprising contacting under transalkylation conditions an aromatic hydrocarbon, a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of a catalyst comprising the zeolite of this invention., preferably in the predominantly hydrogenated form. Additionally provided by this invention a process to convert paraffins to aromatics which comprises contacting paraffins with a catalyst comprising the zeolite of this invention, preferably in the hydrogen form predominantly, said catalyst comprising gallium, zinc, or a compound of gallium or zinc. This invention also provides a process for converting light alcohols and other oxygenated hydrocarbons comprising contacting said lower alcohol or other oxygenated hydrocarbon with a catalyst comprising the zeolite of this invention, preferably in the hydrogen form predominantly under conditions to produce liquid products . Also provided in accordance with this invention a process for isomerizing an isomerization feed comprising an aromatic C8 stream of xylene isomers or mixtures of xylene isomers and ethylbenzene, wherein a ratio of ortho- nearest equilibrium is obtained, meta and para-xylene, said process comprises contacting said feed under isomerization conditions with a catalyst comprising the zeolite of this invention, preferably in the predominant hydrogenated form. The present invention further provides a process for oligomerizing olefins comprising contacting an olefin feed under oligomerization conditions with a catalyst comprising the zeolite of this invention, preferably in the predominantly hydrogenated form. the present invention also provides an improved process for reducing nitrogen oxides contained in a gas stream in the presence of oxygen wherein said process comprises contacting the gas stream with a zeolite process, the improvement comprising using as the zeolite one zeolite having a mole ratio of an oxide of a first element with an oxide of a second tetravalent element or different trivalent from said first tetravalent element, said mole ratio is greater than about 20 and has lines of diffraction X-rays of the Table I. The zeolite may contain a metal or metal ions capable of catalyzing the reduction of the nitrogen oxides, and may be carried out in the presence of a stoichiometric excess of oxygen. In a preferred embodiment, the gas stream is the exhausted current of an internal combustion engine.

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises a family of large crystalline pore zeolites, SSZ-44. As used herein, the term "large pore" means that it has an average pore size diameter greater than about 6 Angstroms, preferably from about 6.5 Angstroms to about 7.5 Angstroms. In the preparation of zeolite SSZ-44, a cation of N, N-dimethyl-cis-2,6,6 dimethyl piperidino is used as a crystallization standard. In general, SSZ-44 is prepared by contacting an active source of one or more oxides selected from the group consisting of oxides of monovalent elements, oxides of divalent elements, oxides of trivalent elements and oxides of tetravalent elements with the standard agent N, N-dimethyl-cis-2,6,6-dimethyl piperidino (look like "Q" below). The SSZ-44 is prepared from a reaction mixture having the composition shown in Table A below.

TABLE A- Reaction Mixture where Y,, a, b, Q and M are as defined below. In practice, SSZ-44 is prepared by a process comprising: (a) preparing an aqueous solution containing at least one oxide capable of forming a crystalline molecular sieve and a cation of N, N-diethyl-cis- 2, β-dimethyl piperidino having an anionic counter which is not detrimental to the formation of SSZ-44; (b) maintaining the aqueous solution under conditions sufficient to form SSZ-44 crystals; and (c) recovery of SSZ-44 crystals. Accordingly, SSZ-44 may comprise the crystalline material and the standard agent in combination with metal and non-metallic oxides linked in tetrahedral coordination through a grid of oxygen atoms to form an interlaced three-dimensional crystal structure. The metal and non-metal oxides comprise one or a combination of oxides of a first tetravalent element (s), and one or a combination of a second (s) trivalent (s) or tetravalent (s) element (s) ) different (s) of the first (s) element (s) tetravalent (s). The first tetravalent element (s) is preferably selected from the group consisting of silicon, germanium and combinations thereof, silicon is more preferred. The second trivalent (s) or tetravalent element (s) (which is different from the first tetravalent element) is preferably selected from the group consisting of aluminum, gallium, iron, boron, titanium, indium, vanadium and combinations thereof, aluminum, boron, or titanium are more preferable. Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, aluminum colloids, aluminum oxides coated with silica solution, hydrated alumina gels such as Al (OH) 3, and aluminum compounds such as A1C13 and A1 ( S0) 3. Typical sources of silicon oxides include silicates, silica hydrogel, silicic acid, smoked silica, colloidal silica, tetralkyl orthosilicates, and silica hydroxides. Boron, such as gallium, germanium, titanium, indium, vanadium and iron, can be added correspondingly to their aluminum and silicon counterparts. A source of reactive zeolite can provide a source of aluminum or boron. In most cases, the source of zeolite can provide a source of silica. The source of silica in its aluminum-free or boronless forms can also be used as a silica source, with the use of the addition of silicon, for example, the conventional sources listed above. The use of a reactive zeolite source as a source of alumina for the current process is fully described in U.S. Patent No. 4,503,024 published March 5, 1985 by Bourgogne, the discussion is incorporated herein by reference. Typically, the hydroxide of an alkali metal and / or a hydroxide of an alkaline earth metal, such as sodium, potassium, lithium, cesium, rubidium, calcium and magnesium hydroxide, is used in the reaction mixture; Nevertheless, this compound can be omitted as long as the equivalent basicity is maintained. The standard agent can be used to provide the hydroxyl ion. Thus, this can benefit the ion exchange, for example, the halide for a hydroxyl ion, thereby reducing or eliminating the required amount of alkali metal hydroxide. The cation of the alkali metal or alkaline earth cation can be part of the synthesized crystalline oxide material, in order to balance the charge of electrons in the valence there.

The reaction mixture is maintained at an elevated temperature until the crystals of the zeolite SSZ-44 are formed. Hydrothermal crystallization is usually carried out under autogenous pressure at a temperature between 100 ° C and 200 ° C, preferably between 135 ° C and 180 ° C. The crystallization period is typically greater than 1 day and preferably from 3 days to about 20 days. Preferably the zeolite is prepared using a gentle movement or stirring. During the hydrothermal crystallization step, SSZ-44 crystals can be allowed to spontaneously form nuclei from the reaction mixture. The use of SSZ-44 crystals as a material for nucleation can be advantageous by decreasing the time necessary for full crystallization to occur. In addition, the sowing of crystals can cause an increase in the purity of the product obtained by promoting nucleation and / or the formation of SSZ-44 on any undesirable phase. When used as crystallization seeds, the SSZ-44 crystals are added in an amount between 0.1 and 10% of the weight of the silica used in the reaction mixture. Once the zeolite crystals have formed, the solid product is separated from the mixing reaction by standard mechanical separation techniques such as filtration. The crystals are washed with water and then dried, for example, from 90 ° C to 150 ° C for 8 to 24 hours, to obtain the SSZ-44 zeolite crystals synthesized. The drying step can be developed at atmospheric or vacuum pressure. The SSZ-44 as prepared has a molar ratio of an oxide selected from silica oxide, germanium oxide and mixtures thereof with an oxide selected from aluminum oxide, gallium oxide, iron oxide, oxide boron, titanium oxide, indium oxide, vanadium oxide, and mixtures thereof are greater than 20; and has the X-ray diffraction lines of Table I below. The SSZ-44 also has a composition, likewise synthesized and in the anhydrous state, in terms of molar ratios, shown in Table B below.

