JP2006512273A - Molecular sieve SSZ-63 - Google Patents

Abstract

The present invention relates to a novel crystalline molecular sieve SSZ-63 produced using N-cyclodecyl-N-methyl-pyrrolidinium cation as a template reagent; a method for synthesizing SSZ-63; and SSZ in the catalyst And a method of using -63.

Description

(Background of the Invention)
(Field of Invention)
The present invention relates to a process for producing SSZ-63 using novel crystalline molecular sieve SSZ-63; and N-cyclodecyl-N-methyl-pyrrolidinium cation as a template directing agent (structure directing agent). And the use of SSZ-63 as a catalyst (for example for hydrocarbon conversion reactions).

(Status of the technology)
Because of their catalytic properties as well as the unique sieving properties of crystalline molecular sieves and zeolites, they are particularly useful in applications such as, for example, hydrocarbon conversion, gas drying and separation. Although many different crystalline molecular sieves are disclosed, there is a continuing need for new zeolites with desirable properties suitable for gas separation and drying, hydrocarbon and chemical conversion, and other applications. ing. New zeolites may have a new internal interstitial structure, giving these methods enhanced selectivity.

  Crystalline aluminosilicates are usually made from aqueous reaction mixtures containing alkali metal oxides, alkaline earth metal oxides, silica and alumina. Crystalline borosilicates are usually produced under similar reaction conditions except that boron is used in place of aluminum. Different zeolites can often be formed by changing the synthesis conditions and the composition of the reaction mixture.

(Outline of the present invention)
The present invention is directed to a group of crystalline molecular sieves having unique properties, referred to herein as “molecular sieve SSZ-63” or simply “SSZ-63”. SSZ-63 is preferably obtained in the form of its silicate, aluminosilicate, titanosilicate, germanosilicate, vanadosilicate or borosilicate. The term “silicate” refers to a molecular sieve having a large molar ratio of [silicon oxide] to [aluminum oxide] (preferably a molar ratio of greater than 100), including molecular sieves composed entirely of silicon oxide. . As used herein, the term “aluminosilicate” refers to a molecular sieve containing both alumina and silica, and the term “borosilicate” refers to a molecular sieve containing both boron and silicon oxides. To tell.
According to the invention, [first tetravalent element oxide (1)] versus [trivalent element; pentavalent element; second tetravalent element different from the first tetravalent element; or a mixture thereof] The molar ratio of oxide (2)] is greater than about 15, and after calcination, a molecular sieve having the X-ray diffraction lines of Table II is provided.

  Further according to the present invention, [oxide (1) selected from silicon oxide, germanium oxide, and mixtures thereof] vs. [aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide, and A molecular sieve having an X-ray diffraction line from Table II below is provided after the molar ratio of the oxide (2)] selected from those mixtures is greater than about 15 and after calcination. The molar ratio of [first oxide or mixture of first oxides] to [second oxides] may be infinite, i.e. no second oxide is present in the molecular sieve It should be noted that there are. In this case, the molecular sieve is either an all-silica molecular sieve or a germanosilicate.

Furthermore, the present invention remains as synthesized and is anhydrous, with the following molar ratio:
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; When c is 1, d is 2 (ie, W is tetravalent), or when c is 2, d is 3 or 5 (ie, when W is trivalent, d Is 3 or when W is pentavalent, d is 5); M is an alkali metal cation, alkaline earth metal cation, or a mixture thereof; n is the valence of M (ie 1 or 2); and Q is an N-cyclodecyl-N-methyl-pyrrolidinium cation).

Further in accordance with the present invention, an oxide selected from silicon oxide, germanium oxide, and mixtures thereof greater than about 15 [aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide, And an oxide selected from a mixture thereof] is a molecular sieve produced by heat-treating a zeolite having a molar ratio of about 200 ° C. to about 800 ° C. The molecular sieve having an X-ray diffraction line of II is provided. The present invention also provides a molecular sieve produced in this way, mostly in the hydrogen form, which is ion-exchanged with an acid; or a solution of an ammonium salt; and then a second calcination. The molecular sieve prepared by carrying out is also included.
Further according to the invention, the oxidation of the oxide (1) of the first tetravalent element and the trivalent element; the pentavalent element; the second tetravalent element different from the first tetravalent element; or a mixture thereof; A crystalline material having a molar ratio of [first oxide] to [second oxide] greater than 15, comprising: There is also provided the above production method comprising contacting the source of the oxides with a template reagent containing an N-cyclodecyl-N-methyl-pyrrolidinium cation under crystallization conditions. The method of the present invention can be used not only to synthesize crystalline materials having the X-ray diffraction lines of Table II after calcination, but also to synthesize crystalline materials having a BEA ^* crystal structure.

According to the present invention, there is provided a method for converting hydrocarbons comprising contacting a hydrocarbon feedstock with a catalyst containing a zeolite according to the present invention under hydrocarbon conversion conditions. Provided. The zeolite may be mostly hydrogen type. The zeolite may not be substantially acidic.
Furthermore, according to the present invention, a hydrocracking process comprising contacting a hydrocarbon feedstock with a catalyst containing a zeolite according to the present invention (preferably mostly in the hydrogen form) under hydrocracking conditions. Is provided.
The present invention also includes a dewaxing process comprising contacting a hydrocarbon feedstock with a catalyst containing a zeolite according to the present invention (preferably mostly in the hydrogen form) under dewaxing conditions. Is included.

