JP2006521275A - Molecular sieve SSZ-65 - Google Patents

Abstract

The present invention uses 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation as a template molecule. The present invention relates to a novel crystalline molecular sieve SSZ-65 prepared using the method for synthesizing SSZ-65 in a catalyst.

Description

  The present invention relates to novel crystalline molecular sieve SSZ-65, 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -Relates to a process for preparing SSZ-65 using pyrrolidinium cations as a structure directing agent (SDA) and to the use of SSZ-65 in catalysts used for example in hydrocarbon conversion reactions.

  Due to the unique sieving and catalytic properties, crystalline molecular sieves and molecular sieves are particularly useful in applications such as hydrocarbon conversion, gas drying and separation. Although many different crystalline molecular sieves have been disclosed, there is a continuing need for new molecular sieves that have desirable properties for gas separation and drying, hydrocarbon and chemical conversion, and other applications. The novel molecular sieve can have a novel internal pore structure, providing further improved selectivity in these processes.

  Crystalline aluminosilicates are usually prepared from water-soluble reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina. Crystalline borosilicates are usually prepared under similar reaction conditions except that boron is used instead of aluminum. Often different molecular sieves can be formed by varying the synthesis conditions and the composition of the reaction mixture.

SUMMARY OF THE INVENTION The present invention is directed to a group of crystalline molecular sieves having unique properties. In the present specification, they are referred to as “molecular sieve SSZ-65” or simply “SSZ-65”. Preferably, SSZ-65 is obtained in the form of silicate, aluminosilicate, titanosilicate, germanosilicate, vanadosilicate or borosilicate. The term “silicate” refers to a molecular sieve having a large molar ratio of silicon oxide as compared to aluminum oxide, preferably a molar ratio exceeding 100, and includes a molecular sieve consisting entirely of silicon oxide. As used herein, the term “aluminosilicate” refers to a molecular sieve containing both aluminum oxide and silicon oxide, and the term “borosilicate” refers to both boron and silicon oxides. Refers to a molecular sieve containing

  According to the present invention, (1) oxidation of the oxide of the first tetravalent element, (2) trivalent element, pentavalent element, second tetravalent element different from the first tetravalent element or a mixture thereof. A molecular sieve is provided having a molar ratio to product of greater than about 15 and, after calcination, having the X-ray diffraction lines of Table II.

  Furthermore, according to the invention, (1) an oxide selected from silicon oxide, germanium oxide and mixtures thereof, (2) aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, oxidation A molecular sieve having an X-ray diffraction line in Table II below is provided after firing with a molar ratio to an oxide selected from vanadium and mixtures thereof of greater than about 15. It should be noted that the molar ratio of the first oxide or mixture of first oxides to the second oxide can be infinite, i.e. no second oxide may be present in the molecular sieve. . In these cases, the molecular sieve is an all-silica molecular sieve or germanosilicate.

The present invention further provides a molecular sieve having the following composition expressed as a molar ratio in an as-synthesized and anhydrous state.
YO ₂ / _W c _O d 15~∞
M ₂ / _n / YO ₂ 0.01~0.03
Q _/ YO 2 0.02~0.05
Wherein Y is silicon, germanium or a mixture thereof, W is aluminum, gallium, iron, boron, titanium, indium, vanadium or a mixture thereof, c is 1 or 2, and c is 1. When d is 2 (ie, W is tetravalent), when c is 2, d is 3 or 5 (ie, when W is trivalent, d is 3 and when W is pentavalent) d is 5), M is an alkali metal cation, alkaline earth metal cation or mixtures thereof, n is the valence of M (ie 1 or 2), and Q is 1- [1- (4 -Chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation.

  According to the present invention, also an oxide selected from silicon oxide, germanium oxide and mixtures thereof, from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof. A molecular sieve prepared by heat treating a molecular sieve having a molar ratio to the selected oxide of greater than about 15 at a temperature of about 200 ° C. to about 800 ° C. is provided, the molecular sieve thus prepared being Has X-ray diffraction lines. The invention also includes a molecular sieve prepared in this way, mainly in hydrogen form, which is prepared by ion exchange with an acid or ammonium salt solution followed by a second calcination. The If the molecular sieve is synthesized under conditions where the ratio of template molecule cation to sodium ion is sufficiently large, calcination alone may be sufficient. In order to obtain high catalytic activity, the SSZ-65 molecular sieve must be mainly in the hydrogen ion form. It is preferred that at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions after calcination. As used herein, the phrase “mainly in hydrogen form” means that after calcination, at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions.

  According to the present invention, (1) an oxide of a first tetravalent element and (2) a trivalent element, a pentavalent element, a second tetravalent element different from the first tetravalent element, or a mixture thereof. A method for preparing a crystalline material comprising an oxide, the molar ratio of the first oxide to the second oxide being greater than 15, wherein the oxide source is 1- [1- (4-chlorophenyl)- Contacting the template molecule comprising cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation under crystallization conditions. Is provided.

  Furthermore, according to the present invention, there is provided a method for converting hydrocarbons comprising contacting a hydrocarbon feedstock with a catalyst comprising the molecular sieve of the present invention under hydrocarbon conversion conditions. The molecular sieve can be mainly in the hydrogen form. In addition, the molecular sieve may be substantially free of acidity.

  Furthermore, the present invention provides a hydrocracking process comprising the step of contacting a hydrocarbon feedstock with a catalyst comprising the molecular sieve of the present invention, preferably a primarily hydroform catalyst, under hydrocracking conditions. The

  The present invention also includes a dewaxing process comprising the step of contacting a hydrocarbon feedstock with a catalyst comprising the molecular sieve of the present invention, preferably in a predominantly hydrogen form, under dewaxing conditions.

  The present invention also includes a step of contacting a waxy hydrocarbon feedstock with a catalyst comprising the molecular sieve of the present invention, preferably a hydrogen form catalyst, under isomerization dewaxing conditions. A method for improving the viscosity index of a hydrogen feed dewaxing product is included.

Furthermore, the present invention provides a process for producing _{C20 +} lubricating oil from a _{C20 +} olefin feedstock comprising the step of isomerizing an olefin feedstock on a catalyst comprising the molecular sieve of the present invention under isomerization conditions. including. The molecular sieve can be mainly in the hydrogen form. The catalyst can include at least one Group VIII metal.

  In accordance with the present invention, a process for catalytic dewaxing of hydrocarbon oil feedstocks boiling at temperatures above about 350 ° F. (177 ° C.) and containing linear and slightly branched chains is added. In the presence of hydrogen gas at a hydrogen pressure of about 15 to 3000 psi (0.103 to 20.7 MPa), said hydrocarbon oil feedstock, a catalyst comprising the molecular sieve of the present invention, preferably primarily in hydrogen form, and A method comprising contacting is also provided. The catalyst can comprise at least one Group VIII metal. The catalyst may be a layered catalyst comprising a first layer comprising the molecular sieve of the present invention and a second layer comprising an aluminosilicate molecular sieve that is more selective in shape than the molecular sieve of the first layer. The first layer may include at least one group VIII metal.

  The present invention also includes hydrocracking a hydrocarbon feedstock in a hydrocracking zone to obtain an effluent containing hydrocracked oil, and at least about 400 ° in the presence of added hydrogen gas. The effluent containing hydrocracked oil is subjected to a catalyst containing the molecular sieve of the present invention at a temperature of F (204 ° C.) under a pressure of about 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge pressure). A method for preparing a lubricating oil is included, comprising the step of contact dewaxing. The molecular sieve can be mainly in the hydrogen form. The catalyst can include at least one Group VIII metal.

  Furthermore, the present invention includes a method for isomerization dewaxing of a raffinate comprising the step of contacting the raffinate with a catalyst comprising the molecular sieve of the present invention in the presence of added hydrogen. The raffinate can be bright stock and the molecular sieve can be predominantly in hydrogen form. The catalyst can include at least one Group VIII metal.

  The present invention also includes a method for producing a product having an increased aromatic content by increasing the octane of the hydrocarbon feedstock, the boiling point being greater than about 40 ° C. and less than about 200 ° C. The molecular sieve of the present invention produced by neutralizing a hydrocarbon feedstock containing normal and slightly branched hydrocarbons with a range to neutralize the molecular sieve with a basic metal so that the molecular sieve has substantially no acidity. A method comprising contacting with a catalyst comprising, under aromatic conversion conditions. Also provided in the present invention is a method wherein the molecular sieve comprises a Group VIII metal component.

  Also, according to the present invention, in the absence of added hydrogen, under catalytic cracking conditions, in the reaction zone, the hydrocarbon feedstock is contacted with a catalyst comprising the molecular sieve of the present invention, preferably primarily in hydrogen form. There is provided a catalytic cracking process comprising the steps of: The present invention also includes a catalytic cracking process in which the catalyst further comprises a large pore size crystalline cracking component.

Furthermore, the present invention contacts a feedstock having normal and slightly branched C _{4 to} C ₇ hydrocarbons under isomerization conditions with a catalyst comprising the molecular sieve of the present invention, preferably primarily in hydrogen form. Provided is an isomerization process for isomerizing C ₄ -C ₇ hydrocarbons comprising steps. The molecular sieve can be impregnated with at least one Group VIII metal, preferably platinum. The catalyst can be calcined in a steam / air mixture at high temperatures after impregnation with a Group VIII metal.

Also, according to the present invention, a catalyst comprising at least a molar excess of aromatic hydrocarbons under alkylation conditions and at least partially in liquid phase, preferably the molecular sieve of the present invention, preferably primarily in hydrogen form. under the existence, comprising contacting an olefin of C ₂ -C _20, a method for the alkylation of aromatic hydrocarbons is provided. Olefin _may be an olefin C 2 -C _4, aromatic hydrocarbons and olefins are each from about 4: may be present in a molar ratio of: 1 to about 20. The aromatic hydrocarbon can be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene or mixtures thereof.

  Furthermore, according to the present invention, a catalyst comprising an aromatic hydrocarbon under transalkylation conditions and at least partially in liquid phase, preferably the molecular sieve of the present invention, preferably mainly in hydrogen form. A method is provided for transalkylating an aromatic hydrocarbon comprising the step of contacting with a polyalkyl aromatic hydrocarbon in the presence. The aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon can each be present in a molar ratio of about 1: 1 to about 25: 1.