TABLE B- as-SSZ-44 synthesized where Y,, a, b, M and Q are as defined above. The SSZ-44 can be made essentially free of aluminum, for example, having a molar ratio of silica and alumina of oo. The term "essentially free of aluminum" means that no aluminum is added intentionally to the reaction mixture, for example, as an alumina or aluminate reagent, and to some extent aluminum is present, this is presented only as a contaminant in the reagents An additional method to increase the molar ratio of silica with alumina is made by using a standard acid grout or grout treatments. The SSZ-44 can also be prepared directly as any aluminosilicate or borosilicate. Low ratios of silica with alumina can be obtained by using methods that insert aluminum into the crystalline structure. For example, the aluminum insert can occur by the thermal treatment of the zeolite in combination with an aluminum binder the source of dissolved aluminum. Such procedures are described in Patent 4,559,315, published on December 17, 1985 by Chang, et. to the.

It is believed that the SSZ-44 is composed of a new structure of the skeleton or topology that is characterized by its X-ray diffraction pattern. The SSZ-44 zeolites synthesized have a crystalline structure whose X-ray powder diffraction pattern exhibits the characteristic lines shown in Table I and is therefore distinguished from other known zeolites.

TABLE I- SSZ-44 Synthesized (a) The pattern of the X-rays provided is based on a scale of relative intensity in which the strongest line in the X-ray pattern is assigned a value of 100: D (weak) is less than 20; M (medium) is between 20 and 40; F (strong) is between 40 and 60; MF (very strong) is greater than 60. After calcination, the SSZ-44 zeolites have a crystal structure whose powder diffraction pattern in the X-rays includes the characteristic lines shown in Table II: TABLE II - Calcined SSZ-44 The refractive patterns of dust in X-rays were determined by standard techniques. The radiation was K-alpha / double copper. Peak height and positions, as a function of 2? where ? is the angle Bragg, was read from the relative intensities of the peaks, and d, the interplanar spacing in Angstroms that corresponds to the registered lines, can be calculated. The variation in the measurements of the dispersion angle (two teta), is due to the error of the instruments and to differentiate the individual samples, it is estimated as +/- 0.20 degrees. Minor variations in the diffraction pattern can result from variations in the molar ratio of silica with alumina or silica with boron from individual samples due to changes in constant networks. In addition, quite a few small crystals can affect the shape and intensity of the peaks, leading to significant spreading of the peak. Calcination can also cause changes in peak intensities when compared to the "already-done" material patterns, as well as minor changes in the diffraction pattern. The zeolite produced by changing the metal or other cations present in the zeolite with other different cations (such as H + or NH4 +) produce essentially the same diffraction pattern, although again, there may be minor changes in the interplanar space and variations in the relative intensities of the peaks. Despite these minor perturbations, the basic crystalline network remains unchanged by these treatments.

The crystalline SSZ-44 can be used synthesized, but preferably it can be thermally treated (calcined). Usually, it is desired to remove the alkali metal cation by ion exchange and replacing at least a portion thereof with hydrogen, ammonium, or other desirable metal ion. The zeolite can be leached with chelating agents, for example, EDTA or dilute acid solutions, to increase the molar ratio of silica to alumina. The zeolite can also be vaporized; vaporization helps to stabilize the crystalline network attacked by acids. The zeolite can be used in intimate combination with hydrogenation compounds, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum, for these applications in which a hydrogenation-dehydrogenation function. The metals can also be introduced into the zeolite by replacing some of the cations in the zeolite with metal cations by means of standard ion exchange techniques (see, for example, US Patent Nos. 3,140,249 published July 7, 1964 by Plank et al. al., 3,140,251 published July 7, 1964 by Plank, et al., and 3,140,253 published July 7, 1964 by Plank, et al.). Typically the replacement of the cations may include the metal cations, for example, rare earth metals, Group IA, Group HA and Group VIII, as well as their mixtures. For the replacement of metal cations, metal cations such as rare earths, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn and Fe are particularly preferred. Hydrogen, ammonium and metal compounds can be exchanged ionically within the SSZ-44. The zeolite can also be impregnated with the metals, or, the metals can physically and intimately be mixed with the zeolite using standard methods known in the art. Despite the presence of cations in the synthesized form of SSZ-44, the spatial arrangement of the atoms that form the basic crystal lattice of the zeolite remains essentially unchanged. The SSZ-44 can be composed of other materials resistant to temperatures and other conditions used in organic conversion processes. Such matrix materials include active and inactive and synthetic materials or naturally zeolites are found as well as inorganic materials such as clays, silica and metal oxides. Examples of such materials and the manner in which they can be used are discussed in US Patent No. 4,910,006, published May 20, 1990 by Zones et. al., and U.S. Patent No. 5,316,753, published on May 31, 1994 by Nikagawa, both were incorporated herein by reference in their totalities.

Processes for the Conversion of Hydrocarbons SSZ-44 zeolites are useful in hydrocarbon conversion reactions. Hydrocarbon conversion reactions are chemical and catalytic processes in which carbon-containing compounds are changed to compounds that contain different carbon. Examples of hydrocarbon conversion reactions in which SSZ-44 are expected to be useful include catalytic thermal fractionation, thermal hydrofraction, dewaxing, alkylation and olefin and aromatics formation reactions. The catalysts are also expected to be useful in other hydrocarbon conversion and petroleum refining reactions such as isomerizing n-paraffins and naphthenes, polymerizing and oligomerizing olefinic and acetylenic compounds such as isobutylene and l-butene, reforming, alkylating (including alkylation) of aromatics by other hydrocarbons), isomerizing polyalkyl substituted aromatics (e.g., m-xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of high molecular weight benzene, xylenes and methylbenzenes and oxidation reactions. Reactions of new arrangement to make various naphthalene derivatives are also included. The SSZ-44 catalyst has great selectivity, and under hydrocarbon conversion conditions it can provide a high percentage of desired products relative to the total products. SSZ-44 zeolites can be used in the processing of hydrocarbonaceous feeds. Hydrocarbon feeds contain carbon compounds and can be made from different sources, such as virgin petroleum fractions, recycled petroleum fractions, bituminous shale oils, liquefied coal vapors, asphalts, NAO synthetic paraffins, recycled plastic feeds and in general, it can be any feed containing carbon susceptible to the catalytic reactions of the zeolite. Depending on the type of processing the hydrocarbon feed experienced, the feed may contain metal or may be free of metals, this may also have a high or low amount of nitrogen and sulfur impurities. This can be appreciated, however, this processing in general can be more efficient (and the catalyst more active) the decrease of the metal, nitrogen and sulfur content of the feed. The conversion of the hydrocarbonaceous feeds can be carried out in any convenient way, for example, in fluidized bed reactors, moving bed, or fixed bed depending on the types of processes desired. The formulation of the particles can vary depending on the conversion process and the method of operation. Other reactions that can be developed using the catalyst of this invention contain a metal, for example, a Group VIII metal such as platinum, including hydrogenation reactions dehydrogenation, denitrogenation reactions and desulphurisation.