The present invention also provides a method for improving the viscosity index of a dewaxed product made from a waxy hydrocarbon feedstock, wherein the waxy hydrocarbon feedstock is subjected to the present invention under isomerization dewaxing conditions. The improved method comprising contacting with a catalyst containing a zeolite according to (preferably mostly in the hydrogen form) is included.
The present invention further provides a process for producing _{C20 +} lubricating oil from a _{C20 +} olefin feedstock, wherein the olefin feedstock is isomerized under isomerization conditions with a catalyst containing zeolite according to the present invention. The manufacturing method is included. The zeolite may be mostly hydrogen type. The catalyst may contain at least one Group VIII metal.

In accordance with the present invention, there is provided a process for catalytic dewaxing of hydrocarbon feeds boiling above about 350 ° F. and containing linear and slightly branched chain hydrocarbons, comprising the presence of added hydrogen gas The catalytic dehydration comprising contacting the hydrocarbon oil feedstock with a catalyst containing a zeolite according to the present invention (preferably mostly in hydrogen form) at a hydrogen pressure of about 15 to 3000 psi. A brazing method is also provided. The catalyst may contain at least one Group VIII metal. The catalyst comprises a first layer containing a zeolite according to the present invention; and a second layer containing an aluminosilicate zeolite having a shape selectivity higher than that of the zeolite of the first layer. It may be. The first layer may contain at least one Group VIII metal.
The present invention also provides a method for producing a lubricating oil comprising hydrocracking a hydrocarbon feedstock in a hydrocracking zone to obtain an effluent containing hydrocracked oil; Catalytically dewaxing the hydrocracked oil effluent with a zeolite-containing catalyst according to the present invention in the presence of gas at a temperature of at least about 400 ° F. and a pressure of about 15 psig to about 3000 psig; The manufacturing method is included. The zeolite may be mostly hydrogen type. The catalyst may contain at least one Group VIII metal.

The present invention further relates to a process for isomerization dewaxing of a raffinate comprising contacting the raffinate with a catalyst containing a zeolite according to the present invention in the presence of added hydrogen gas. A dewaxing method is included. The raffinate may be bright stock and the zeolite may be mostly in the hydrogen form. The catalyst may contain at least one Group VIII metal.
The present invention also includes a method for increasing the octane number of a hydrocarbon feedstock to produce a product having an increased aromatic hydrocarbon content, wherein the boiling point is greater than about 40 ° C and less than about 200 ° C. Containing a range of linear hydrocarbons and slightly branched hydrocarbons according to the present invention, which are rendered substantially non-acidic by neutralizing the zeolite with a basic metal And the production method comprising contacting the catalyst with a catalyst under conditions of conversion to an aromatic hydrocarbon. According to the present invention, there is also provided a process wherein the zeolite contains a Group VIII metal component.

Also according to the present invention, the catalyst containing the hydrocarbon feedstock in the reaction zone under catalytic cracking conditions and in the absence of added hydrogen gas, the zeolite according to the present invention (preferably mostly hydrogen type). There is provided a catalytic cracking method comprising contacting with a catalyst. The present invention also includes a catalytic cracking method in which the catalyst further contains a coarse pore crystalline cracking component.
The invention further provides a isomerization process for isomerizing C ₄ -C ₇ hydrocarbons under isomerization conditions, a feedstock having C ₄ -C ₇ hydrocarbons linear or slightly branched Providing an isomerization process comprising contacting with a catalyst containing a zeolite according to the present invention (preferably mostly in the hydrogen form). The zeolite can be impregnated with at least one Group VIII metal (preferably platinum). The catalyst can be calcined at high temperature in a steam / air mixture after impregnation with a Group VIII metal.

According to the present invention, there is also provided a method for alkylating an aromatic hydrocarbon according to the present invention under alkylation conditions, at least partially under liquid phase conditions (preferably mostly in hydrogen form). in a) in the presence of a catalyst containing a zeolite, the alkylation process comprises contacting at least a molar excess of the aromatic hydrocarbon and C ₂ -C ₂₀ olefins is provided. The olefins may be the C ₂ -C ₄ olefins, also each aromatic hydrocarbons and olefins is from about 4: 1 to about 20: may be present in a molar ratio. 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, there is provided a method for conducting an alkyl exchange reaction of an aromatic hydrocarbon according to the present invention, preferably at least partly in liquid phase under alkyl exchange reaction conditions. There is provided a process comprising contacting an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon in the presence of a catalyst containing a zeolite (which is in hydrogen form). The aromatic hydrocarbon and polyalkyl aromatic hydrocarbon may 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.

Furthermore, according to the present invention, there is provided a method for converting paraffin to aromatic hydrocarbon, which is a catalyst containing the zeolite according to the present invention under the conditions for converting paraffin to aromatic hydrocarbon, and comprises gallium, zinc, Alternatively, the conversion process comprising contacting paraffin with the catalyst containing a compound of gallium or zinc is provided.
According to the present invention, there is also provided a method for isomerizing an olefin, the method comprising contacting the olefin with a catalyst containing the zeolite according to the present invention under conditions for isomerizing the olefin. Provided.
Further according to the present invention, an aromatic hydrocarbon C ₈ stream of xylene isomers; or a mixture of xylene isomers and ethylbenzene, wherein a closer equilibrium ratio of ortho-xylene, meta-xylene and para-xylene is obtained. A process for isomerizing an isomerization feed containing a stream comprising contacting said feed with a catalyst containing a zeolite according to the present invention under isomerization conditions Is provided.

The present invention further provides a method for oligomerizing an olefin comprising contacting an olefin feedstock with a catalyst containing the zeolite according to the present invention under oligomerization conditions. To do.
The present invention also provides a method for converting oxygenated hydrocarbons, comprising a catalyst containing the zeolite according to the present invention under conditions for producing a liquid product, and the oxygenated hydrocarbons. There is also provided such a conversion process comprising contacting.