  The aromatic hydrocarbon can be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the polyalkyl aromatic hydrocarbon can be a dialkylbenzene.

  Further, according to the present invention, the paraffin is obtained by contacting the paraffin with the molecular sieve of the present invention and a catalyst containing gallium, zinc, or a compound of gallium or zinc under conditions that convert the paraffin to an aromatic compound. A method is provided for conversion to an aromatic compound.

  The present invention also provides a process for isomerizing an olefin comprising the step of contacting the olefin with a catalyst containing the molecular sieve of the present invention under conditions that cause isomerization of the olefin.

Furthermore, according to the present invention, the isomerization feed comprising a flow of aromatic C ₈ is a mixture of xylene isomers or isomeric xylenes and ethylbenzene and isomerization, closer to equilibrium ortho -, meta - and para A method is provided for obtaining a xylene ratio comprising contacting the feedstock with a catalyst containing the molecular sieve of the invention under isomerization conditions.

  Furthermore, the present invention provides a process for oligomerizing olefins comprising contacting an olefin feedstock with a catalyst containing the molecular sieve of the present invention under oligomerization conditions.

  The present invention also provides a method for converting an oxygenated hydrocarbon comprising the step of contacting the oxygenated hydrocarbon with a catalyst comprising the molecular sieve of the present invention under conditions that produce a liquid product. Provide a method. The oxygenated hydrocarbon can be a lower alcohol.

Furthermore, according to the present invention,
(A) introducing a gas containing a lower molecular weight hydrocarbon into the reaction zone, and subjecting the gas to a higher concentration of the catalyst and the lower molecular weight hydrocarbon in the zone under C 2 ₊ hydrocarbon synthesis conditions; A lower molecular weight hydrocarbon comprising: contacting with a metal or metal compound that can be converted to a molecular weight hydrocarbon; and (b) withdrawing a stream containing a higher molecular weight hydrocarbon from the reaction zone A process for producing higher molecular weight hydrocarbons from is provided.

  In addition, according to the present invention, the gas flow is (1) an oxide of a first tetravalent element, (2) a second tetravalent element, a trivalent element, or a pentavalent element different from the first tetravalent element. Or the molar ratio of the mixture to the oxide is greater than about 15 and is contained in the gas stream in the presence of oxygen, including the step of contacting with a molecular sieve having the X-ray diffraction lines of Table II after firing. A method is provided for reducing oxides of nitrogen. Molecular sieves are metals or metal ions (eg, cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof) that can catalyze the reduction of oxides of nitrogen. The method can be carried out in the presence of a stoichiometric excess of oxygen. In a preferred embodiment, the gas flow is an exhaust flow of an internal combustion engine.

Detailed Description of the Invention The present invention comprises a group of crystalline large pore molecular sieves, referred to herein as "molecular sieve SSZ-65" or simply "SSZ-65". As used herein, the term “large pore” means having an average pore size greater than about 6.0 mm, preferably from about 6.5 mm to about 7.5 mm.

In preparing SSZ-65, 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidi The nium cation is used as a template molecule (“SDA”), also known as a crystallization template. SDA useful for the production of SSZ-65 has the following structure:

SDA cations, anions (X ^-) and have been associated, the anion (X ^-) is no harm in forming the molecular sieve, it may be any anion. Typical anions include halogens such as fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate and the like. Hydroxide is the most preferred anion.

  In general, SSZ-65 is one or more selected from the group consisting of monovalent element oxides, divalent element oxides, trivalent element oxides, tetravalent element oxides and / or pentavalent element oxides. The active source of the oxide of 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation Prepared by contact with SDA.

ただし、Ｙ、Ｗ、Ｑ、Ｍ及びｎは、上で定義されたとおりであり、ａは１又は２であり、ａが１（すなわち、Ｗは４価である）のときｂは２であり、ａが２（すなわち、Ｗは３価である）のときｂは３である。 SSZ-65 is prepared from a reaction mixture having the composition shown in Table A below.

Where Y, W, Q, M and n are as defined above, a is 1 or 2, and b is 2 when a is 1 (ie, W is tetravalent). , A is 2 (ie, W is trivalent), b is 3.

In fact, SSZ-65 is
(A) 1- [1- (4-chlorophenyl) having at least one oxide source capable of forming a crystalline molecular sieve and an anionic counterion that does not harm the formation of SSZ-65 Preparing an aqueous solution containing -cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation;
(B) maintaining the aqueous solution under conditions sufficient to form SSZ-65 crystals; and (c) recovering SSZ-65 crystals;
Prepared by a method comprising:

Therefore, SSZ-65 includes a combination of a crystalline material and SDA and a metal and a non-metal oxide that form a bridged three-dimensional crystal structure by bonding in a tetrahedral coordination via a shared oxygen atom. Can do. Metals and non-metal oxides are one or a combination of oxides of the first tetravalent elements, and trivalent elements, pentavalent elements, second tetravalent elements different from the first tetravalent elements or mixtures thereof. Including one or a combination thereof.
The first tetravalent element is preferably selected from the group consisting of silicon, germanium and combinations thereof. More preferably, the first tetravalent element is silicon. The trivalent element, pentavalent element and second tetravalent element (different from the first tetravalent element) are preferably selected from the group consisting of aluminum, gallium, iron, boron, titanium, indium, vanadium and combinations thereof. Is done. More preferably, the second trivalent or tetravalent element is aluminum or boron.

Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, aluminum colloids, aluminum oxide coated on silica sol, hydrated alumina gels such as Al (OH) ₃ and AlCl ₃ and Al ₂ ( aluminum compounds such as SO _{4) 3} are included. Typical sources of silicon oxide include silicates, silica hydrosols, silicic acid, fumed silica, colloidal silica, tetraalkylorthosilicates, and silica hydroxides. Boron and gallium, germanium, titanium, indium, vanadium and iron can be added in forms corresponding to their aluminum and silicon equivalents.

  The source molecular sieve reagent can provide a source of aluminum or boron. In most cases, the source molecular sieve is also a source of silica. Source molecular sieves in the form of dealuminated or deboronated can also be used as a source of silica, for example, with the addition of additional silicon using the conventional sources listed above. The use of a source molecular sieve reagent as the source of alumina in this process is entitled “Method of Making Molecular Sieves” issued to Nagaoka on July 6, 1993. More fully described in US Pat. No. 5,225,179, the disclosure of which is incorporated herein by reference.

  Typically, alkali metal hydroxides and / or alkaline earth metal hydroxides such as sodium, potassium, lithium, cesium, rubidium, calcium, and magnesium hydroxides are used in the reaction mixture. However, this component can be omitted if the equivalent basicity is maintained. SDA can be used to provide hydroxide ions. Thus, for example, it may be beneficial to ion exchange halide ions to hydroxide ions, thereby reducing or eliminating the amount of alkali metal hydroxide required. The alkali metal cation or alkaline earth cation can be part of the as-synthesized crystalline oxide material and balance the charge of valence electrons.

  The reaction mixture is maintained at an elevated temperature until SSZ-65 crystals are formed. Hydrothermal crystallization is usually carried out at a temperature of 100 ° C. to 200 ° C., preferably at a temperature of 135 ° C. to 160 ° C., under an autogenous pressure. The crystallization period is typically greater than 1 day, preferably from about 3 days to about 20 days.

  Preferably, the molecular sieve is prepared using gentle mixing and stirring.

  During the hydrothermal crystallization step, SSZ-65 crystals can spontaneously nucleate from the reaction mixture. Using SSZ-65 crystals as the seed material can be advantageous in reducing the time required for complete crystallization to occur. In addition, seeding can improve the purity of the resulting product by promoting nucleation and / or formation of SSZ-65 over undesired phases. When used as a seed crystal, SSZ-65 crystals are added in an amount of 0.1 to 10% of the weight of the first tetravalent element oxide used in the reaction mixture, such as silica.

  Once the molecular sieve crystals are formed, the solid product is separated from the reaction mixture by standard mechanical separation methods such as filtration. The crystals are washed with water and then dried, for example, at 90 ° C. to 150 ° C. for 8 to 24 hours to obtain as-synthesized SSZ-65 crystals. The drying step can be performed at atmospheric pressure or under vacuum.

ただし、Ｙ、Ｗ、ｃ、ｄ、Ｍ、ｎ及びＱは、上で定義したとおりである。 The prepared SSZ-65 is an oxide selected from silicon oxide, germanium oxide and mixtures thereof, from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof. The molar ratio to the selected oxide exceeds about 15, and after calcination has the X-ray diffraction lines of Table II below. Further, SSZ-65 is synthesized (ie, prior to removal of SDA from SSZ-65) and expressed in molar ratios in the anhydrous state to give the composition shown in Table B below. Have.

However, Y, W, c, d, M, n, and Q are as defined above.

SSZ-65 is a _YO 2 _/ W c _{O d} molar ratio of ∞ (infinity), i.e., can be manufactured as not exist essentially _W c _{O d} in SSZ-65. In this case, SSZ-65 will be an all-silica material or germanosilicate. Thus, in the typical case where silicon and aluminum oxides are used, SSZ-65 can be made to be essentially free of aluminum, i.e., having a molar ratio of ∞ to silica alumina. . A method for increasing the molar ratio of silica to alumina is by using standard acid leaching or chelation. However, SSZ-65 that is essentially free of aluminum can be synthesized using a silicon source that is essentially free of aluminum as the main tetrahedral metal oxide if boron is also present. The boron is then removed, if desired, by treating the borosilicate SSZ-65 with acetic acid at an elevated temperature (as described in Jones et al., Chem. Mater. 2001, 13: 1041-1050). As such, an all silica form of SSZ-65 is obtained. SSZ-65 can also be prepared directly as a borosilicate. If desired, the boron can be removed as described above and replaced by metal atoms by techniques known in the art to make, for example, an aluminosilicate form of SSZ-65. SSZ-65 can also be prepared directly as an aluminosilicate.