The following Table indicates conditions of the typical reactions that can be employed when catalysts comprising SSZ-44 are used in the conversion reactions of this invention. The preferred conditions are indicated in parentheses. 1 Several hundred atmospheres 2 Gas phase reaction 3 Hydrocarbon partial pressure 4 Liquid phase reaction 5 WHSV Other conditions and reaction parameters are provided below.

Thermal Hydro-cracking Using a catalyst comprising SSZ-44 in hydrogenated form and a hydrogenation promoter, the residual heavy oil feeds, cyclic feeds and other feeds of the feedstock can be hydrofractioned using the process conditions and catalyst components discussed in the aforementioned in U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753. The thermal hydrofraction catalyst contains an effective amount of at least one hydrogenation compound of the type commonly used in thermal hydrofraction catalysts. The hydrogenation compounds are generally selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, which include the salts, complexes and solutions that contain these. The hydrogenation catalyst is preferably selected from the group of metals, salts and complexes thereof of the group consisting of at least one of these platinum, palladium, rhodium, iridium, ruthenium and mixtures thereof or the group consisting at least of nickel, molybdenum , cobalt, tungsten, titanium, chromium, and mixtures of these. With reference to catalytically active metals or metals, it is intended to encompass such metal or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate and the like. The hydrogenation catalyst is present in an amount effective to provide the hydrogenation function of the thermal hydrofraction catalyst, and preferably in the range of 0.05 to 25% by weight.

Dewaxing SSZ-44 in the hyenated form can be used to dewax hyarbonaceous feeds by selective removal of straight paraffin chains. Typically, the viscosity index of the dewaxed product (compared to the fatty feed) is improved when the fat feed is contacted with the SSZ-44 under dewaxing and isomerization conditions. The conditions of the catalytic dewaxing are dependent to a great extent on the feed used and on the desired pour point. The hyen is preferably present in the reaction zone during the catalytic dewaxing process. The feed ratio with hyen is typically between about 500 and about 30,000 SCF / bbl (cubic feet per barrel), preferably about 1000 to about 20,000 SCF / bbl. Generally hyen can be separated from the product and recycled to the reaction zone. Typically feeds include light gas oil, heavy gas oil and reduced crude oils that have boiling points above 350 ° F. A typical dewaxing process is the catalytic dewaxing of a hyarbon feed having boiling points above 350 ° F and containing straight chain hyarbons and slightly branched hyarbon chains by contacting the hyarbon feedstock in the presence of the hyarbon gas. hyen added at a hyen pressure of 15-3000 psi with a catalyst comprising SSZ-44 and at least one metal of group VIII.

Hyesparaffinizer SSZ-44 may optionally contain a hyenation compound of the type commonly employed in dewaxing catalysts. See the aforementioned US Patent No. 4,910,006 and Patent No. 5,316,753 for example of these hyenation compounds. The hyenation compound is present in an effective amount to provide an effective hysomerization and hyewaxing catalyst preferably in the range of from about 0.05 to 5% by weight. The catalyst can be tested in such a way as to increase the isodesparaffin in the expense of thermal fractionation reactions.

The feed can be thermally hyractionated, followed by dewaxing. This type of two-stage process and the typical thermal hyraction conditions are described in US Patent No. 4,921,594, published May 1, 1990 by Miller, which is incorporated herein by reference in its entirety. SSZ-44 can also be used as a deparaffinizing catalyst in the form of a stratified catalyst. That is, the catalyst comprises a first layer comprising zeolite SSZ-44 and at least one Group VIII metal, and a second layer comprising an aluminosilicate zeolite having a more selective form than the zeolite SSZ-44. The use of a stratified catalyst is discussed in U.S. Patent No. 5,149,421, published September 22, 1992 by Miller, which is incorporated herein in its entirety. The stratification may also include a bed of SSZ-44 laminated with a non-zeolitic compound designed for thermal hyraction or hyinishing.

SSZ-44 can also be used for the dewaxing of refined products, including the oil supply of oil shale, under conditions such as those discussed in US Patent No. 4,181,598, published January 1, 1980 by Gillespie et. al., which is incorporated herein by reference in its entirety. It is frequently desired to use medium hyenation (sometimes referred to as hyinishing) to produce more stable dewaxed products. The hyinishing step can be carried out before or after the dewaxing step, and preferably afterwards. Hyinishing is typically performed at temperatures in the range from about 190 ° C to about 340 ° C at pressures from about 400 psig to about 3000 psig at spaces speeds (LHSV) between approximately 0.1 and 20 and a recycled hydrogen velocity of approximately 400 to 1500 SCF / bbl. The hydrogenation catalyst employed can be active enough not only to hydrogenate the olefins, diolefins and color bodies that may be present, but also to reduce the aromatic content. Suitable hydrogenation catalysts are discussed in U.S. Patent No. 4,921,594, published May 1, 1990 by Miller, which is incorporated herein by reference in its entirety. The step of hydrofinishing is beneficial to prepare an acceptable stable product (eg, a lubricating oil) since the dewaxed products prepared from thermal hydrofraction feeds tend to be unstable in the air and light and tend to form sediments spontaneously and rapidly. Lubricating oil can be prepared using the SSZ-44. For example, a C20 + lubricating oil can be made by isomerizing a C20 + olefin fed on a catalyst comprising SSZ-44 in the hydrogenated form and at least one Group VIII metal. Alternatively, the lubricating oil can be made by thermal hydrofraction in a hydrocarbonaceous feed in a thermal hydrofraction zone to obtain an effluent comprising a thermally hydrofracted oil, and catalytically dewaxing the effluent at a temperature of at least about 400 ° F and a pressure of 15 psig to about 3000 psig in the presence of hydrogen gas added with a catalyst comprising SSZ-44 in the hydrogenated form and at least one Group VIII metal.

Formation of aromatics SSZ-44 can be used to convert straight light weight naphthas and similar mixtures to high molecular weight aromatic mixtures. Thus, hydrocarbons of normal and slightly branched chains, preferably having a boiling range above about 40 ° C and less than about 200 ° C, can be converted to products having a substantially large octane aromatic content upon contacting the hydrocarbon feed with a catalyst comprising the SSZ-44. It is also possible to convert heavier feeds into BTX or valuable naphthalene derivatives when using catalysts containing SSZ-44. The conversion of the catalyst preferably contains a Group VIII metal compound having sufficient activity for commercial use. By metal compound of Group VIII as used herein it refers to the metal itself or a compound thereof. The noble metals of Group VIII and its compounds, platinum, palladium and iridium, or combinations of these can be used. The rhenium or tin or a mixture thereof may also be used in conjunction with the Group VIII metal and preferably a noble metal compound. The most preferred metal is platinum. Most Group VIII metals present in the catalyst conversion may be within the normal range for use in reforming catalysts, from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent. It is critical for the selective production of aromatics in useful amounts that the conversion of the catalyst is substantially free of acidity, for example, by neutralizing the zeolite with a basic metal compound, for example, an alkali metal. Methods for providing the acid free catalyst are known in the art. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for a description of these methods. The preferred alkali metals are sodium, potassium, rubidium and cesium. The zeolite itself may be substantially free of acidity only at very large molar ratios of silica alumina.