Further in accordance with the present invention, there is provided a process for producing a higher molecular weight hydrocarbon from a lower molecular weight hydrocarbon comprising:
(A) introducing a gas containing a smaller molecular weight hydrocarbon into the reaction zone, and then in the zone under conditions of synthesis of C ₂₊ hydrocarbons; and the smaller molecular weight Contacting the gas with a metal or metal compound capable of converting hydrocarbons to higher molecular weight hydrocarbons; and (b) recovering a stream containing higher molecular weight hydrocarbons from the reaction zone. Is provided.

  According to the present invention, there is an improved method for reducing nitrogen oxides contained in a gas stream in the presence of oxygen, comprising contacting the gas stream with a zeolite comprising: The molar ratio of the oxide of the first tetravalent element] to [the second tetravalent element different from the first tetravalent element; trivalent element; pentavalent element; or oxide thereof] is about 15 There is provided an improved method as described above, which comprises using a zeolite having a larger X-ray diffraction line of Table II after calcination. The zeolite may contain a metal or metal ion (eg, cobalt, copper, or a mixture thereof) that can catalyze the reduction of nitrogen oxides; and the improved method comprises stoichiometry. Can be carried out in the presence of an 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 encompasses a group of crystalline coarse pore molecular sieves referred to herein as “molecular sieve SSZ-63” or simply “SSZ-63”. As used herein, the term “large pore” means having an average pore diameter greater than about 6.0 mm (preferably from about 6.5 mm to about 7.5 mm).
Without wishing to be bound by any theory, it is believed that the crystal structure of SSZ-63 consists of two polymorphs of zeolite β. A typical zeolite β (BEA ^* ) has a crystal structure consisting of about 50/50 combinations of two polymorphic phases, polymorphic phase A and polymorphic phase B. The crystal structure of SSZ-63 consists of about 60-70% of the β polymorphic phase, referred to herein as β-C [Higgins], and the remaining β polymorphic phase B. The β polymorph phase C (Higgins) is different from the β polymorph phase C. The structure of polymorphic form C (Higgins) has been claimed in the literature, but polymorphic form C (Higgins) does not appear to have ever been made. For a description of polymorphic phase C (Higgins), see Higgins et al .: “The framework topology of zeolite β”, Zeolites, Vol. 446-452 (1988); and “The framework of the topology of Zeolites Beta-A Correction”, Zeolites, Vol. 9, page 358 (1989), corrected by Higgins et al. Can be found in;

  When producing SSZ-63, N-cyclodecyl-N-methyl-pyrrolidinium cation is used as a template reagent (SDA), also known as a crystallization template. SSZ-63 is generally an active source of one or more oxides selected from the group consisting of monovalent element oxides, divalent element oxides, trivalent element oxides, tetravalent element oxides and pentavalent element oxides. (Active source) is prepared by contacting with N-cyclodecyl-N-methyl-pyrrolidinium cation template reagent.

［表中、Ｙ、Ｗ、Ｑ、Ｍ及びｎは、上記に定義される通りであり；ａは、１又は２であり；ｂは、ａが１である（即ち、Ｗが４価である）とき、２であり、ａが２である（即ち、Ｗが３価である）とき、３である］に示される組成を持つ反応混合物から製造する。 SSZ-63 has the following Table A:

[Wherein Y, W, Q, M and n are as defined above; a is 1 or 2; b is 1 (ie, W is tetravalent) And when a is 2 (that is, when W is trivalent), it is 3].

In fact, SSZ-63 is
(A) containing at least one oxide source capable of forming a crystalline molecular sieve and an N-cyclodecyl-N-methyl-pyrrolidinium cation having an anion counterion that is not detrimental to the formation of SSZ-63 Preparing an aqueous solution to be used;
(B) maintaining the aqueous solution under conditions sufficient to form SSZ-63 crystals; and (c) recovering SSZ-63 crystals;
It is manufactured by the method including.

  Therefore, SSZ-63 is a crystalline material and a template reagent for forming a cross-linked three-dimensional crystal structure, and is composed of a metal oxide and a non-metal oxide that are bonded in a tetrahedral coordination by a shared oxygen atom. The bound crystalline material and the template reagent can be included. The metal oxide and the non-metal oxide are one kind or combination of oxides of the first tetravalent element (one kind or plural kinds); trivalent element (one kind or plural kinds), pentavalent element (one kind) Or one or a combination of oxides of a second tetravalent element (one or more) different from the first tetravalent element (one or more), or a mixture thereof. To do. The first tetravalent element (s) 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 selected from the group consisting of aluminum, gallium, iron, boron, titanium, indium, vanadium, and combinations thereof Is preferred. More preferably, the second trivalent or tetravalent element is aluminum or boron.

Typical sources of aluminum oxide for the reaction mixture include aluminate; alumina; aluminum colloid; aluminum oxide coated with silica sol; alumina hydrate such as Al (OH) ₃ ; AlCl ₃ and Al ₂ Aluminum compounds such as (SO ₄ ) ₃ are included. Typical sources of silicon oxide include silicates, silica hydrogels, silicic acid, fumed silica, colloidal silica, tetraalkylorthosilicates, silica hydroxide. In addition to boron, gallium, germanium, titanium, indium, vanadium and iron can also be added in forms corresponding to their aluminum and silicon counterparts.
The source zeolitic reagent can provide a source of aluminum or boron. In most cases, the source zeolite can also provide a silica source. The source zeolite in a dealuminated or deboronated form of the source zeolite can also be used as a silica source, for example, with additional silicon added using the conventional sources described above. The use of a source zeolite reagent as the alumina source for this process is described in US Pat. No. 6, issued to Nakagawa, July 6, 1993, entitled “Method of Making Molecular Sieves”. More fully described in US Pat. No. 5,225,179. The disclosure of this US patent specification is incorporated herein by reference.