  A lower ratio of silica to alumina is obtained by using a method of inserting aluminum into the crystal skeleton. For example, aluminum insertion may occur by heat treating the molecular sieve with an alumina binder or a dissolved alumina source. Such a procedure is described in US Pat. No. 4,559,315 issued December 17, 1985 to Chang et al.

^（ｂ）与えられたＸ線パターンは、Ｘ線パターンにおける最強線を１００という数値に指定した相対的強度スケールに基づく。Ｗ（弱い）は２０未満である、Ｍ（中程度）は２０〜４０である、Ｓ（強い）は４０〜６０である、ＶＳ（非常に強い）は６０を超える。 SSZ-65 is believed to consist of a new skeletal structure or topology characterized by its X-ray diffraction pattern. As-synthesized SSZ-65 has a crystal structure whose powder X-ray diffraction pattern exhibits the characteristic lines shown in Table I, thereby distinguishing it from other molecular sieves.

^{(B) The} given X-ray pattern is based on a relative intensity scale in which the strongest line in the X-ray pattern is designated as a numerical value of 100. W (weak) is less than 20, M (medium) is 20-40, S (strong) is 40-60, VS (very strong) is more than 60.

Table IA below shows the powder X-ray diffraction lines of as-synthesized SSZ-65, including the actual relative intensities.

After firing, the SSZ-65 molecular sieve has a crystal structure whose powder X-ray diffraction pattern includes the characteristic lines shown in Table II.

Table IIA below shows the powder X-ray diffraction lines of calcined SSZ-65, including the actual relative intensities:

  The powder X-ray diffraction pattern was measured by standard techniques. Radiation was copper K-α / doublet. As a function of 2θ where θ is the Bragg angle, the peak height and position are read from the relative intensity of the peaks and d corresponding to the recorded line and d, which is the face spacing expressed by Å. it can.

  Variation in scattering angle (2θ) measurements due to instrument error and differences between individual samples is estimated to be ± 0.1 °.

  The X-ray diffraction pattern of Table I shows representative examples of “as-synthesized” or “as-made” SSZ-65 molecular sieves. Small variations in the diffraction pattern can result from variations in the specific sample silica to alumina or silica to boron molar ratio due to changes in the lattice constant. In addition, when the crystal is sufficiently small, the peak shape and intensity are affected, and the peak width is greatly increased.

Representative peaks from the X-ray diffraction pattern of calcined SSZ-65 are shown in Table II. Also, firing can result in a change in peak intensity and a small shift in the diffraction pattern compared to the pattern of “as-made” material. Molecular sieves made by exchanging metals or other cations present in molecular sieves with various other cations (such as H ⁺ or NH ₄ ⁺ ) result in essentially the same diffraction pattern, Small shifts in interplanar spacing and changes in peak relative intensity can occur. Despite these small variations, the basic crystal lattice is maintained unchanged by these processes.

  Crystalline SSZ-65 can be used as synthesized, but is preferably heat treated (fired). It is usually desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or the desired metal ion. The molecular sieve can be leached with a chelating reagent such as EDTA or dilute acid solution to increase the silica to alumina molar ratio. The molecular sieve can also be treated with steam, which helps to stabilize the crystal lattice against attack from acids.

  Molecular sieves are desired to have a hydrogenation-dehydrogenation function in close combination with, for example, hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals such as palladium or platinum. Can be used for applications.

  Metals can also be introduced into the molecular sieve by replacing some of the molecular sieve cations with metal cations using standard ion exchange techniques (see, for example, Plank et al. On July 7, 1964). U.S. Pat. No. 3,140,249 issued to U.S. Pat. No. 3,140,251 issued to Plank et al. On July 7, 1964, and U.S. Pat. No. 3,140,251 issued to Plank et al. (See Japanese Patent No. 3140253). Typical substituted cations include, for example, metal cations such as rare earths, Group IA, Group IIA and Group VIII metals, and mixtures thereof. Among the substituted metal cations, metal cations such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe are particularly preferable.

  Hydrogen, ammonium, and metal components can be ion exchanged into SSZ-65. SSZ-65 can also be impregnated with metal using standard methods known in the art, or the metal can be physically intimately mixed with SSZ-65.

  Typical ion exchange techniques require that the synthetic molecular sieve be contacted with a solution containing the desired substituted cation or salt of the cation. A wide variety of salts can be used, but chlorides and other halides, acetates, nitrates, and sulfates are particularly preferred. By doing so, since the efficiency of ion exchange is improved, the molecular sieve is usually baked prior to the ion exchange procedure to remove organic substances present in the flow path and the surface. Exemplary ion exchange techniques include U.S. Pat. No. 3,140,249 issued to Plank et al. On July 7, 1964, U.S. Pat. No. 3,140,251 issued to Plank et al. On July 7, 1964, And in various patents, including US Pat. No. 3,140,253 issued July 7, 1964 to Plank et al.

  After contacting the salt solution of the desired substituted cation, the molecular sieve is typically washed with water and dried at a temperature ranging from 65 ° C to about 200 ° C. After washing, the molecular sieve is calcined in air or inert gas at a temperature in the range of about 200 ° C. to about 800 ° C. for 1 to 48 hours or longer to produce a catalytically active product that is particularly useful in the hydrocarbon conversion process. Can be produced.

  Regardless of the cations present in the synthetic form of SSZ-65, the spatial arrangement of the atoms forming the basic crystal lattice of the molecular sieve remains essentially unchanged.

  SSZ-65 can be molded into various physical shapes. Generally speaking, the molecular sieve has a particle size sufficient to pass through a powder, granule, or 2 mesh (Tyler) sieve and be retained on a 400 mesh (Tyler) sieve. It can take the form of a molded product such as an extrudate. If the catalyst is formed, for example, by extrusion with an organic binder, SSZ-65 was extruded before drying, or after drying or partially dried Later, it can be extruded.

  SSZ-65 can be composited with other materials that are durable to the temperatures and other conditions used in organic conversion processes. Such matrix materials include active and inert materials, as well as synthetic and naturally occurring molecular sieves, and inorganic materials such as clays, silica and metal oxides. Examples of such materials and the manner in which they can be used are described in US Pat. No. 4,911,0006 issued to Zones et al. On May 20, 1990, and Nakagawa on May 31, 1994. U.S. Pat. No. 5,316,753, both of which are incorporated herein by reference in their entirety.

  SSZ-65 molecular sieve is useful for hydrocarbon conversion reactions. Hydrocarbon conversion is a chemical and catalytic process in which a carbon-containing compound is converted to another carbon-containing compound. Examples of hydrocarbon conversion reactions for which SSZ-65 is expected to be useful include hydrocracking, dewaxing, catalytic cracking and olefin and aromatics production reactions. Catalysts also include other petroleum refining and isomerization of n-paraffins and naphthenes, polymerization and oligomerization of olefins or acetylene compounds such as isobutylene and butene-1, modification, polyalkyl substituted aromatic compounds (e.g., m-xylene) isomerization, and expected to be useful in hydrocarbon conversion reactions such as disproportionation and oxidation reactions of aromatic compounds (eg toluene) to obtain mixtures of benzene, xylene and higher methylbenzenes Is done. Also included are rearrangement reactions to make various naphthalene derivatives and the formation of higher molecular weight hydrocarbons from lower molecular weight hydrocarbons (eg, upgrade of methane). The SSZ-65 catalyst can have high selectivity and can obtain the desired product at a high percentage of the total product under hydrocarbon conversion conditions.

  In order to obtain high catalytic activity, the SSZ-65 molecular sieve must be mainly in the hydrogen ion form. In general, molecular sieves are converted to the hydrogen form by calcination after ammonium exchange. If the molecular sieve is synthesized with a sufficiently large ratio of SDA cation to sodium ion, calcination alone may be sufficient. After calcination, preferably at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions. As used herein, the phrase “primarily in hydrogen form” means that after calcination, at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions.

  SSZ-65 molecular sieves can be used to process hydrocarbon feedstocks. The hydrocarbon feedstock contains carbon compounds such as virgin petroleum fraction, recycled petroleum fraction, shale oil, liquefied coal, tar sand oil, synthetic paraffin from NAO, recycled plastic feedstock, etc. It can be any carbon-containing feedstock that originates from many different sources and generally undergoes zeolitic catalysis. Depending on the type of treatment to be received by the hydrocarbon feedstock, the feedstock may contain metals or may contain no metals and may contain high or low concentrations of nitrogen or sulfur impurities. it can. However, it can be understood that in general, the lower the metal, nitrogen, and sulfur content of the feedstock, the more general processing will become more efficient (the catalyst will become more active).

  The conversion of the hydrocarbon feed can be carried out in any conventional manner, for example in a fluidized bed, moving bed or fixed bed reactor, depending on the type of process desired. The formulation of the catalyst particles will vary depending on the conversion method and operating method.

  Other reactions that can be carried out using the catalysts of the present invention comprising a metal, for example a Group VIII metal such as platinum, include hydrogenation-dehydrogenation reactions, denitrogenation and desulfurization reactions.

^１数百気圧
^２気相反応
^３炭化水素の分圧
^４液相反応
^５重量空間速度
その他の反応条件及びパラメータは、以下に与えられている。 The table below shows typical reaction conditions that can be used when using a catalyst comprising SSZ-65 in the hydrocarbon conversion reaction of the present invention. Preferred conditions are indicated in parentheses.

¹ hundred barometric pressure
^Two gas phase reaction
³ Hydrocarbon partial pressure
⁴ liquid phase reaction
^{The 5} weight space velocity and other reaction conditions and parameters are given below.

Hydrocracking Using a catalyst and hydrogenation promoter, preferably comprising SSZ-65, preferably mainly in the hydrogen form, with the process conditions and catalyst components disclosed in the aforementioned U.S. Pat. No. 4,911,0006 and U.S. Pat. No. 5,316,753. It can be used to hydrocrack heavy petroleum residue feedstocks, cyclic stocks, and other hydrocracking charge stocks.