Thermal Fractionation eat-alit-tt-f-Thermal fractionation feeds of the hydrocarbon can be fractionated thermally and catalytically in the absence of hydrogen, using SSZ-44 in the hydrogen form. When SSZ-44 is used as a catalytic thermal fractionation catalyst in the absence of hydrogen, the catalyst can be used in conjunction with traditional thermal fractionation catalysts, for example, any aluminosilicate hitherto employed as a component in thermal fractionation catalysts. Typically, there are crystalline aluminosilicates, with large pores. Examples of these traditional thermal fractionation catalysts are discussed in the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753. When a conventional traditional thermal fractionation catalyst (TC) is employed, the relative weight ratio of the TC to the SSZ-44 is generally between about 1:10 and about 500: 1, desirably between about 1:10 and about 200: 1. , preferably between about 1: 2 and about 50: 1, and more preferably between 1: 1 and about 20: 1. The zeolite and / or the traditional thermal fractionation compound can also be exchanged ionically with rare earth ions to modify the selectivity. Thermal fractionation catalysts are typically employed with a thermally fractionated compound of inorganic oxide. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for examples of such matrix compounds.

Oligomerization It is expected that SSZ-44 in the hydrogenated form can also be used to oligomerize straight and branched chain olefins containing from 2 to 21 and preferably 2-5 carbon atoms. The oligomers that are the products of the process are high and intermediate molecular weight olefins that are useful for both fuels, for example, gasoline or a mixed feed of gasolines and chemicals. The oligomerization process comprises contacting the olefin feed in liquid or gaseous phase with a catalyst comprising SSZ-44.

The zeolite may have the original cations associated with those replaced by a wide variety of other cations according to techniques well known in the art. Typically the cations may include hydrogen, ammonium and metal cations including mixtures thereof. Of the metal cations that are replaced, particular preference is given to the cations of metals such as rare earth metals, manganese, calcium, as well as of Group II of the Periodic Table, for example, zinc, and of Group VIII of the Table Periodic, for example, nickel. One of the first requirements is that the zeolite possesses a rather low aromatization activity, for example, wherein the amount of aromatics produced is not more than about 20% by weight. This is accomplished by using a zeolite with controlled acid activity (alpha value) from about 0.1 to about 120, preferably from about 0.1 to about 100, as measured by its ability to fractionate n-hexane.

The alpha values are defined by a standard test known in the art, for example, as shown in U.S. Patent No. 3,960,978 published June 1, 1976 by Givens, et. to the. which is fully incorporated here by reference. If required, such zeolites may be obtained by vaporization, which is used in a conversion process or by any other method that may be found by some person skilled in the art.

Conversion of Paraffins to aromatics SSZ-44 in the hydrogenated form can be used to convert C2-C6 light gas paraffins to high molecular weight hydrocarbons including aromatics. Preferably, the zeolite may contain a metal or metal oxide catalyst wherein said metal is selected from a group consisting of Group IB, IIB, VIII and IIIA of the Periodic Table. Preferably, the metal is gallium, niobium, indium or zinc in the range from about 0.05 to 5% by weight.

Condensation of Alcohols SSZ-44 can be used to condense light aliphatic alcohols having from 1 to 10 carbon atoms in a hydrocarbon product with a boiling point as gasoline comprises mixtures of aliphatic and aromatic hydrocarbons. The process discussed in US Patent No. 3,894,107 published July 8, 1975 by Butter et. al., describes the process conditions used in this process, whose patent is fully incorporated herein in the reference. The catalyst may be in the hydrogenated form or may have an interchanged or impregnated base to contain ammonium complement or a metal cation, preferably in the range from about 0.05 to 5% by weight. Metal cations that may be present include any of the metals of Groups Y through VIII of the Periodic Table. However, in the case of Group IA metals, the content of the cation should in no case be as great as the effective inactivation of the catalyst, the exchange should not be to eliminate the total acidity. There may be other processes that involve treating oxygenated substrates where a basic catalyst is desired.

Isomerization The current catalyst is highly active and highly selective to isomerize hydrocarbons from C4 to C7. The activity means that the catalyst can operate at a relatively low temperature which thermodynamically favors branched paraffins of high molecular weight. Therefore, the catalyst can produce a high molecular weight octane product. The high selectivity means that relatively high molecular weight liquid can be made when the catalyst is tested with a high molecular weight octane. The present process comprises contacting the isomerization catalyst, for example, a catalyst comprising SSZ-44 in the hydrogenated form, with a hydrocarbon feed under isomerization conditions. The feed is preferably a straight fraction of light, which has boiling point within the range of 30 ° F to 250 ° F and preferably from 60 ° F to 200 ° F.

Preferably, the hydrocarbon feed for the process comprises a substantial amount of slightly branched low octane hydrocarbons.

C4 to C7, more preferably C5 to C6 hydrocarbons. It is preferred to perform the isomerization reaction in the presence of hydrogen. Preferably, the hydrogen is added to give a hydrogen reaction with hydrocarbon (H 2 / HC) of between 0.5 and 10 (H 2 / HC), more preferably between 1 and 8 (H 2 / HC). See the aforementioned US Patent No. 4,910,006 and US Patent No. 5, 316, 753 for further discussion of the isomerization conditions. A low sulfur content feed is especially preferred in the present process. The feed preferably contains less than 10 ppm, more preferably less than 0. 1 ppm sulfur. In the case of a feed that is not already low in sulfur, acceptable levels can be sought by hydrogenating the feed in a presaturation zone with a hydrogenation catalyst that is resistant to sulfur poisoning. see the aforementioned US Patent No. 4,910,006 and US Patent No. 5,316,753 for further discussion of this hydrodesulfurization process. It is preferred to limit the nitrogen level and the water content of the feed. Catalysts and processes that are suitable for these purposes are known to persons skilled in the art. After a period of operation, the catalyst can start to be deactivated by sulfur and coke. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for further discussion of methods for removing this sulfur and coke, and for regenerating the catalyst. The conversion of the catalyst preferably contains a compound with a Group VIII metal to have sufficient activity for commercial use. By compound with a Group VIII metal as used herein it refers to itself or to a compound thereof. The noble metals of Group VIII and its compounds, platinum, palladium, and iridium, or combinations thereof, may be used. Rhenium and tin can also be used in conjunction with noble metals. The most preferred metal is platinum. The amount of group VIII metal present in the conversion catalyst should be within the normal range for use in isomerization catalysts of from about 0.05 to 2.0 weight percent, preferably from 0.2 to 0.8 weight percent.