Typically, alkali metal hydroxides and / or alkaline earth metal hydroxides (eg, sodium, potassium, lithium, cesium, rubidium, calcium and magnesium hydroxides) are used in the reaction mixture. However, this component can be excluded as long as equivalent basicity is maintained. A template reagent can be used to provide hydroxide ions. Thus, for example, it may be beneficial to reduce or eliminate the required amount of alkali metal hydroxide by ion-exchanging halide ions to hydroxide ions and so on. The alkali metal cation or alkaline earth metal cation may be part of the crystalline oxide material during synthesis in order to keep the valence charge balance in it.
The reaction mixture is held at an elevated temperature until SSZ-63 crystals are formed. Hydrothermal crystallization is usually carried out at a temperature between 100 ° C. and 200 ° C. (preferably between 135 ° C. and 160 ° C.) under natural pressure. The duration of the crystallization is typically longer than 1 day, preferably from about 3 days to about 20 days.

The molecular sieve is preferably made by gentle stirring.
During the hydrothermal crystallization process, SSZ-63 crystals can spontaneously nucleate from the reaction mixture. Using SSZ-63 crystals as seed material may be advantageous to reduce the time required for complete crystallization to occur. In addition, seeding can increase the purity of the resulting product by promoting nucleation and / or formation of SSZ-63 over any undesirable phase. SSZ-63 crystals, when used as seed crystals, are added in an amount between 0.1 and 10% of the weight of silica used in the reaction mixture.
Once the molecular sieve crystals are formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques (eg, filtration). The crystals are washed with water and then dried at, for example, 90 ° C. to 150 ° C. for 8 to 24 hours to obtain synthetic SSZ-63 crystals. The drying step can be performed at atmospheric pressure or in vacuum.

  As-produced SSZ-63 is a [oxide selected from silicon oxide, germanium oxide, and mixtures thereof] versus [aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide. And an oxide selected from mixtures thereof] greater than about 15; and after calcining, it has the X-ray diffraction lines of Table II below. SSZ-63 further has the composition shown in Table B below in terms of molar ratio, as-synthesized (ie, before removing the template reagent from SSZ-63) and in an anhydrous state.

表中、Ｙ、Ｗ、ｃ、ｄ、Ｍ、ｎ及びＱは、上記で定義した通りである。

In the table, Y, W, c, d, M, n and Q are as defined above.

SSZ-63 can be made essentially without using aluminum (ie, the [silica] to [alumina] molar ratio is ∞). There are ways to increase the [silica] to [alumina] molar ratio by using standard acid leaching or chelation. However, SSZ-63 that is essentially free of aluminum can be synthesized directly using a silicon source that is essentially free of aluminum as the main tetrahedral metal oxide component if boron is also present. . The boron is then optionally [Jones et al .: Chem. Mater. , Vol. 13, pp. 1041 to 1050 (2001)] The borosilicate SSZ-63 was removed by treatment with acetic acid at high temperature to produce SSZ-63 which was all silica. can do. SSZ-63 can also be produced directly as a borosilicate. The boron can be removed if desired as described above and replaced with metal atoms by techniques known in the art to make SSZ-63, for example in aluminosilicate. SSZ-63 can also be produced directly as an aluminosilicate.
Even smaller [silica] to [alumina] ratios can also be obtained using the method of inserting aluminum into the crystal skeleton. For example, aluminum insertion may occur by heat treating the zeolite in combination with an alumina binder or an alumina dissolution source. Such a method is described in US Pat. No. 4,559,315 issued December 17, 1985 to Chang et al.

  SSZ-63 appears to be composed of a novel skeletal structure or topology characterized by its X-ray diffraction pattern. As-synthesized SSZ-63 has the crystal structure in which the X-ray powder diffraction pattern of the crystal structure exhibits the characteristic line shown in Table I, thereby distinguishing it from other molecular sieves. .

Table IA below shows the x-ray powder diffraction lines of as-synthesized SSZ-63, including the actual relative intensities.

After calcination, the SSZ-63 molecular sieve has the crystal structure in which the X-ray powder diffraction pattern of the crystal structure has the characteristic lines shown in Table II.

Table IIA below shows the X-ray powder diffraction lines of calcined SSZ-63, including the actual relative intensities.

Their X-ray powder diffraction patterns were determined by standard techniques. The radiation was copper K-α / doublet. The peak height and its position were read from the relative intensity of the peak as a function of 2θ (where θ is the Bragg angle). Also, d (lattice unit lattice spacing) corresponding to these recorded lines can be calculated.
Variations in the scattering angle (2θ) measurements are estimated to be ± 0.20 ° due to instrument error and differences between individual samples.

The X-ray diffraction patterns in Table I represent SSZ-63 molecular sieves “as-synthesized” or “as-made”. Slight variations in the diffraction pattern may be caused by variations in the molar ratio of [silica] to [alumina] or [silica] to [boron] for a particular sample due to changes in the lattice constant. In addition, a sufficiently small crystal will adversely affect the shape and intensity of the peak and significantly broaden the peak width.
Table II shows typical peaks from the X-ray diffraction pattern of calcined SSZ-63. Calcination can also cause a slight shift in the diffraction pattern as well as a change in the intensity of those peaks as compared to a pattern of “as-manufactured” material. Molecular sieves produced by exchanging metals or other cations present in the molecular sieve with various other cations (eg, H ⁺ or NH ₄ ⁺ ) produce essentially similar diffraction patterns. Nevertheless, there may still be a slight shift in the lattice spacing and fluctuations in the relative intensity of the peaks. Despite these slight perturbations, the basic crystal lattice remains unchanged by these treatments.