  The hydrocracking catalyst contains an effective amount of at least one hydrocracking component of the type commonly used in hydrocracking catalysts. The hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, including salts, complexes and solutions containing them. Preferably, the hydrogenation catalyst consists of at least one of the group consisting of at least one of platinum, palladium, rhodium, iridium, ruthenium and mixtures thereof or nickel, molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof. Selected from the group of metals, salts, and complexes thereof. References to catalytically active metals or metals are intended to include some form of metal or metals, such as elemental state or oxides, sulfides, halides, carboxylates, etc. . The hydrogenation catalyst is present in an amount effective to provide the hydrogenation function of the hydrocracking catalyst, preferably in the range of 0.05 to 25% by weight.

Dewaxing SSZ-65, preferably predominantly in hydrogen form, SSZ-65 can be used to dewax hydrocarbon feedstock by selectively removing linear paraffins. Typically, when the waxy feedstock is contacted with SSZ-65 under isomerization dewaxing conditions, the viscosity index of the dewaxed product is improved (compared to the waxy feedstock). The

  Catalyst dewaxing conditions are highly dependent on the feedstock used and the desired pour point. Preferably, hydrogen is present in the reaction zone during the catalytic dewaxing step. The ratio of hydrogen to feedstock is typically about 500 to about 30,000 SCF / bbl (standard cubic feet / barrel) (0.089 to 5.34 SCM / liter (standard cubic meter / liter)), preferably About 1000 to about 20,000 SCF / bbl (0.178 to 3.56 SCM / liter). In general, hydrogen is separated from the product and recycled to the reaction zone. Typical feedstocks include light oils, heavy gas oils, and atmospheric residues that boil at temperatures above about 350 ° F. (177 ° C.).

  A typical dewaxing process involves a hydrocarbon oil feedstock with SSZ-65 and at least one species in the presence of added hydrogen gas at a hydrogen pressure of about 15 to 3000 psi (0.103 to 20.7 MPa). Of hydrocarbon oil feedstocks boiling at temperatures above about 350 ° F. (177 ° C.) and containing linear and slightly branched hydrocarbons by contact with a catalyst comprising a Group VIII metal. It is to wax.

  The SSZ-65 hydrodewaxing catalyst can optionally contain a type of hydrogenation component commonly used in dewaxing catalysts. For examples of these hydrogenation components, see the aforementioned US Pat. No. 4,910,0006 and US Pat. No. 5,316,753.

  The hydrogenation component is present in an amount effective to provide an effective hydrodewaxing and hydroisomerization catalyst, preferably in an amount ranging from about 0.05 to 5% by weight. The catalyst can be used in a manner that increases isomerization dewaxing at the expense of cracking reactions.

  The feedstock can be hydrocracked and then dewaxed. This type of two-step process and typical hydrogenolysis conditions are described in US Pat. No. 4,921,594 issued to Miller on May 1, 1990, which is incorporated herein by reference in its entirety. .

  SSZ-65 can also be utilized as a dewaxing catalyst in the form of a layered catalyst. That is, the catalyst includes a first layer containing molecular sieve SSZ-65 and at least one Group VIII metal, and a second layer containing aluminosilicate molecular sieve having a shape selectivity higher than that of molecular sieve SSZ-65. . The use of a layered catalyst is disclosed in US Pat. No. 5,149,421 issued to Miller on September 22, 1992, which is incorporated herein by reference in its entirety. Layering also includes a bed of SSZ-65 layered with non-zeolite-type components designed for hydrocracking or hydrorefining.

  SSZ-65 can also be used under conditions such as those disclosed in US Pat. No. 4,181,598 issued to Gillespie et al. On Jan. 1, 1980, which is incorporated herein by reference in its entirety, It can be used to dewax raffinates including bright stock.

  It is often desirable to utilize mild hydrogenation (sometimes referred to as hydrorefining) to produce a more stable dewaxed product. The hydrorefining step can be performed either before or after the dewaxing step, preferably after. Hydrorefining typically involves a temperature in the range of about 190 ° C. to about 340 ° C., a pressure of about 400 psig to about 3000 psig (2.76 to 20.7 MPa gauge), a space velocity of about 0.1 to 20 ( LHSV) and a hydrogen recycle ratio of about 400-1500 SCF / bbl (0.071-0.27 SCM / liter). The hydrogenation catalyst used must be active enough not only to hydrogenate olefins, diolefins and colorants that may be present, but also to reduce the aromatic content. Suitable hydrogenation catalysts are disclosed in US Pat. No. 4,921,594 issued to Miller on May 1, 1990, which is incorporated herein by reference in its entirety. Dewaxed products prepared from hydrocracked feeds are unstable to air and light and tend to spontaneously and quickly form sludge, so that products that are reasonably stable ( For example, the hydrorefining step is beneficial when preparing lubricating oils).

Lubricating oil can be prepared using SSZ-65. For example, a _{C20 +} lubricating oil can be produced by isomerizing a _{C20 +} olefin feedstock over a catalyst comprising hydrogen form of SSZ-65 and at least one Group VIII metal. Alternatively, the lubricating oil hydrocrackes the hydrocarbon feedstock in the hydrocracking zone to obtain an effluent containing hydrocracked oil that is at least about 400 ° F. (204 ° C.). ) At a temperature of about 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge) in the presence of added hydrogen gas, the hydrogen form of SSZ-65 and at least one Group VIII metal It can be produced by dewaxing using a catalyst containing.

Aromatic Compound Formation SSZ-65 can be used to convert LSR naphtha (light straight run naphthas) and similar mixtures into aromatic-rich mixtures. Accordingly, normal and slightly branched chain hydrocarbons preferably have a boiling range of greater than about 40 ° C. and less than about 200 ° C. By contacting with a catalyst comprising SSZ-65, it can be converted to a product having a substantially higher octane aromatic content. It is also possible to convert heavier feedstocks to BTX (a mixture of benzene, toluene, xylene) or valuable naphthalene derivatives using a catalyst comprising SSZ-65.

  The conversion catalyst preferably contains a Group VIII metal compound so that it has sufficient catalytic activity for commercial use. As used herein, a Group VIII metal compound means the metal itself or a compound thereof. Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium or tin or mixtures thereof can also be used with Group VIII metal compounds, preferably with noble metal compounds. The most preferred metal is platinum. The amount of Group VIII metal present in the conversion catalyst should be within the normal range used for reforming catalysts, and is about 0.05 to 2.0% by weight, preferably 0.2 to 0.8%. It is in the range of wt%.

  For example, by neutralizing the molecular sieve with a basic metal, such as an alkali metal compound, it is a practical amount that the conversion catalyst is substantially free of acidity. It is critically important when producing aromatic compounds selectively. Methods for making a catalyst non-acidic are known in the art. For a description of such methods, see the aforementioned U.S. Pat. No. 4,910,0006 and U.S. Pat. No. 5,316,753.

  Preferred alkali metals are sodium, potassium, rubidium and cesium. The molecular sieve itself has substantially no acidity only where the silica: alumina molar ratio is very high.

Catalytic cracking The hydrocarbon cracking feedstock can be catalytically cracked in the absence of hydrogen, preferably primarily using hydrogen form of SSZ-65.

  When SSZ-65 is used as a catalytic cracking catalyst in the absence of hydrogen, the catalyst is a traditional cracking catalyst such as any aluminosilicate that has been used previously as a component in the cracking catalyst. Can be used with salt. Typically these are large pore size crystalline aluminosilicates. Examples of traditional cracking catalysts are disclosed in the aforementioned US Pat. No. 4,910,0006 and US Pat. No. 5,316,753. When traditional cracking catalyst (TC) components are used, the relative weight ratio of TC to SSZ-65 is generally about 1:10 to about 500: 1, preferably about 1:10. To about 200: 1, preferably about 1: 2 to about 50: 1, most preferably about 1: 1 to about 20: 1. New molecular sieves and / or traditional degradation components can be further ion exchanged with rare earth ions to alter the selectivity.

  Typically, cracking catalysts are used with inorganic oxide matrix components. For examples of such matrix components, see the aforementioned US Pat. No. 4,910,0006 and US Pat. No. 5,316,753.

Isomerization The present catalyst is a highly active, highly selective catalyst for isomerizing C _{4 to} C ₇ hydrocarbons. This activity means that the catalyst can function at relatively low temperatures which are thermodynamically favored for highly branched paraffins. Thus, this catalyst can produce a high octane product. A high degree of selectivity means that relatively high liquid yields can be achieved when the catalyst is used in high octane.

The method includes contacting an isomerization catalyst, ie, a catalyst comprising hydrogen form of SSZ-65, with a hydrocarbon feedstock under isomerization conditions. Preferably, the feedstock will boil within the range of 30 ° F to 250 ° F (-1 ° C to 121 ° C), preferably 60 ° F to 200 ° F (16 ° C to 93 ° C). (Light straight run fraction). Preferably, the hydrocarbon feed for this process is a substantial amount of C _{4 to} C ₇ normal and slightly branched low octane hydrocarbons, more preferably C ₅ and C ₆ hydrocarbons.

It is preferred to carry out the isomerization reaction in the presence of hydrogen. Hydrogen is added such that the ratio of hydrogen to hydrocarbon (H ₂ / HC) is preferably 0.5 to 10 H ₂ / HC, more preferably 1 to 8 H ₂ / HC. For further discussion of the conditions of the isomerization process, see the aforementioned US Pat. No. 4,911,0006 and US Pat. No. 5,316,753.

  In the present method, low sulfur feedstocks are particularly preferred. The feedstock preferably contains less than 10 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm sulfur. For feedstocks that are not yet low in sulfur, acceptable levels can be obtained by hydrogenating the feedstock with a hydrogenation catalyst that is durable against sulfur poisoning in the presaturation zone. Can be reached. For further discussion of this hydrodesulfurization process, see the aforementioned US Pat. No. 4,910,0006 and US Pat. No. 5,316,753.

  It is preferred to limit the nitrogen concentration and water content of the feedstock. Suitable catalysts and methods for these purposes are known to those skilled in the art.

  After the run period, the catalyst can be deactivated by sulfur or coke. See the aforementioned U.S. Pat. No. 4,910,0006 and U.S. Pat. No. 5,316,753 for further discussion of how to remove this sulfur and coke and how to regenerate the catalyst.

  The conversion catalyst preferably contains a Group VIII metal compound in order to provide sufficient activity for commercial use. As used herein, a Group VIII metal compound means the metal itself or a compound thereof. Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin can also be used 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 used for isomerization catalysts, in the range of about 0.05 to 2.0% by weight, preferably 0.2 to 0.8% by weight. Should.