Alkylation and Transalkylation SSZ-44 can be used in a process for the alkylation or transalkylation of an aromatic hydrocarbon. The process comprises contacting the aromatic hydrocarbon with an olefin alkylation agent of C2 to Cie or a transalkylation agent of a polyalkyl aromatic hydrocarbon, under at least partial liquid phase conditions, and in the presence of a catalyst comprising SSZ -44. SSZ-44 can also be used to remove benzene from gasoline by alkylating benzene as described above and removing the alkylated product from gasoline. For high catalytic activity, zeolite SSZ-44 must be predominantly in its hydrogen ion form. It is preferred that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions. Examples of suitable aromatic hydrocarbon feeds that can be alkylated or transalkylated by the process of the invention include aromatic compounds such as benzene, toluene and xylene. The preferred aromatic hydrocarbon is benzene. There may be occasions where naphthalene derivatives may be desirable. Mixtures of aromatic hydrocarbons can also be used. The olefins suitable for the alkylation of the aromatic hydrocarbons are those containing from 2 to 20, preferably from 2 to 4 carbon atoms., such as ethylene, propylene, l-butene, 2-trans-butene and 2-cis-butene, or mixtures thereof. There may be examples where pentenes are desirable. The preferred olefins are ethylene and propylene. Long chain alpha olefins can also be used. When desired for transalkylation, the transalkylation agent is a polyalkyl aromatic hydrocarbon containing 2 or more alkyl groups each of which may have from 2 to 4 carbon atoms. For example, suitable polyalkano-aromatic hydrocarbons include di-, tri-, and tetra-alkyl aromatic hydrocarbons, such as diethyl benzene, di-isopropyl toluene, dibutylbenzene, and the like. Preferred polyalkyl aromatic hydrocarbons are dialkyl benzenes. A particularly preferred polyalkyl aromatic hydrocarbon is di-isopropyl benzene. When the alkylation is the process performed, the reaction conditions are as follows. The aromatic hydrocarbon feed must be presented with a stoichiometric excess. It is preferred that the molar ratio of aromatics to olefins be greater than four to one to prevent rapid contamination of the catalyst. The reaction temperature may be in the range from 100 ° F to 600 ° F, preferably from 250 ° F to 450 ° F. The reaction pressure must be sufficient to maintain at least a partial liquid phase in order to retard catalyst contamination. This is typically 50 psig to 1000 psig depending on the feed and the reaction temperature. The contact time can range from 10 seconds to 10 hours, but is usually from 5 minutes to 1 hour. The space rate of weight per hour (WHSV), in terms of grams (pounds) of aromatic hydrocarbon and olefin per gram (pounds) of catalyst per hour, is generally within the range of about 0.5 to 50. When transalkylation is the process performed, the molar ratio of the aromatic hydrocarbon can generally have a range of approximately 1: 1 to 25: 1, and preferably from 2: 1 to 20: 1. The reaction temperature may range from about 100 ° F to 600 ° F, but is preferably close to 250 ° F to 450 ° F. The reaction pressure should be sufficient to maintain at least one partial liquid phase, typically in the range of about 50 psig to 1000 psig, preferably 300 psig to 600 psig. The space velocity of the weight per hour can have a range of approximately 0.1 to 10, US Patent No. 5,082,990 published on January 21, 1992 by Hsieh, et. to the. describes such processes and is incorporated herein by reference.

Isomerization of Xylene.

SSZ-44 in the hydrogenated form may also be useful in a process to isomerize one to more isomers of xylene in a C8 aromatic feed to obtain ortho-, meta-, and para-xylene in a ratio that approximates the equilibrium value . In particular, isomerization of Xylene is used in conjunction with a separate process for manufacturing para-xylene. For example, a part of the para-xylene in a stream of mixed C8 aromatics can be recovered by crystallization and centrifugation. The mother liquor of the crystallizer is then reacted under xylene isomerization conditions to re-establish ortho-, meta- and para-xylenes at a close equilibrium ratio. At the same time, part of the ethyl benzene in the mother liquor is converted into xylenes or products that are easily separated by filtration. The isomerate is mixed with a fresh feed and the combined stream is distilled to remove the heavy and light sub products. The resultant C8 aromatic stream is then sent to the crystallizer to repeat the cycle. Optionally, isomerization in the vapor phase is carried out in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (for example, ethylbenzene). If the hydrogen is used the catalyst should comprise about 0.1 to 2.0% by weight of a hydrogenation / dehydrogenation compound selected from the metal compound of Group VIII (from the Periodic Table), especially platinum or nickel. Group VIII metal compound means metal and its compounds such as oxides and sulfides. Optionally, the isomerization feed may contain from 10 to 90% by weight of a diluent such as toluene, trimethylbenzene, naphthenes or paraffins.

Other Uses for the SSZ-44.

SSZ-44 can also be used as an adsorbent with high selectivities based on molecular screening behavior and also based on preferential hydrocarbon packing within the pores. SSZ-44 can also be used for the catalytic reduction of nitrogen oxides in a gas stream. Typically, the gas stream may contain oxygen, often a stoichiometric excess thereof. Also, the SSZ-44 may contain a metal or metal ions within or in it that are capable of catalyzing the reduction of nitrogen oxides.

Examples of such metals or metal ions include copper, cobalt and mixtures thereof. An example of a process for the catalytic reduction of nitrogen oxides in the presence of a zeolite is discussed in U.S. Patent No. 4,297,328, published on October 27, 1981 by Ritscher et. to the. which is incorporated here by reference. There is, the catalytic process is the combustion of carbon monoxide and hydrocarbons and the catalytic reduction of nitrogen oxides contained in a gas stream, such as the spent gas of an internal combustion engine. The zeolite used is an ionically exchanged metal, is varnished or charged sufficiently to provide an effective amount of copper metal or catalytic copper ions in or on the zeolite. In addition, the process is carried out with an excess of oxidant, for example, oxygen.

EXAMPLES The following examples demonstrate but do not limit the present invention.

Example 1 Synthesis of N, N-diethyl-cis-2,6, dimethyl piperidino hydroxide (Standard A) Thirty-six grams of cis-2,6-dimethylpiperidino were mixed with 320 ml of methanol and 64 grams of potassium bicarbonate. Ethyl iodide (199 grams) was added dropwise to the reaction mixture and, following the complete addition, the reaction was heated with reflux for three days. Then the desired product was isolated, the acetone salt and hot ether were recrystallized with a small amount of methanol and the iodide salt was converted to the hydroxide salt by a treatment with ion exchange resin Bio-Rad AGI-X8 . The concentration of the hydroxide ion was determined by titration of the resulting solution using phenolphthalein as an indicator.

Example 2 Preparation of the aluminosilicate SSZ-44 Initiating Si02 / Al203 = 100 Four grams of a standard A solution (0.56 mmol OH "/ g) were mixed with 6.4 grams of water and 1.5 grams of 1.0 N NaOH. They were added to this solution (0.029 grams) of hydrated aluminum hydroxide Reheis F2000 and, the solution of the solid was completed, 0.92 grams of Carbosil M-5 smoked silica was added. The resulting reaction mixture was sealed in a Parr 4745 reactor and heated to 170 ° C and rotated at 43 r.p.m. After seven days, a stable product was obtained and determined by XRD to determine SSZ-44. The analysis of this product shows the Si02 / Al203 molar ratio which is 80. Representative X-ray diffraction data for the product are shown in Table III below. In Table III and the subsequent Tables, the intensity of each peak is expressed as 100 x I / Is, where Ic is the intensity of the strongest line or peak.