Crystalline SSZ-63 can be used as synthesized, but is preferably heat treated (calcined). It is usually desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any desired metal ion. Molecular sieves can be leached with a chelating agent (eg, EDTA) or dilute acid solution to increase the [silica] to [alumina] molar ratio. Molecular sieves can also be treated with steam. Steam treatment helps stabilize the crystal lattice from being attacked by acid.
For molecular sieve applications where a hydrogenation-dehydrogenation function is desired, the molecular sieves are hydrogenating components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese. , Or in a state of being intimately coupled with a noble metal (for example, palladium or platinum).

Metals can also be introduced into the molecular sieve by replacing some of the cations in the molecular sieve with metal cations by standard ion exchange techniques [eg, July 7, 1964, Plank et al. No. 3,140,249 issued July 7, 1964 No. 3,140,251 issued to Planck, etc. No. 3,140,251 issued July 7, 1964 to Planck, etc. No. 3,140,253]. Typical replacing cations may include metal cations (eg, rare earth metals, Group IA metals, Group IIA metals and Group VIII metals) as well as mixtures thereof. Of these substituting cations, cations of metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn and Fe are particularly preferred.
Hydrogen, ammonium, and metal components can be ion exchanged into SSZ-63. SSZ-63 can also be impregnated with these metals. Alternatively, the metals can be physically mixed with SSZ-63 physically using standard methods known in the art.

A typical ion exchange technique involves contacting a synthetic molecular sieve with a solution containing the desired salt of one or more replaceable cations. A wide variety of salts can be used, but chlorides and other halides, acetates, nitrates, and sulfates are particularly preferred. Molecular sieves are usually calcined prior to ion exchange to remove organic material present in or on the channels. This is because more effective ion exchange is achieved. Typical ion exchange techniques are disclosed in U.S. Pat. No. 3,140,249, issued July 7, 1964, to Plank et al .; third, issued July 7, 1964, to Planck et al. 140,251; July 7, 1964, disclosed in various patent specifications including No. 3,140,253 issued to Planck et al.
The molecular sieve is typically contacted with a salt solution of the desired displacing cation, then washed with water and then dried at a temperature in the range of 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 a time in the range of 1 to 48 hours or more. Catalytically active products that are particularly useful for hydrogen conversion processes can be produced.

Regardless of the presence of cations in the synthesized form of SSZ-63, the configuration of the atoms forming the basic crystal lattice of the molecular sieve is essentially unchanged.
SSZ-63 can be formed into various physical shapes. Generally speaking, the molecular sieve is in the form of a powder, granule, or molding [eg, enough particles to pass through a 2 mesh (Tyler) sieve and be retained on a 400 mesh (Tyler) sieve. An extrudate having a diameter. For example, when forming a catalyst by extrusion with an organic binder, SSZ-63 may be extruded before drying; or drying or partial drying, then May be extruded.

  SSZ-63 can be combined with other materials that can withstand the temperatures and other conditions used in organic conversion processes. Such matrix materials include active materials and inert materials, as well as synthetic or naturally occurring zeolites, as well as inorganic materials such as clays, silica, and metal oxides. Examples of such materials and the ways in which they can be used are described in US Pat. No. 4,910,006 issued to Zones et al., May 20, 1990, and May 1994. This is disclosed in US Pat. No. 5,316,753 issued to Nakagawa on March 31. Both of these US patent specifications are hereby incorporated by reference in their entirety.

Hydrocarbon Conversion Process SSZ-63 zeolite is useful in hydrocarbon conversion reactions. Hydrocarbon conversion is a chemical catalytic process in which a carbon-containing compound is converted to another carbon-containing compound. Examples of hydrocarbon conversion reactions where SSZ-63 is expected to be useful include hydrocracking reactions; dewaxing reactions; catalytic cracking reactions; and reactions that form olefins and aromatic hydrocarbons. Is done. The catalysts can also be used in other petroleum refining and hydrocarbon conversion reactions [eg isomerization of n-paraffins and naphthenes; polymerization and oligomerization of olefinic or acetylenic compounds (eg isobutylene and butene-1); Reforming and isomerizing aromatic hydrocarbons (eg m-xylene); and disproportionating aromatic hydrocarbons (eg toluene) to give a mixture of benzene, xylene and higher methylbenzene], It is also useful in oxidation reactions. Also included are rearrangement reactions to produce naphthalene derivatives; and the formation of higher molecular weight hydrocarbons from lower molecular weight hydrocarbons (improving methane quality).
The SSZ-63 catalyst can have high selectivity and can provide the desired product at high rates relative to the total product under hydrocarbon conversion conditions.

SSZ-63 zeolite can be used to treat hydrocarbon feedstocks. Hydrocarbon feedstocks contain carbon compounds; from many different sources [eg, from unused petroleum fractions, recycled petroleum fractions, shale oil, liquefied coal, tar sand oil, NAO Synthetic paraffin, recycled plastic feedstock]; and generally any carbon-containing feedstock that is susceptible to catalytic reactions with zeolites. Depending on the type of treatment that the hydrocarbon feedstock is expected to receive, the feedstock may contain metal or no metal; the feedstock may also contain large or small amounts of nitrogen or sulfur impurities. May contain. However, in general, it can be determined that the lower the metal, nitrogen and sulfur content of the feed, the more effective the treatment (and the more active the catalyst).
Conversion of the hydrocarbon feed may occur in any convenient manner (eg, fluid bed reactor, moving bed reactor or fixed bed reactor, depending on the type of method desired). The formulation of the catalyst particles varies and depends on the conversion method and operating method.