Alkylation and transalkylation SSZ-65 can be used in processes for alkylation and transalkylation of aromatic hydrocarbons. The process comprises converting an aromatic hydrocarbon to a C _{2 to} C ₁₆ olefin alkylating agent or polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of a catalyst comprising SSZ-65. Contacting with a transalkylating agent.

  SSZ-65 can also be used to remove benzene from gasoline by alkylating benzene as described above and to recover alkylated products from gasoline.

  In order to obtain high catalytic activity, the SSZ-65 molecular sieve must be mainly in the hydrogen ion form. After calcination, preferably at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions.

  Examples of suitable aromatic hydrocarbon feedstocks that can be alkylated or transalkylated by the process of the present invention include aromatic compounds such as benzene, toluene and xylene. A preferred aromatic hydrocarbon is benzene. Naphthalene or naphthalene derivatives such as dimethylnaphthalene may be desirable. Mixtures of aromatic hydrocarbons can also be used.

  Suitable olefins for the alkylation of aromatic hydrocarbons are 2-20, preferably 2 such as ethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, or mixtures thereof. It contains ˜4 carbon atoms. Penten may be desirable. Preferred olefins are ethylene and propylene. Longer chain α-olefins can also be used.

  Where transalkylation is desired, the transalkylating agent is a polyalkyl aromatic hydrocarbon containing two or more alkyl groups, each of which can have from 2 to about 4 carbon atoms. . For example, suitable polyalkyl aromatic hydrocarbons include di-, tri-, and tetra-alkyl such as diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene, dibutylbenzene, and the like. Aromatic hydrocarbons are included. A preferred polyalkyl aromatic hydrocarbon is dialkylbenzene. A particularly preferred polyalkyl aromatic hydrocarbon is di-isopropylbenzene.

  When the alkylation is performed, the reaction conditions are as follows. Aromatic hydrocarbon feedstock must be present in stoichiometric excess. The molar ratio of aromatic compound to olefin is preferably greater than 4: 1 to prevent rapid fouling of the catalyst. The reaction temperature can range from 100 ° F to 600 ° F (38 ° C to 315 ° C), preferably from 250 ° F to 450 ° F (121 ° C to 232 ° C). The reaction pressure must be sufficient to maintain at least a partial liquid phase to delay catalyst fouling. This is typically 50 psig to 1000 psig (0.345 to 6.89 MPa gauge) depending on the feedstock and reaction temperature. The contact time can range from 10 seconds to 10 hours, but is usually 5 minutes to 1 hour. The weight hourly space velocity (WHSV) is generally in the range of about 0.5-50 expressed in grams of aromatic hydrocarbons and olefins per gram of catalyst per pound.

  When transalkylation is the process performed, the aromatic hydrocarbon molar ratio will generally range from about 1: 1 to 25: 1, preferably from about 2: 1 to about 20: 1. The reaction temperature can range from about 100 ° F. to 600 ° F. (38 ° C. to 315 ° C.), but is preferably about 250 ° F. to 450 ° F. (121 ° C. to 232 ° C.). The reaction pressure must be sufficient to maintain at least a partial liquid phase, typically in the range of about 50 psig to 1000 psig (0.345 to 6.89 MPa gauge), preferably 300 psig to 600 psig (2 0.07 to 4.14 MPa gauge). The weight hourly space velocity will range from about 0.1 to 10. US Pat. No. 5,082,990, issued to Hsieh et al. On Jan. 21, 1992, describes such a method and is incorporated herein by reference.

Conversion SSZ-65 to aromatics paraffins, light gas (light _gas) C 2 ~C ₆ paraffins, aromatic compounds, can be used to more conversion to higher molecular weight hydrocarbons. Preferably, the molecular sieve will contain a catalytic metal or metal oxide of a metal selected from the group consisting of groups IB, IIB, VIII and IIIA of the periodic table. Preferably, the metal is gallium, niobium, indium or zinc in the range of about 0.05 to 5% by weight.

Olefin Isomerization SSZ-65 can be used to isomerize olefins. The feed stream is a hydrocarbon stream containing at least one C _4-6 olefin, preferably a C _4-6 normal olefin, more preferably normal butene. As used herein, normal butene refers to any form of normal butene, such as 1-butene, cis-2-butene, and trans-2-butene. Typically, hydrocarbons other than normal butene or other _C4-6 normal olefins will be present in the feed. Other hydrocarbons can include, for example, alkanes, other olefins, aromatics, hydrogen, and inert gases.

  Typically, the feed stream can be the effluent from a fluid catalytic cracker or a methyl-tert-butyl ether unit. Fluid catalytic cracker effluents typically contain about 40-60% by weight normal butene. The methyl-tert-butyl ether unit effluent typically contains 40-100% by weight normal butene. The feed stream preferably contains at least about 40% by weight normal butene, more preferably at least about 65% by weight normal butene. In this specification, the terms iso-olefin and methyl-branched iso-olefin may be used interchangeably.

  This process is carried out under isomerization conditions. The hydrocarbon feedstock is contacted in the gas phase with a catalyst comprising SSZ-65. This method is generally used for butenes at temperatures of about 625 ° F to about 950 ° F (329 ° C to 510 ° C), preferably about 700 ° F to about 900 ° F (371 ° C to 482 ° C). And for hexene, it can be carried out at a temperature of about 350 ° F. to about 650 ° F. (177 ° C. to 343 ° C.). The pressure is from subatmospheric to about 200 psig (1.38 MPa gauge), preferably from about 15 psig to about 200 psig (0.103 to 1.38 MPa gauge), more preferably from about 1 psig to about 150 psig (0.00689-1). .03 MPa gauge).

The liquid hourly space velocity during contact is generally about 0.1 to about 50 hr ⁻¹ , preferably about 0.1 to about 20 hr ⁻¹ , more preferably about 0.2, based on the hydrocarbon feedstock. to about 10 hr ^-1, and most preferably from about 1 to about ^{5 hr -1.} The hydrogen / hydrocarbon molar ratio is maintained from about 0 to about 30 or higher. Hydrogen can be added directly to the feed stream or directly to the isomerization zone. The reaction is preferably substantially anhydrous, typically less than about 2% moisture by weight based on the feedstock. This step can be carried out in a packed bed reactor, a fixed bed, a fluidized bed reactor, or a moving bed reactor. The catalyst bed can move up or down. For example, the molar% conversion of normal butene to iso-butene is at least 10, preferably at least 25, more preferably at least 35.

Isomerization SSZ-65 in xylene, and isomerizing one or more xylene isomers in C ₈ aromatic feedstock, ortho at a rate approaching the equilibrium value -, meta -, and para - methods for obtaining xylene Is also useful. In particular, xylene isomerization is used in conjunction with another method for producing para-xylene. For example, para in the flow of mixed C ₈ aromatics - Some xylene may be recovered by crystallization and centrifugation. The mother liquor from the crystallizer is then reacted under xylene isomerization conditions to bring the ortho, meta-, and para-xylene back to near equilibrium ratios. At the same time, some of the ethylbenzene in the mother liquor is converted to xylene or a product that is easily separated by filtration. The isomerate is mixed with fresh feed and the combined stream is distilled to remove heavy and light by-products. Flow of the resulting C ₈ aromatics is then sent to the crystallizer to repeat the cycle.

  Optionally, isomerization in the gas phase is carried out in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (e.g. ethylbenzene). If hydrogen is used, the catalyst must contain about 0.1 to 2.0% by weight of a Group VIII metal component (of the periodic table), particularly a hydrogenation / dehydrogenation component selected from platinum or nickel. . Group VIII metal component means metals and metal compounds such as oxides and sulfides.

  Optionally, the isomerization feedstock is diluted with a diluent such as toluene, trimethylbenzene, naphthene or paraffin at 10-90 wt. Can be contained.

It is expected that SSZ-65 can also be used to oligomerize linear and branched olefins having about 2 to 21, preferably 2 to 5 carbon atoms. The oligomers that are the product of this process are medium to heavy olefins that are useful in fuels, either gasoline or gasoline blending stocks and chemicals.

  The method of oligomerization involves contacting a gas phase or liquid phase olefin feed with a catalyst comprising SSZ-65.

  The molecular sieve can have the original cation associated with it replaced by a wide variety of other cations by techniques known in the art. Typical cations include hydrogen, ammonium, metal cations and mixtures thereof. Among the substituted metal cations, cations of rare earth metals, manganese, calcium, and metals such as Group II metals of the periodic table, such as zinc, and Group VIII metals of the periodic table, such as nickel, are particularly preferred. One of the first requirements is that the aromatization activity of the molecular sieve is quite low, i.e. the amount of aromatic compound produced therein does not exceed about 20% by weight. This uses a molecular sieve having a controlled acidity (alpha value) that is about 0.1 to about 120, preferably about 0.1 to about 100, as measured by its ability to decompose n-hexane. Is achieved.

  α values are known in the art, for example, as shown in US Pat. No. 3,960,978 issued to Givens et al. on June 1, 1976, which is incorporated herein by reference in its entirety. Defined by standard tests. If necessary, such molecular sieves can be obtained by steaming, use in the conversion process or any other method that would occur to those skilled in the art.

Condensation of alcohols SSZ-65 can be used to condense lower aliphatic alcohols having 1 to 10 carbon atoms to gasoline boiling hydrocarbon products containing mixed aliphatic and aromatic hydrocarbons. it can. The method disclosed in US Pat. No. 3,894,107 issued July 8, 1975 to Butter et al., Which is incorporated herein by reference in its entirety, describes the process conditions used in this method. Has been.

  The catalyst may be in hydrogen form or exchanged or impregnated with a base to contain ammonium or metal cation complement, preferably in the range of about 0.05 to 5% by weight. Metal cations that can be present include any metal from Group I to Group VIII of the Periodic Table. However, in the case of Group IA metals, the cation content should never be so high as to practically deactivate the catalyst, and the exchange must also be such that all acidity is lost. . If a basic catalyst is desired, there can be other methods including treatment of oxygenated substrates.