TABLE III Example 3 Preparation of the aluminosilicate SSZ-44 Starting with SiO2 / A12Q3 = 100 Four grams of a standard A solution (0.56 mmol 0H "/ g) were mixed with 4.3 grams of water and 1.5 grams of 1.0 N NaOH. They were added to this solution (0.029 grams) of Reheis F2000 and, the solution of the solid, 3.0 grams of aqueous colloidal silica Ludox AS-30 (Dupont) was added.The mixture was heated to 170 ° C and turned at 43 rpm After 12 days, a stable product was obtained.XRX analysis revealed that the product is SSZ-44.

Example 4 Preparation seeded with crystals of Aluminosilicate SSZ-44 The reaction described in Example 2 was repeated, with the exception that it was seeded with 0.006 grams of SSZ-44 crystals. In this case, the SSZ-44 was obtained in five days.

Example 5 Preparation of Aluminosilicate SSZ-44 Starting with SÍO2 / AI2O3 = 67 The reaction was repeated as described in Example 4, with the exception that 0.044 grams of Reheis F2000 silica was used in the reaction mixture. This resulted in a molar ratio of Si02 / Al203 in the reaction mixture of 67. After six days a 170 ° C (43 r.p.m.) a product was isolated and determined by the X-ray diffraction data that is SSZ-44. The X-ray diffraction data for this product is shown in Table IV below.

TABLE IV Example 6 Preparation of Aluminosilicate SSZ-44 Starting with SIO2 / AI2O3 = 50 The reaction described in Example 2 was repeated, with the exception that 0.058 grams of Reheis F2000 was used. This resulted in an initial molar ratio Si02 / Al203 of 50. After 11 days at 170 ° C and 43 r.p.m. a product was isolated and determined by XRD which is SSZ-44. The product was analyzed and found to have a molar ratio of Si02 / Al203 of 51.

Example 7 Preparation of Aluminosilicate SSZ-44 Starting with SIO2 / AI2O3 = 40 The reaction described in Example 2 was repeated, with the exception that 0.073 grams of Reheis F2000 was used. This resulted in an initial molar ratio Si02 / Al203 of 40. After 11 days at 170 ° C and 43 r.p.m. a product was isolated and determined by XRD which is SSZ-44. The product was analyzed and found to have a molar ratio of Si02 / Al203 of 38.

Example 8 Preparation of borosilicate SSZ-44 Starting Si02 / B203 = 50 Three millimoles of a solution of the Standard A (5.33 grams, 0.562 millimoles 0H "/ g) with 5.4 grams of water and 1.2 grams of 1.0 N NaOH. To this solution (0.057 grams) of sodium borate decahydrate was added and stirred until all the solids were added. dissolved, then Carbosil M-5 smoked silica (0.92 grams) was added to the solution and the resulting mixture was heated to 160 ° C and rotated at 43 rpm. 14 days. A stable product was obtained which was filtered, washed, dried and determined by XRD to determine SSZ-44. The product found has a Si02 / Al203 molar ratio of 63. The representative X-ray diffraction pattern of the material that was made is tabulated in Table V below.

TABLE V Example 9 Preparation of all SSZ-44 silicas Three millimoles of a standard A solution (5.24 grams, 0.572 millimoles 0H "/ g) were mixed with 5.87 grams of water and 0.75 grams of 1.0 N KOH. Then (0.92 grams) of Carbosil M-5 smoked silica was added to the solution. solution, followed by sowing 0.005 grams of SSZ-44 crystals and the resulting mixture was heated to 150 ° C for 31 days.The resulting stable product was filtered, washed and dried and the presence of SSZ- was determined by XRD. 44 with a trace amount of the stratified material.

Example 10 Calcination of the SSZ-44 The material of Example 5 was calcined in the following manner. A thin bed of material was heated in a muffle furnace from room temperature to 120 ° C at a rate of 1 ° C per minute and maintained at 120 ° C for three hours. The temperature was then raised to 540 ° C at the same rate and maintained at that temperature for 5 hours, after which it was increased to 594 ° C and held there for another 5 hours. A 50/50 mixture of air and nitrogen was passed over the zeolite at a rate of 20 standard cubic feet per minute during heating. The representative XRD data for the calcined product are given in Table VI below.

TABLE VI Example 11 Calcination of the B-SSZ-44 The procedure described in Example 10 was followed with the exception that the calcination was carried out under a nitrogen atmosphere.

Example 12 Volume of the N2 micropore The product of Example 10 was subjected to a surface area and the volume of the micropore was analyzed using N2 as an adsorbent and by means of the BET method. The surface area of the zeolitic material was 430 M2 / g, the micropore volume was 0.185 cc / g, thus exhibiting a considerable void volume.

Example 13 Exchange with NH4 The exchanged ion of the calcined material SSZ-44 (prepared in Example 10) was developed using NH4NO3 to convert the zeolite from its Na + form to the NH4 + form, and ultimately, the H + form. Typically, the same mass of NH4NO3 as zeolite was stirred in water in a ratio of 25-50: 1 water in zeolite. This procedure can be repeated up to three times. Following the final exchange, the zeolite was washed several times with water and dried. This NH4 + form of SSZ-44 can then be converted to the H + form by calcination at 540 ° (as described in Example 10).

Example 14 Interchange of NH4 of B-SSZ-44 The procedure described in Example 13 for ion exchange was followed with the exception that NH4OAc was used in place of NHN03.

Example 15 Determination of the limitation index The hydrogenated form of the zeolite of Example 7 (after the treatment according to examples 10 and 13) was formed into pellets in 2-3 KPSI, ground and sieved 20-40, and then> 0.50 grams were calcined at about 540 C in air for four hours and cooled in a desiccator. The 0.50 grams were packed in a 3/8 inch stainless steel tube with aluminum on both sides of the zeolite bed. A Lindburg furnace was used to heat the tubular reactor. Helium was introduced into the tubular reactor at 10 cc / min. and at atmospheric pressure. The reactor was heated to about 315 ° C, and a 50/50 (w / w) feed of n-hexane and 3-methylpentane was introduced into the reactor at a rate of 8 μl / min. The supply of the feeding was done by means of a Brownlee pump. A sample is taken directly on a gas chromatograph, starting 10 minutes after the introduction of the feed. The value of the limitation index was calculated from the gas chromatography data using methods known in the art, and found to be 0.2. At 315 ° C and 40 minutes in the stream, the feed conversion was greater than 85%. After 430 minutes, the conversion was even greater than 60%. It can be seen that the SSZ-44 has a high thermo-fractionation activity, indicative of strongly acidic sites. In addition, the low contamination rate indicates that this catalyst has good stability. The low I.C. of 0.2 shows a preference for the thermo-fractionation of the branched alkane (3-methylpentane) on the linear n-hexane, whose behavior is typical of large pore zeolites.