Other reactions that can be performed using the catalysts of the present invention containing a metal (eg, a Group VIII metal such as platinum) include hydrogenation-dehydrogenation, denitrogenation and desulfurization. Reaction is included.
The following table shows typical reaction conditions that can be used when using a catalyst containing SSZ-63 in the hydrocarbon conversion reaction of the present invention. Preferred conditions are shown in parentheses.

下記に、他の反応条件及びパラメータを与える。

Other reaction conditions and parameters are given below.

The use of a catalyst containing hydrocracking SSZ-63 (preferably one in which the hydrogen type is dominant) and a hydrogenation promoter, makes use of the aforementioned US Pat. No. 4,910,006 and US Pat. , 316, 753, the heavy oil residue feedstock, the cyclic feedstock, and other hydrocracking feedstocks can be hydrocracked using the process conditions and catalyst components disclosed in US Pat.
These hydrocracking catalysts contain an effective amount of at least one hydrocracking component of the type commonly used for hydrocracking catalysts. The hydrocracking component is usually selected from the group of hydrogenation catalysts consisting of one or more metals from Group VIB and Group VIII and salts, complexes and solutions of these metals. The hydrogenation catalyst is preferably a group consisting of at least one of platinum, palladium, rhodium, iridium, ruthenium, and mixtures thereof, or at least one of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. The group consisting of species is selected from the group consisting of metals, salts, and complexes thereof. When referring to one or more metals that are active as a catalyst, it is one or more of the metals described above in the elemental state; or some form of oxide, sulfide, halide, carboxylate, etc. It is intended to include the metal. 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 wt%.

SSZ-63 (preferably one in which the hydrogen type is dominant) can be used to dewax the hydrocarbon feedstock by selectively removing dewaxed linear paraffins. When the waxy feed is contacted with SSZ-63 under isomerization dewaxing conditions, the viscosity index of the dewaxed product is typically improved (compared to the waxy feed).
The conditions for catalyst dewaxing are largely determined by the feedstock used and the desired pour point. It is preferred that hydrogen be present in the reaction zone during the catalyst dewaxing process. The ratio of [hydrogen] to [feedstock] is typically between about 500 and about 30,000 SCF / bbl (standard cubic feet / barrel), preferably between about 1000 and about 20,000 SCF / bbl. Hydrogen is usually separated from the product and recycled to the reaction zone. Typical feedstocks include light gas oil; heavy gas oil; and atmospheric distillation residue that boils at temperatures above about 350 ° F.

A typical dewaxing process is a hydrocarbon oil feedstock that boils at a temperature above about 350 ° F., which contains linear and slightly branched chain hydrocarbons, which are added hydrogen gas (added). catalytic dewaxing of the feedstock by contacting with a catalyst containing SSZ-63 and at least one Group VIII metal in the presence of hydrogen gas) at a hydrogen pressure of about 15 to 3000 psi.
The SSZ-63 hydrodewaxing catalyst may optionally contain a type of hydrogenation component commonly used in dewaxing catalysts. See the aforementioned U.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 for examples of these hydrogenation components.

The hydrogenation component is present in an amount effective to provide an effective hydrodewaxing and hydroisomerization catalyst (preferably in an amount of about 0.05 to 5% by weight). The catalyst can be operated in such a way as to enhance isomerization dewaxing at the expense of cracking reactions.
The feedstock may be hydrocracked and then dewaxed. This type of two-stage process and typical hydrocracking conditions are described in US Pat. No. 4,921,594, issued May 1, 1990 to Miller. This US patent specification is hereby incorporated by reference in its entirety.
SSZ-63 can also be used as a dewaxing catalyst in the form of a layered catalyst. That is, the catalyst comprises a first layer containing zeolite SSZ-63 and at least one Group VIII metal, and a second layer containing an aluminosilicate that is more shape selective than zeolite SSZ-63; Contains. The use of a layered catalyst is described in US Pat. No. 5,149,421 issued September 22, 1992 to Miller. This US patent specification is hereby incorporated by reference in its entirety. The layer also includes a layer of SSZ-63 laminated together with a non-zeolite component designed for hydrocracking or hydrofinishing.

SSZ-63 is bright stock under conditions [e.g., conditions disclosed in US Pat. No. 4,181,598 issued to Gillespie et al., Jan. 1, 1980]. It can also be used to dewax raffinates containing. This US patent specification is hereby incorporated by reference in its entirety.
In order to produce a more stable dewaxed product, it is often desirable to use mild hydrogenation (sometimes referred to as hydrofinishing). The hydrofinishing step can be performed before or after (preferably after) the dewaxing step. Hydrofinishing typically has a temperature in the range of about 190 ° C. to about 340 ° C., a pressure of about 400 psig to about 3000 psig, a space velocity (LHSV) of between about 0.1-20, about 400-1500 SCF / bbl. The hydrogen recycle ratio is performed. The hydrogenation catalyst used is not only sufficiently active to hydrogenate olefins, diolefins and color bodies that may be present, but also to reduce the content of aromatic hydrocarbons. Must be sufficiently active. A suitable hydrogenation catalyst is disclosed in US Pat. No. 4,921,594, issued May 1, 1990 to Miller. This US patent specification is hereby incorporated by reference in its entirety. The hydrofinishing process is beneficial for producing an acceptable stable product (e.g., a lubricating oil). This is because the dewaxed product produced from hydrocracked feedstock tends to be unstable to air and light and tends to spontaneously and rapidly form sludge.