Methane Upgrade Lower molecular weight hydrocarbons by contacting lower molecular weight hydrocarbons with catalysts containing metals or metal compounds that can convert SSZ-65 and lower molecular weight hydrocarbons to higher molecular weight hydrocarbons. Higher molecular weight hydrocarbons can be formed from these hydrocarbons. Examples of such reactions include the conversion of methane to C ₂₊ hydrocarbons such as ethylene or benzene or both. Examples of useful metals and metal compounds include lanthanides and / or actinide metals or metal compounds.

  These reactions, the metals or metal compounds used and the conditions under which they can be used are described in US Pat. No. 4,734,537 issued to Devries et al. On March 29, 1988; Washecheck et al. On July 3, 1990. U.S. Pat. No. 4,939,311; U.S. Pat. No. 4,962,261 issued to Abrevaya et al. On Oct. 9, 1990; U.S. Patent issued to Abrevaya et al. US Pat. No. 5,095,161; US Pat. No. 5,105,044 issued to Han et al. On April 14, 1992; US Pat. No. 5,105,046 issued to Washech on April 14, 1992; August 24, 1993 US Pat. No. 5,238,898 issued to Han et al. U.S. Pat. No. 5,321,185 issued to van der Vaart on June 14, and U.S. Pat. No. 5,336,825 issued on August 9, 1994 to Choudhary et al. Is incorporated herein by reference in its entirety.

  SSZ-65 can be used for the catalytic reduction of nitrogen oxides in a gas stream. Typically, the gas stream also contains oxygen, often stoichiometric excess oxygen. SSZ-65 can also contain a metal or metal ion capable of catalyzing the reduction of nitrogen oxides in or on its surface. Examples of such metals or metal ions include copper, cobalt, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium and mixtures thereof.

  An example of such a method for the catalytic reduction of nitrogen oxides in the presence of molecular sieves is described in US Pat. No. 5,037,028 issued to Ritscher et al. On Oct. 27, 1981, which is incorporated herein by reference. No. 4297328. There, the catalytic process is to burn carbon monoxide and hydrocarbons and to catalytically reduce nitrogen oxides contained in a gas stream such as exhaust gas from an internal combustion engine. The used molecular sieve is sufficiently ion-exchanged, doped or filled with metal to provide an effective amount of catalytic copper metal or copper ions inside or on the surface of the molecular sieve. In addition, the process is carried out in the presence of an excess of oxidant, for example oxygen.

  The following examples are illustrative of the invention and are not limiting.

(Example 1)
Synthesis of SDA 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium cation

  Template molecules were synthesized according to the following synthesis scheme (Scheme 1).

1- [1- (4-Chloro-phenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium iodide is replaced with the parent amine 1- [1- (4-chloro-phenyl) -cyclopropylmethyl]. -Prepared by reacting pyrrolidine and ethyl iodide. The amine 1- [1- (4-chloro-phenyl) -cyclopropylmethyl] -pyrrolidine 100 gm (0.42 mol) was added to a 3 liter three-necked reaction flask equipped with a mechanical stirrer and reflux condenser. ) In 1000 ml of anhydrous methanol. To this solution is added 98 gm (0.62 mol) of ethyl iodide and the mixture is stirred at room temperature for 72 hours. Then 39 gm (0.25 mol) of ethyl iodide is added and the mixture is heated at reflux for 3 hours. The reaction mixture is cooled and excess ethyl iodide and solvent are removed under reduced pressure using a rotary evaporator. The resulting dark tan solid (162 gm) is further purified by dissolving in acetone (500 ml) and then precipitating with the addition of diethyl ether. The resulting solid was filtered and air dried to give the desired 1- [1- (4-chloro-phenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium iodide 153 gm (93% yield). ) Is obtained as a white powder. ^The product is pure according to ¹ H and ¹³ C-NMR analysis.

  The salt of iodide is subjected to ion exchange treatment using Ion-Exchange Resin (ion exchange resin) -OH (BIO RAD (registered trademark) AH1-X8) to give 1- [1- (4-chloro-phenyl). ) -Cyclopropylmethyl] -1-ethyl-pyrrolidinium cation hydroxide form. In a 1 liter plastic bottle, 100 gm (255 mmol) of 1- [1- (4-chloro-phenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium iodide was added to 300 ml of deionized water. Dissolve in Then 320 gm of ion exchange resin is added and the solution is gently stirred overnight. The mixture is then filtered and the resin cake is rinsed with a minimum amount of deionized water. A small sample of the solution is titrated with 0.1N HCl and the filtrate is analyzed for hydroxide concentration. According to this reaction, 96% (245 mmol) of the desired 1- [1- (4-chloro-phenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium hydroxide (0.6 mol of hydroxy) Density).

The precursor amide [1- (4-chloro-phenyl) -cyclopropyl] -pyrrolidin-1-yl-methanone is reduced with LiAlH ₄ to give the parent amine 1- [1- (4-chloro-phenyl) -cyclopropyl. Methyl] -pyrrolidine is obtained. In a 3 liter three-necked reaction flask equipped with a mechanical stirrer and reflux condenser, 45.5 gm (1.2 mol) of LiAlH ₄ is suspended in 750 ml of anhydrous tetrahydrofuran (THF). The suspension was cooled to 0 ° C. (ice bath) and [1- (4-chloro-phenyl) -cyclopropyl] -pyrrolidin-1-yl-methanone 120 gm (0.48 mol) dissolved in 250 ml THF. Is added dropwise (to the suspension) through an addition funnel. After all the amide solution is added, the ice bath is replaced with a heating mantle and the reaction mixture is heated to reflux overnight. The reaction solution is then cooled to 0 ° C. (the heating mantle is replaced with an ice bath) and the mixture is diluted with 500 ml of diethyl ether. The reaction is worked up by adding 160 ml of a 15% by weight aqueous NaOH solution dropwise (through an addition funnel) with vigorous stirring. The starting gray reaction solution turns into a colorless liquid with a white powdery precipitate. The solution mixture is filtered and the filtrate is dried over anhydrous magnesium sulfate. The filtrate was filtered and concentrated to give 106 gm (94% yield) of the desired amine 1- [1- (4-chloro-phenyl) -cyclopropylmethyl] -pyrrolidine as a pale yellow oily substance. It is done. The amine is pure as shown by clean ¹ H and ¹³ C-NMR spectral analysis.

  The parent amide [1- (4-chloro-phenyl) -cyclopropyl] -pyrrolidin-1-yl-methanone is prepared by reacting pyrrolidine with 1- (4-chloro-phenyl) -cyclopropanecarbonyl chloride. . A 2 liter reaction flask equipped with a mechanical stirrer is charged with 1000 ml dry benzene, 53.5 gm (0.75 mol) pyrrolidine and 76 gm (0.75 mol) triethylamine. To this mixture (at 0 ° C.) 108 gm (0.502 mol) of 1- (4-chloro-phenyl) -cyclopropanecarbonyl chloride (dissolved in 100 ml of benzene) is added dropwise (through an addition funnel). After the addition is complete, the resulting mixture is stirred at room temperature overnight. The reaction mixture (two-phase mixture: liquid and brown precipitate) is concentrated under reduced pressure on a rotary evaporator to remove excess pyrrolidine and solvent (usually hexene or benzene). The remaining residue is diluted with 750 ml of water and extracted with 750 ml of chloroform in a separatory funnel. The organic layer is washed twice with 500 ml water and once with brine. The organic layer is then dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure on a rotary evaporator to give 122 gm (0.49 mol, 97% yield) of the amide as a tan solid.

The 1- (4-chloro-phenyl) -cyclopropanecarbonyl chloride used in the synthesis of the amine is converted to the parent acid 1- (4-chloro-phenyl) -cyclopropanecarboxylic acid as follows: thionyl chloride (SOCl ₂ ) to synthesize. 100 g of 1- (4-chloro-phenyl) -cyclopropanecarboxylic acid (0.51 mol) is added to 200 gm of thionyl chloride and 200 ml of dichloromethane in a three-necked reaction flask equipped with a mechanical stirrer and a reflux condenser. Add in small portions (5 gm at a time) over 15 minutes. After all the acid has been added, the reaction mixture is heated at reflux. The reaction vessel is equipped with a trap (filled with water) used to collect and trap acidic gaseous by-products and monitor the reaction. The reaction is usually terminated once the evolution of gaseous byproducts has stopped. The reaction mixture is then cooled and concentrated under reduced pressure using a rotary evaporator to remove excess thionyl chloride and dichloromethane. In this reaction, 109 gm (98%) of 1- (4-chloro-phenyl) -cyclopropanecarbonyl chloride is produced as a reddish viscous oil.

(Example 2)
Synthesis of SDA 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation The synthesis procedure of Example 1 was used except that the synthesis started from 1-phenyl-cyclopropanecarbonyl chloride and pyrrolidine. SDA1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation is synthesized.

(Example 3)
Synthesis of SSZ-65 In 23 cc of Teflon liner, 5.4 gm of a 0.6M aqueous solution of 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium hydroxide was added (3 g Mmol SDA), 1.2 gm of 1M NaOH in water (1.2 mmol NaOH) and 5.4 gm of deionized water. To this mixture, 0.06 gm sodium borate decahydrate (Na ₂ B ₄ O ₇ · 10H ₂ O 0.157 mmol; ˜0.315 mmol B ₂ O ₃ ) is added and completely dissolved. Stir until. CAB-O-SIL® M-5 fumed silica 0.9 gm (˜14.7 mmol SiO ₂ ) is then added to the solution and the mixture is stirred thoroughly. The resulting gel cover is removed and the gel is placed in a Parr bomb steel reactor and heated at 160 ° C. in an oven rotating at 43 rpm. The reaction is monitored by examining the pH of the gel and looking for crystal formation using a scanning electron microscope (SEM). Usually, the reaction is complete after heating for 9-12 days under the above conditions. Once crystallization is complete, the starting reaction gel changes to a mixture containing a clear liquid and a powder precipitate. The mixture is filtered through a fritted-glass funnel. The collected solids are washed thoroughly with water and then rinsed with acetone (10 ml) to remove organic residues. The solid is air dried overnight and then dried in an oven at 120 ° C. for 1 hour. The reaction gives 0.85 g of fine powder. According to SEM, there is only one kind of crystal phase. Powder XRD data analysis identifies the product as SSZ-65.