Example 16 Use of SSZ-44 to Convert Methanol The hydrogenated form of the zeolite of Example 6 (after the treatment according to examples 10 and 13) was formed into pellets in 2-3 KPSI, ground and sieved 20-40. The 0.50 grams were loaded into a 3/8 inch stainless steel tubular reactor with aluminum on both sides of the zeolite bed where the feed was introduced. The tubular reactor was heated in a Lindburg furnace at 1000 ° F for three hours in air, and then the temperature was reduced to 400 ° C in a stream of nitrogen at 20cc / min. A 22.1% methanol feed (22.1 g of methanol / 77.9 g of water) was introduced to the reactor at a rate of 1. 31cc / hr. The conversion to 10 minutes was 100%, and after 11 hours it was even greater than 95%. The SSZ-44 forms very little light gas and produces considerable liquid product under these conditions.

A large proportion of product is due to the formation of dúrenos, penta- and hexametilbenzene (see Table C below). The formation of penta- and hexamethylbenzene is again indicative of a large pore zeolite, as the equilibrium diameter of the latter is 7.1 Angstroms (Chang, C.D., "Methanol to Hydrocarbons", Marcel Dekker, 1983).

TABLE C Example 17 Pd Exchange 1.0 Grams of SSZ-44 calcined and exchanged with ammonium (made as described in Example 2) were added to 10.0 grams of water and 1.0 grams of a 0.148M solution of NHOH to give a buffered solution at pH 9.5. Approximately 0.5% by weight of Pd was loaded into the zeolite by ion exchange using a 0.05 M solution of Pd (NH3) 42N03. The mixture was stirred at room temperature for 16 hours. The solids were filtered and washed with 1 liter of water, dried and calcined at about 482 ° C in air for three hours.

Example 18 Conversion of n-C? 6- Thermal Hydro-cracking The product of Example 17 was heated to 650 ° F in a hydrogen atmosphere for two hours. The product was then tested for its activity as a compound in the thermal hydrofraction. 0.5 grams of catalyst was used for the test consisting of testing lmL / hour of n-hexandecane feeding with 160 mL / minute of H2 under the following conditions: Temperature 650 ° F WHSV 1.55 PSIG 1200 The results of the test are shown below.

Conversion of nC? 6 97% Selectivity of Isomerization 28% Selectivity of Thermal Fractionation 72% Conversion of nC? 6 Thermal Fractionation 70% C5 + / C4 3.3 C4 i / n 1.3 C5 i / n 1.7 C6 i / n 1.8 As shown above with the nC? 6 feed test, SSZ-44 can be used as a thermal hydrofraction catalyst.

Example 19 Pt-B-SSZ-44 One gram of B-SSZ-44 exchanged with ammonium and calcined (prepared as described in Examples 8, 11 and 14) was added to 10.0 grams of water and 1.0 grams of a solution of a 0.148M solution of NH4OH to give a buffered solution at pH 9.5. Approximately 0.5% by weight of Pt was charged into the zeolite by ion exchange using a 0.05 M solution of Pt (NH3) 2N03. The mixture was stirred at room temperature overnight. The solids were filtered and washed with 1 liter of water, dried and calcined at about 288 ° C in air for three hours.

Example 20 Limitation index and Activity of Pt-B-SSZ-44 The product of Example 19 was formed into pellets in 2-3 KPSI, crushed and sieved 20-40. After 0.50 grams, they were calcined at about 400 ° F in air for four hours and cooled in a desiccator. The 0.47 grams were packed in the center of a 3/8 inch stainless steel tube with aluminum on both sides of the zeolite bed. A Lindburg furnace was used to heat the tubular reactor. Helium was introduced to the tubular reactor at 9.4 cc / in. and at atmospheric pressure. The reactor was brought to 800 ° C, and a 50/50 (w / w) feed of n-hexane and 3-methylpentane was introduced to the reactor at a rate of 10 μl / min. The supply of the feeding was done by means of a piston pump. The sample is taken directly into a gas chromatograph after the introduction of the feed. The Limit Index value was calculated from gas chromatography data using methods known in the art, and was found to be 1.9.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (60)

1. A zeolite, characterized in that it has an average pore size greater than 6 Angstroms and that it has the X-ray diffraction lines of Table I.

2. A zeolite, characterized in that it has a mole ratio greater than about 20 of an oxide of a first tetravalent element with an oxide of a second trivalent or tetravalent element, and that it has the X-ray diffraction lines of Table I.

3. A zeolite, characterized in that it has a mol ratio greater than about 20 of an oxide selected from the group consisting of silicon oxide, germanium oxide and mixtures thereof with an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof, and having the X-ray diffraction lines of Table I.

4. A zeolite according to claim 3, characterized in that the oxides comprise the silicon oxide and the aluminum oxide.

5. A zeolite according to the claim, characterized in that the oxides comprise the silicon oxide and the boron oxide.

6. A zeolite according to claim 3, characterized in that the oxides comprise the silicon oxide and the titanium oxide.

7. A zeolite, characterized in that it has a composition, synthesized and in an anhydrous state, in terms of molar ratio as follows: Y02 / Wa Ob > 20 M + / Y02 < 0.05 Q / Y02 0.01-0.10 where Q comprises a cation of N, N-dimethyl-cis-2,6,6-dimethyl piperidinium; M is a cation of a metallic alkali; W is selected from the group of aluminum, gallium, iron, boron, titanium, indium, vanadium, and mixtures thereof; A = l or 2, b = 2 when a is 1 and b = 3 when a is 2; and Y is selected from the group consisting of silicon, germanium, and mixtures thereof.

8. A zeolite according to claim 7, characterized in that W is aluminum and Y is silicon.

9. A zeolite according to claim 7, characterized in that W is boron and Y is silicon.

10. A zeolite according to claim 7, characterized in that W is titanium and Y is silicon.

11. A zeolite, characterized in that it has an average pore size greater than 6 Angstroms and that it has, after calcining, the X-ray diffraction lines of Table II.

12. A zeolite, characterized in that it has a mol ratio greater than about 20 of an oxide selected from the group consisting of silicon oxide, germanium oxide and mixtures thereof with an oxide selected from the group consisting of aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table II.

13. A zeolite according to claim 11, characterized in that said zeolite is predominantly in the hydrogenated form.

14. A zeolite according to claim 12, characterized in that said zeolite is predominantly in hydrogenated form.

15. A zeolite according to the claim 11, characterized in that it is made substantially free of acidity by the neutralization of said zeolite with a basic metal.

16. A zeolite according to the claim 12, characterized in that it is made substantially free of acidity by the neutralization of said zeolite with a basic metal. 17. A method for preparing a crystalline material, comprising one or a combination of oxides selected from the group consisting of oxides of one or more of the first (s) tetravalent oxide (s) and one or more of the second trivalent element (s) or tetravalent element (s), which is different from said first tetravalent element, said method, is characterized in that it comprises contacting under crystallization conditions the oxide sources and a standard agent comprising a cation of

N, N-diethyl-cis-2,6,6-diethyl piperidinium.

18. The method according to claim 17, characterized in that the first tetravalent element is selected from the group consisting of silicon, germanium and combinations thereof.

19. The method according to claim 17, characterized in that the second tetravalent or trivalent element is selected from the group consisting of aluminum, gallium, iron, boron, titanium, indium, vanadium and combinations thereof.

20. The method according to claim 17, characterized in that the second tetravalent or trivalent element is selected from the group consisting of aluminum, boron, titanium and combinations thereof.