A lubricating oil can be produced using SSZ-63. For example, _{C20 +} lubricating oil can be produced by isomerizing a _{C20 +} olefin feedstock with a catalyst containing hydrogen-type SSZ-63 and at least one Group VIII metal. Alternatively, the lubricating oil hydrocrackes the hydrocarbon feedstock in a hydrocracking zone to obtain an effluent containing hydrocracked oil; then, in the presence of added hydrogen gas, at least about 400 Catalytic dewaxing of the effluent with a catalyst containing SSZ-63 in hydrogen form and at least one Group VIII metal at a temperature of ° F and a pressure of about 15 psig to about 3000 psig; can do.

Aromatic Hydrocarbon Formation SSZ-63 can be used to convert light straight run naphtha and similar mixtures to mixtures of higher aromatic hydrocarbons. For example, the carbonization may be achieved by contacting a linear and slightly branched hydrocarbon (preferably having a boiling range above about 40 ° C. and below about 200 ° C.) with a catalyst containing SSZ-63. The hydrogen feed can be converted to a product having a substantially higher octane aromatic hydrocarbon content. It is also possible to convert heavier feedstocks to BTX (benzene-toluene-xylene) or valuable naphthalene derivatives using a catalyst containing SSZ-63.
The conversion catalyst preferably contains a Group VIII metal compound so that it has 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. Further, rhenium or tin, or a mixture thereof can be used together with a Group VIII metal compound (preferably a noble metal compound). The most preferred metal is platinum. The amount of Group VIII metal present in the conversion catalyst is within the normal range used in reforming catalysts (about 0.05 to 2.0 wt%, preferably about 0.2 to 0.8 wt%). It is desirable that

For example, by neutralizing a zeolite with a basic metal (eg, alkali metal, compound), the conversion catalyst is not substantially acidic to selectively produce useful amounts of aromatic hydrocarbons. Is serious. Methods for ensuring that the catalyst is not acidic are known in the art. For a description of such methods, see the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753.
Preferred alkali metals are sodium, potassium, rubidium and cesium. The zeolite itself may not be substantially acidic only at very large [silica]: [alumina] molar ratios.

The catalytic cracking hydrocarbon cracking feedstock can be catalytically cracked in the absence of hydrogen using SSZ-63 (preferably, mostly hydrogen type).
When SSZ-63 is used as a catalytic cracking catalyst in the absence of hydrogen, the catalyst is a traditional cracking catalyst (eg, any aluminosilicate conventionally used as a component of cracking catalyst). Can be used together. These are typically coarse pore crystalline aluminosilicates. Examples of these traditional cracking catalysts are disclosed in the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753. When using traditional cracking catalyst (TC) components, the relative weight ratio of [TC] to [SSZ-63] is generally between about 1:10 and about 500: 1, preferably about 1:10. Between about 200: 1, preferably between about 1: 2 to about 50: 1, most preferably between about 1: 1 to about 20: 1. New zeolites and / or traditional cracking components can be further ion exchanged with rare earth ions to modify selectivity.
These cracking catalysts are typically used with an inorganic oxide matrix component. For examples of such matrix components, see the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753.

Isomerization The present catalyst is very active and is very selective for the isomerization of C _{4 to} C ₇ hydrocarbons. By activity is meant that the catalyst can operate at relatively low temperatures that are thermodynamically favorable to highly branched paraffins. As a result, the catalyst can produce a high octane product. High selectivity means that a relatively high liquid yield can be obtained with a high octane number when the catalyst is operating.
The method includes contacting an isomerization catalyst (eg, a catalyst containing hydrogen-type SSZ-63) with a hydrocarbon feedstock under isomerization conditions. The feedstock is preferably a light straight fraction that boils within the range of 30 ° F to 250 ° F, preferably 60 ° F to 200 ° F. The hydrocarbon feed for the process is linear; and slightly branched; preferably contains a significant amount of C ₄ -C ₇ low octane hydrocarbons, C ₅ -C ₆ Hydrocarbons are more preferred.

It is preferred to carry out the isomerization reaction in the presence of hydrogen. By addition of hydrogen, 0.5~10 _(H 2 / HC) of between [hydrogen] versus [hydrocarbons] ratio _(H 2 / HC during more preferably 1~8 _(H 2 / HC) ) Is preferred. For further discussion on isomerization process conditions, see the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753.
Low sulfur feedstocks are particularly preferred in the present process. The feedstock preferably contains less than 10 ppm sulfur, more preferably less than 1 ppm, and most preferably less than 0.1 ppm. For feedstocks where sulfur is still not low, acceptable concentrations can be achieved by hydrogenating the feedstock in a pre-saturation zone with a hydrogenation catalyst that is resistant to sulfur poisoning. For further discussion on this hydrodesulfurization process, see the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753.

It is preferred to limit the nitrogen concentration and moisture content of the feedstock. Suitable catalysts and methods for these purposes are known to those skilled in the art.
The catalyst may be deactivated by sulfur or coke after an operating period. For further discussion regarding this method of removing sulfur and coke, see the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753.

  The conversion catalyst preferably contains a Group VIII metal compound so that it has sufficient activity for commercial use. As used herein, “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. Along with the noble metal, rhenium and tin can also be used. The most preferred metal is platinum. The amount of Group VIII metal present in the conversion catalyst is within the normal range used for isomerization catalysts (about 0.05-2.0 wt%, preferably 0.2-0.8 wt%). Is desirable.