(Example 4)
Synthesis of Borosilicate SSZ-65 by Seed Addition Borosilicate SSZ as described in Example 3 above, except that 0.04 gm of SSZ-65 is added as a seed crystal to speed up the crystallization process. Repeat the synthesis of -65 (B-SSZ-65). The reaction conditions are exactly the same as in the previous example. Crystallization is complete after 4 days, yielding 0.9 gm of B-SSZ-65.

(Example 5)
Synthesis of aluminosilicate SSZ-65 A 23 cc Teflon liner was charged with 4 gm of a 0.6 M aqueous solution of 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium hydroxide. 2.25 mmol SDA), 1.5 gm of 1M NaOH in water (1.5 mmol NaOH) and 2 gm of deionized water. To this mixture, 0.25 gm of Na-Y molecular sieve (Union Carbide LZY-52; SiO ₂ / Al ₂ O ₃ = 5) is added and stirred until completely dissolved. Then CAB-O-SIL® M-5 fumed silica 0.85 gm (˜14 mmol SiO ₂ ) is added to the solution and the mixture is stirred thoroughly. The resulting gel cover is removed and the gel is placed in a Parr bomb steel reactor and heated at 160 ° C. in an oven rotating at 43 rpm. Examining the pH of the gel (an increase in pH usually results from condensation of silicate species during crystallization, and a decrease in pH often indicates that SDA is degrading) and scanning The reaction is monitored by looking for the formation of crystals using an electron microscope. Usually, after heating for 12 days under the above conditions, the reaction is complete. Once crystallization is complete, the starting reaction gel changes to a mixture containing liquid and powder precipitates. The mixture is filtered through a fritted-glass funnel. The collected solids are washed thoroughly with water and then rinsed with acetone (10 ml) to remove organic residues. The solid is air dried overnight and then dried in an oven at 120 ° C. for 1 hour. This reaction yields 0.8 gm SSZ-65.

⁻ＯＨ／ＳｉＯ_２＝０．２８、Ｒ^＋／ＳｉＯ_２＝０．２、Ｈ_２Ｏ／ＳｉＯ_２＝４４
（Ｒ^＋＝有機カチオン（ＳＤＡ）） (Examples 6 to 15)
Changing the _SiO 2 _/ B 2 _{O 3} molar ratio of the synthesis starting synthesis gel SiO ₂ / _{B 2} SSZ-65 _{which O 3} ratio changes to synthesize SSZ-65. This is achieved by using the synthesis conditions described in Example 3 while keeping everything the same while changing the SiO ₂ / B ₂ O ₃ molar ratio of the starting gel. This is achieved by keeping the amount of CAB-O-SIL® M-5 (98% SiO ₂ and 2% H ₂ O) the same while varying the amount of sodium borate in each synthesis. To do. Thus, changing the amount of sodium borate will cause a change in the SiO ₂ / Na molar ratio of the starting gel. Table 1 below shows some synthesis results with varying starting SiO ₂ / B ₂ O ₃ in the synthesis gel.

^{_{- OH / SiO 2 = 0.28,}} R + / SiO 2 = 0.2, H 2 O / SiO 2 = 44
(R ⁺ = organic cation (SDA))

(Example 16)
Calcination of SSZ-65 As described below, the SSZ-65 synthesized in Example 3 is baked to remove template molecules (SDA). A thin bed of SSZ-65 on a baking dish is heated from room temperature to 120 ° C. at a rate of 1 ° C./min in a muffle furnace and held for 2 hours. Next, the temperature is rapidly increased to 540 ° C. at 1 ° C./min and held for 5 hours. The temperature is then ramped up again to 595 ° C. at 1 ° C./min and held at that temperature for 5 hours. During the firing process, a 50/50 mixture of air and nitrogen passes through the muffle furnace at a rate of 20 standard cubic feet (0.57 standard cubic meters) / minute.

(Example 17)
Conversion of Borosilicate SSZ-65 to Aluminosilicate SSZ-65 The calcined form of borosilicate SSZ-65 (synthesized as in Example 3 and calcined as in Example 16) is aluminum nitrate nonahydrate. to a 1M solution _{(1M Al (NO 3) 3} · 9H 2 O solution 15ml / 1gm SSZ-65), by suspending the borosilicate SSZ-65, easily converted into aluminosilicate SSZ-65 form . The suspension is heated overnight at reflux. The resulting mixture is then filtered and the collected solid is thoroughly rinsed with deionized water and air dried overnight. The solid is further dried in an oven at 120 ° C. for 2 hours.

(Example 18)
Ammonium ion exchange of SSZ-65 The Na ⁺ form of SSZ-65 (prepared as in Example 3 or Example 5 and calcined as in Example 16) has its material in aqueous NH ₄ NO ₃ (typically , by heating for 2-3 hours at _NH 4 _NO 3 / 20ml 90 ℃ in _{H 2} SSZ-65 of 1gm in O) in the the ^1gm, converted to NH4 + -SSZ-65 form. The mixture is then filtered and the resulting NH ₄ -exchanged product is washed with deionized water and dried. The NH ₄ ⁺ form of SSZ-65 can be converted to the H ⁺ form by calcination to 540 ° C. (as described in Example 16).

(Example 19)
Argon Adsorption Analysis The micropore volume of SSZ-65 based on the argon adsorption isotherm at 87.5 ° K (−186 ° C.) recorded with an ASAP 2010 instrument from Micromerites is 0.16 cc / gm. The sample is first degassed at 400 ° C. for 16 hours prior to argon adsorption. The amount used at low pressure is 6.00 cm ³ / g (standard condition; STP = Standard Temperature and Pressure). The maximum value for one hour of equilibration time per usage is used and the total operating time is 35 hours. Developed for activated carbon slits by Olivier (Porous Mater. Vol. 1995, Vol. 9, p. 931) using Adaptation of Saito Foley in Horvarth-Kawazoe format (Micropoor Materials, Vol. 3, p. 531) Argon adsorption isotherms are analyzed using density functional theory (DFT) format and parameters, as well as conventional t-plot methods (J. Catalysis, 1965, vol. 319).

(Example 20)
Constraint index
The hydrogen form of SSZ-65 of Example 3 (after treatment according to Examples 16, 17 and 18) is pelletized with 3K PSI, ground and granulated to 20-40 mesh. A 0.6 gm sample of the granulated material is fired in air at 540 ° C. for 4 hours and cooled in a desiccator to ensure drying. Then, 0.5 gm is filled into a 3/8 inch diameter stainless steel tube with alundum on both sides of the molecular sieve bed. The reaction tube is heated using a Lindburg furnace. Helium is introduced into the reaction tube at a rate of 10 cc / min at atmospheric pressure. The reaction tube is heated to about 315 ° C. and a 50/50 feed of n-hexane and 3-methylpentane is introduced into the reactor at a rate of 8 μl / min. The feed is delivered with a Brownlee pump. After 10 minutes of feed introduction, start sampling directly into the GC. Constraint index (CI) values are calculated from the GC data using methods known in the art. SSZ-65 has a CI of 0.67 and a conversion rate of 92% after 20 minutes in operation. This material is quickly soiled, with a CI of 0.3 and a conversion of 15.7% at the end of 218 minutes. This data suggests a large pore molecular sieve, possibly with large cavities.

(Example 21)
Hydrogenolysis of n-hexadecane A 1 gm sample of SSZ-65 (prepared as in Example 3 and treated as in Examples 16, 17, and 18) is suspended in 10 gm of deionized water. To this suspension, a solution of Pd (NH ₃ ) ₄ (NO ₃ ) ₂ is added at a concentration that would give 0.5% by weight Pd based on the dry weight of the molecular sieve sample. The pH of the solution is adjusted to ~ 9 by adding dropwise ammonium hydroxide diluted solution. The mixture is then heated in an oven at 75 ° C. for 48 hours. The mixture is then filtered through a glass frit, washed with deionized water and air dried. The collected sample of Pd-SSZ-65 is slowly fired in air to 482 ° C. and held at that temperature for 3 hours.

  The calcined Pd / SSZ-65 catalyst is pelletized with a Carver press and granulated to produce particles having a size of 20/40 mesh. A tubular reactor of 1/4 inch outer diameter in a micro unit for n-hexadecane hydroconversion is charged with a predetermined size catalyst (0.5 g). The table below shows the hydrocracking test operating conditions and product data for n-hexadecane.

After testing the catalyst for n-hexadecane, titrate with a solution of butylamine in hexane. The temperature increases and the titration conditions and product data are again evaluated under titration conditions. From the results shown in the table below, it can be seen that SSZ-65 is effective as a catalyst for hydrocracking.

(Example 22)
Synthesis of SSZ-65 SSZ-65 was synthesized in the same manner as in Example 3 using 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium cation as SDA. To do.