21. The method according to claim 20, characterized in that the first tetravalent element is silicon.

22. The method of claim 17, characterized in that the crystalline material has the X-ray diffraction lines of Table Y.

23. A process for converting hydrocarbons, characterized in that it comprises contacting a hydrocarbonaceous feed at hydrocarbon conversion conditions with a catalyst comprising the zeolite of claim 1.

24. The process of claim 23, characterized in that the catalyst comprises the zeolite of claim 14.

25. The process of claim 23, characterized in that the catalyst comprises the zeolite of claim 16.

26. A thermal hydrofraction process, characterized by comprising contacting a hydrocarbon feed under thermal hydrofraction conditions with a catalyst comprising the zeolite of claim 1.

27. A dewaxing process, characterized in that it comprises contacting a hydrocarbon feed under dewaxing conditions with a catalyst comprising the zeolite of claim 1.

28. A process characterized in that it improves the viscosity index of the dewaxed product of the hydrocarbon feed with paraffins under conditions of dewaxing isomerization with a catalyst comprising the zeolite of claim 1.

29. A process to produce a lubricating oil C2o + from the C2o + olefin feed, characterized in that it comprises isomerizing said feed of the olefin onto a catalyst comprising the zeolite of claim 1 and at least one Group VIII- metal.

30. A process for catalytically dewaxing a hydrocarbon oil feed, having a boiling point about 350 ° F and containing straight chain and slightly branched chain hydrocarbons, characterized in that it comprises contacting said hydrocarbon oil feed in the presence of hydrogen gas added at a hydrogen pressure of about 15-3000 psi with a catalyst comprising the zeolite of claim 1 and at least one Group VIII metal.

31. A process according to claim 30, characterized in that said catalyst comprises a stratified catalyst comprising a first layer comprising the zeolite of claim 1 and at least one Group VIII metal, and a second layer comprising an aluminosilicate zeolite which it has a more selective shape than the zeolite of said first layer.

32. A process for preparing a lubricating oil characterized in that it comprises: the thermal hydrofraction in a hydrofractionation zone of a hydrocarbonaceous feed to obtain an effluent comprising a thermally hydrofractioned oil; and catalytically dewatering said effluent comprising the hydrofracted oil at a temperature of at least about 400 ° F and a pressure of about 15 psig to about 3000 psig in the presence of hydrogen gas added with a catalyst comprising the zeolite of claim 1 and at least one Group VIII metal.

33. A dewaxing process by isomerization of a raffinate, characterized in that it comprises contacting said raffinate in the presence of hydrogen added with a catalyst comprising the zeolite of claim 1 and at least one Group VIII metal.

34. The process of claim 33, characterized in that the refining is unrefined cylinder oil.

35. A process for increasing the octane of an id.drocarbon feed to produce a product, characterized in that it has a high content of aromatics comprising normal and slightly branched hydrocarbons having a boiling point in the above range of about 40 ° C and less than about 200 ° C, under conditions of aromatic conversion with the zeolite of claim 1.

36. The process of claim 35, characterized in that the catalyst comprises the zeolite of claim 16.

37. The process of claim 35, characterized in that the zeolite contains a compound of a metal of the Group VIII.

38. A catalytic thermal fractionation process, characterized in that it comprises contacting a hydrocarbon feed in a reaction zone under catalytic thermal fractionation conditions in the absence of the hydrogen added with a catalyst comprising the zeolite of claim 1.

39. The process of claim 38, characterized in that the catalyst additionally comprises a large pore crystalline thermal fractionation compound.

40. An isomerization process for isomerizing C4 to C7 hydrocarbons, characterized in that it comprises contacting a catalyst, comprising at least one Group VIII metal impregnated in the zeolite of claim 1, with a feed having normal and slightly branched hydrocarbons of C4 to C7 under isomerization conditions.

41. The process of claim 40, characterized in that the catalyst has been calcined in a vapor / air mixture at a high temperature after impregnation of the Group VIII metal.

42. The process of claim 41, characterized in that the Group VIII metal is platinum.

43. A process for alkylating an aromatic hydrocarbon, characterized in that it comprises contacting under alkylation conditions at least one mole in excess of an aromatic hydrocarbon with a C2 to C20 olefin under at least partial liquid phase conditions and in the presence of a catalyst which comprises the zeolite of claim 1.

44. The process of claim 43, characterized in that the olefin is a C2 to C4 olefin.

45. The process of claim 44, characterized in that the aromatic hydrocarbon and the olefin are present in a molar ratio of about 4: 1 to 20: 1, respectively.

46. The process of claim 44, characterized in that the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, xylene, or mixtures thereof.

47. A process for transalkylating an aromatic hydrocarbon, characterized in that it comprises contacting under transalkylation conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least conditions of the partial liquid phase and in the presence of the zeolite of claim 1.

48. The process of claim 47, characterized in that the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon are present in a molar ratio of about 1: 1 to 25: 1, respectively.

49. The process of claim 47, characterized in that the aromatic hydrocarbon is a member selected from the group consisting of benzene, toluene, xylene, or mixtures thereof.

50. The process of claim 47, characterized in that the polyalkyl aromatic hydrocarbon is a dialkyl benzene.

51. A process for converting paraffins to aromatics, characterized in that it comprises the zeolite of claim 1 and gallium, zinc, or a gallium or zinc compound.

52. A process for converting light alcohols and other oxygenated hydrocarbons, characterized in that it comprises contacting said light alcohol or other oxygenated hydrocarbon with a catalyst comprising the zeolite of claim 1 under conditions to produce liquid products.

53. A process for isomerizing olefins, characterized in that it comprises contacting said olefin with a catalyst comprising the zeolite of claim 1 under conditions that cause isomerization of the olefin.

54. A process for isomerizing an isomerization feed, characterized in that it comprises a C8 stream of xylene isomers or mixtures of isomers of xylenes and ethylbenzene, where a closer ratio of ortho-, meta- and para-xylenes is obtained, said process comprises contacting said feed under isomerization conditions with a catalyst comprising the zeolite of claim 1.

55. A process for oligomerizing olefins, characterized in that it comprises contacting an olefin feed under oligomerization conditions with a catalyst comprising the zeolite of claim 1.

56. The process of claim 26, 27, 28, 29, 30, 32, 33, 38, 40, 43, 47, 51, 52, 53, 54, or 55, characterized in that the zeolite is predominantly in the hydrogenated form.

57. In a process for the reduction of nitrogen oxides contained in a gas stream in the presence of oxygen, characterized in that said process comprises contacting the gas stream with a zeolite, the improvement comprises using as the zeolite a zeolite having a molar of an oxide of a first tetravalent element with an oxide of a second trivalent or tetravalent element that is different from said first tetravalent element, said molar ratio is greater than about 20 and that it has the diffraction lines of the X-rays of the Table I.

58. The process of claim 57, characterized in that said zeolite contains a metal or ions of a metal capable of catalyzing the reduction of the nitrogen oxides.

59. The process of claim 58, characterized in that the metal is copper, cobalt or mixtures thereof.

60. The process of claim 58, characterized in that the gas stream is the exhausted current of an internal combustion engine.