Claims (69)

  (1) The molar ratio of the oxide of the first tetravalent element to the oxide of (2) the trivalent element, the pentavalent element, the second tetravalent element different from the first tetravalent element or a mixture thereof is about A molecular sieve having an X-ray diffraction line of Table II after firing, greater than 15.   (1) an oxide selected from the group consisting of silicon oxide, germanium oxide and mixtures thereof; (2) aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof. A molecular sieve having an X-ray diffraction line of Table II after firing, the molar ratio to an oxide selected from   The molecular sieve according to claim 2, wherein the oxide comprises silicon oxide and aluminum oxide.   The molecular sieve according to claim 2, wherein the oxide comprises silicon oxide and boron oxide.   The molecular sieve according to claim 2, wherein the oxide comprises silicon oxide.   2. The molecular sieve according to claim 1 which is predominantly in the hydrogen form.   2. The molecular sieve of claim 1 having substantially no acidity.   The molecular sieve of claim 2 which is predominantly in the hydrogen form.   The molecular sieve according to claim 2, which has substantially no acidity. A molecular sieve having the following composition in a molar ratio as synthesized and in an anhydrous state.
YO ₂ / W _c O _d > 15
M ₂ / _n / YO ₂ 0.01~0.03
Q _/ YO 2 0.02~0.05
Wherein Y is silicon, germanium or a mixture thereof, W is aluminum, gallium, iron, boron, titanium, indium, vanadium or a mixture thereof, c is 1 or 2, and c is 1. When d is 2, when c is 2, d is 3 or 5, M is an alkali metal cation, alkaline earth metal cation or a mixture thereof, n is the valence of M, Q Is 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation.)   The molecular sieve according to claim 10, wherein W is aluminum and Y is silicon.   The molecular sieve according to claim 11, wherein W is boron and Y is silicon.   The molecular sieve according to claim 11, wherein Q is 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium cation.   The molecular sieve according to claim 11, wherein Q is 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation.   (1) an oxide of a first tetravalent element and (2) a trivalent element, a pentavalent element, an oxide of a second tetravalent element different from the first tetravalent element or a mixture thereof, and the first oxidation For preparing a crystalline material having a molar ratio of the product to the second oxide of greater than 15, wherein the source of the oxide is 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1- Contacting a template molecule comprising ethyl-pyrrolidinium or 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation under crystallization conditions.   16. The method of claim 15, wherein the first tetravalent element is selected from the group consisting of silicon, germanium, and combinations thereof.   16. The method of claim 15, wherein the trivalent element, pentavalent element, or second tetravalent element is selected from the group consisting of aluminum, gallium, iron, boron, titanium, indium, vanadium, and combinations thereof.   The method of claim 17, wherein the trivalent element, pentavalent element, or second tetravalent element is selected from the group consisting of aluminum, boron, titanium, and combinations thereof.   The method according to claim 16, wherein the first tetravalent element is silicon.   16. The method of claim 15, wherein the template molecule comprises 1- [1- (4-chlorophenyl) -cyclopropylmethyl] -1-ethyl-pyrrolidinium cation.   16. The method of claim 15, wherein the template molecule comprises 1-ethyl-1- (1-phenyl-cyclopropylmethyl) -pyrrolidinium cation.   The method of claim 15, wherein the crystalline material has the X-ray diffraction lines of Table II after firing.   The hydrocarbon feedstock is, under hydrocarbon conversion conditions, (1) an oxide of a first tetravalent element, (2) a trivalent element, a pentavalent element, and a second tetravalent element different from the first tetravalent element. A process for converting hydrocarbons comprising the step of contacting a catalyst comprising a molecular sieve having an X-ray diffraction line of Table II after calcination, wherein the molar ratio of the element or mixture thereof to oxide exceeds about 15.   24. The method of claim 23, wherein the molecular sieve has substantially no acidity.   24. The process of claim 23, wherein the process is a hydrocracking process comprising contacting the catalyst with a hydrocarbon feedstock under hydrocracking conditions.   24. The process of claim 23, wherein the process is a dewaxing process comprising contacting the catalyst with a hydrocarbon feedstock under dewaxing conditions.   24. A method for improving the viscosity index of a waxy hydrocarbon feed dewaxed product comprising the step of contacting the catalyst with a waxy hydrocarbon feedstock under isomerization dewaxing conditions. The method described. _24. The method of claim 23, wherein the method is for producing a _{C20 +} lubricating oil from a _{C20 +} olefin feedstock comprising isomerizing the _{C20 +} olefin feedstock on a catalyst under isomerization conditions.   30. The method of claim 28, wherein the catalyst further comprises at least one Group VIII metal.   A process for catalytic dewaxing of a hydrocarbon oil feedstock containing linear and slightly branched hydrocarbons boiling at a temperature above about 350 ° F. (177 ° C.), comprising: 24. A process comprising contacting the hydrocarbon oil feedstock with a catalyst under dewaxing conditions in the presence of hydrogen pressure of about 15 to 3000 psi (0.103 to 20.7 MPa). The method described in 1.   32. The method of claim 30, wherein the catalyst further comprises at least one Group VIII metal.   A layered catalyst comprising: a first layer comprising a molecular sieve and at least one Group VIII metal; and a second layer comprising an aluminosilicate molecular sieve that is more selective in shape than the first molecular sieve. 32. The method of claim 30, comprising: Hydrocracking a hydrocarbon feedstock in a hydrocracking zone to obtain an effluent containing hydrocracked oil, and a temperature of at least about 400 ° F. (204 ° C.) in the presence of added hydrogen gas; A process for preparing a lubricating oil comprising catalytically dewaxing the effluent containing hydrocracked oil with a catalyst at a pressure of about 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge). 24. The method of claim 23, wherein   34. The method of claim 33, wherein the catalyst further comprises at least one Group VIII metal.   24. The method of claim 23, wherein the method is for isomerizing and dewaxing raffinate comprising contacting the raffinate with a catalyst in the presence of added hydrogen under isomerization and dewaxing conditions.   36. The method of claim 35, wherein the catalyst further comprises at least one Group VIII metal.   36. The method of claim 35, wherein the raffinate is bright stock.   A process for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatic content, comprising normal and slightly branched having a boiling range above about 40 ° C. and below about 200 ° C. 24. The method of claim 23, wherein the method comprises the step of contacting a hydrocarbon feedstock comprising the selected hydrocarbon with a catalyst under aromatic conversion conditions.   40. The method of claim 38, wherein the molecular sieve is substantially free of acid.   40. The method of claim 38, wherein the molecular sieve contains a Group VIII metal component.   24. The process of claim 23, wherein the process comprises contacting the hydrocarbon feedstock with a catalyst in the reaction zone under catalytic cracking conditions in the absence of added hydrogen.   42. The method of claim 41, wherein the catalyst further comprises a large pore size crystalline cracking component. Isomerization conditions, a feedstock having a hydrocarbon C ₄ -C ₇ branched normal and slightly comprising contacting with the catalyst, with C ₄ -C ₇ isomerization process for isomerizing hydrocarbons 24. The method of claim 23, wherein:   44. The method of claim 43, wherein the molecular sieve is impregnated with at least one Group VIII metal.   44. The method of claim 43, wherein the catalyst is impregnated with a Group VIII metal and then calcined in a steam / air mixture at an elevated temperature.   45. The method of claim 44, wherein the Group VIII metal is platinum. Alkylation conditions, at least a molar excess of aromatic hydrocarbon, under conditions that are at least partially liquid phase, in the presence of a catalyst, comprising contacting an olefin of C ₂ -C _20, aromatic 24. The method of claim 23, wherein the method is for alkylating a group hydrocarbon. Olefin _is an olefin of C 2 -C _4, The method of claim 47.   49. The method of claim 48, wherein the aromatic hydrocarbon and olefin are each present in a molar ratio of about 4: 1 to about 20: 1.   49. The method of claim 48, wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene, or mixtures thereof.   Transforming the aromatic hydrocarbon under transalkylation conditions comprising contacting the aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon in the presence of a catalyst at least partially in a liquid phase. 24. The method of claim 23, wherein the method is for alkylation.   52. The method of claim 51, wherein the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon are each present in a molar ratio of about 1: 1 to about 25: 1.   52. The method of claim 51, wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof.   52. The method of claim 51, wherein the polyalkyl aromatic hydrocarbon is a dialkylbenzene.   A method for converting paraffins to aromatics comprising contacting the paraffins with molecular sieves and a catalyst comprising a compound of gallium, zinc, or gallium or zinc under conditions that convert the paraffins to aromatics 24. The method of claim 23, wherein   24. The method of claim 23, wherein the method is for isomerizing an olefin comprising the step of contacting the olefin with a catalyst under conditions that cause isomerization of the olefin. The isomerization feed comprising a flow of aromatic C ₈ is a mixture of xylene isomers or isomeric xylenes and ethylbenzene and isomerization, closer to equilibrium ortho -, meta - and para - methods for obtaining xylene ratio 24. The method of claim 23, comprising contacting the feedstock with a catalyst under isomerization conditions.   24. The method of claim 23, wherein the method is for oligomerizing an olefin comprising contacting an olefin feedstock with a catalyst under oligomerization conditions. (A) introducing a gas containing a lower molecular weight hydrocarbon into the reaction zone, and subjecting the gas to a higher concentration of the catalyst and the lower molecular weight hydrocarbon in the zone under C 2 ₊ hydrocarbon synthesis conditions; A lower molecular weight hydrocarbon comprising: contacting with a metal or metal compound that can be converted to a molecular weight hydrocarbon; and (b) withdrawing a stream containing a higher molecular weight hydrocarbon from the reaction zone 24. The method according to claim 23, wherein the method is for producing higher molecular weight hydrocarbons from the process.   60. The method of claim 59, wherein the metal or metal compound comprises a lanthanide or actinide metal or metal compound.   60. The method of claim 59, wherein the lower molecular weight hydrocarbon is methane.   52. The method according to claim 23, 25, 26, 27, 28, 30, 33, 35, 41, 43, 47 or 51, wherein the molecular sieve is predominantly in the hydrogen form.   A second tetravalent element, a trivalent element, and a pentavalent element of the oxide of the first tetravalent element, which is different from the first tetravalent element, under the conditions for producing the oxygenated hydrocarbon under the conditions for producing a liquid product Or to convert the oxygenated hydrocarbon comprising a step in which the molar ratio of oxide to oxide exceeds about 15 and after calcination is contacted with a catalyst comprising a molecular sieve having the X-ray diffraction lines of Table II the method of.   64. The method of claim 63, wherein the oxygenated hydrocarbon is a lower alcohol.   65. The method of claim 64, wherein the lower alcohol is methanol.   The gas flow is directed to (1) the oxide of the first tetravalent element, (2) the trivalent element, the pentavalent element, the second tetravalent element different from the first tetravalent element or a mixture thereof To reduce oxides of nitrogen contained in a gas stream in the presence of oxygen, the step comprising contacting the molecular sieve having a molar ratio greater than about 15 and after firing with an X-ray diffraction line of Table II the method of.   68. The method of claim 66, wherein the molecular sieve contains a metal or metal ion that can catalyze the reduction of nitrogen oxides.   68. The method of claim 67, wherein the metal is copper, cobalt, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium, or mixtures thereof.   68. The method of claim 67, wherein the gas stream is an exhaust stream of an internal combustion engine.