Alkylation and alkyl exchange reaction SSZ-63 can be used in a method for carrying out alkylation and alkyl exchange reactions of aromatic hydrocarbons. Method, under at least partially liquid phase conditions, in the presence of a catalyst containing SSZ-63, and C ₂ -C ₁₆ olefin alkylating agent or a polyalkyl aromatic hydrocarbon transalkylation agent, aromatic hydrocarbons Including contacting with hydrogen.
SSZ-63 can also be used to remove benzene from gasoline by alkylating benzene as described above and then removing the alkylated product from the gasoline.
In order to obtain high catalytic activity, it is desirable that the SSZ-63 zeolite is mostly in its 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, for example, benzene, toluene, and xylene. A preferred aromatic compound is benzene. Naphthalene or a naphthalene derivative (eg, dimethylnaphthalene) may be desirable. Mixtures of various aromatic hydrocarbons can also be used.
Suitable olefins for the alkylation of aromatic hydrocarbons are those containing 2 to 20, preferably 2 to 4 carbon atoms (eg, ethylene, propylene, butene-1, trans-butene-2, and cis). -Butene-2, or a mixture thereof). Penten may be desirable. Preferred olefins are ethylene and propylene. Longer chain alpha olefins can also be used.

If an alkyl exchange reaction is desired, the alkyl exchange reagent is a polyalkyl aromatic carbonization containing two or more alkyl groups, each of which may have from 2 to about 4 carbon atoms. Hydrogen. Suitable polyalkyl aromatic hydrocarbons include, for example, dialkyl aromatic hydrocarbons, trialkyl aromatic hydrocarbons, and tetraalkyl aromatic hydrocarbons [eg, diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene), diisopropyl Benzene, diisopropyltoluene, dibutylbenzene, etc.]. Preferred polyalkyl aromatic hydrocarbons are those dialkylbenzenes. An especially preferred polyalkyl aromatic hydrocarbon is diisopropylbenzene.
When the process carried out is alkylation, the reaction conditions are as follows: The aromatic hydrocarbon feedstock is preferably present in a stoichiometric excess. The molar ratio of [aromatic hydrocarbon] to [olefin] is preferably greater than 4: 1 to prevent rapid catalyst fouling. The reaction temperature may range from 100 ° F to 600 ° F, preferably from 250 ° F to 450 ° F. The reaction pressure is desirably sufficient to maintain at least a partial liquid phase to retard catalyst fouling. This depends on the feedstock and reaction temperature, but is typically 50 psig to 1000 psig. The contact time may range from 10 seconds to 10 hours, but is usually 5 minutes to 1 hour. The weight based space velocity (WHSV) as grams (lb) of aromatic hydrocarbons and olefins per gram (pound) of catalyst per hour is typically in the range of about 0.5-50.

  When the process carried out is an transalkylation reaction, the molar ratio of aromatic hydrocarbons usually ranges from about 1: 1 to 25: 1, preferably from about 2: 1 to 20: 1. The reaction temperature may range from about 100 ° F to 600 ° F, but is preferably in the range of about 250 ° F to 450 ° F. The reaction pressure is desirably sufficient to maintain at least a partial liquid phase, and typically ranges from about 50 psig to 1000 psig, preferably from 300 psig to 600 psig. Weight based space velocities range from about 0.1-10. US Pat. No. 5,082,990, issued January 21, 1992 to Hsieh et al., Describes such a method. That US patent specification is incorporated herein by reference.

Aromatic conversion light gas C ₂ -C ₆ paraffins to hydrocarbon paraffin, to be converted into hydrocarbons even greater molecular weight includes aromatic compounds, can be used SSZ-63. The zeolite preferably contains a catalyst metal or a catalyst metal oxide in which the metal is selected from the group consisting of groups IB, IIB, VIII and IIIA of the periodic table. The metal is preferably gallium, niobium, indium or zinc in the range of about 0.05 to 5% by weight.

Isomerization SSZ-63 in xylene also isomerizing one or more xylene isomers _{C 8} aromatic hydrocarbon feedstock, ortho-xylene, meta-xylene and para-xylene, close to the equilibrium value (equilibrium value) May be useful in methods to obtain ratios. Xylene isomerization is used, inter alia, in conjunction with a separate process for producing para-xylene. For example, a portion of paraxylene in the mixed C ₈ aromatic hydrocarbon stream may be recovered by crystallization and centrifugation. The mother liquor from the crystallizer is then reacted under xylene isomerization conditions to recover orthoxylene, metaxylene and paraxylene to near equilibrium ratio. At the same time, a portion 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 mixed stream is distilled to remove heavy and light by-products. The resulting C ₈ aromatic hydrocarbon stream is then sent to the crystallizer to repeat the cycle.

The isomerization in the gas phase is optionally carried out in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (e.g. ethylbenzene). When using hydrogen, the catalyst preferably contains about 0.1 to 2.0 weight percent of a hydrogenation / dehydrogenation component selected from Group VIII metal components (particularly platinum or nickel) of the periodic table. Group VIII metal component means these metals; and compounds of these metals (eg, oxides and sulfides).
The isomerization feed may optionally contain a diluent (eg, toluene, trimethylbenzene, naphthene or paraffin).

It is believed that the oligomerized SSZ-63 can also be used to oligomerize linear and branched olefins having about 2 to 21, preferably 2 to 5 carbon atoms. The oligomer that is the product of the process is a medium for heavy olefins that are useful for both fuels (ie gasoline; or feedstock gasoline) and chemicals.
The oligomerization process involves contacting the olefin feed in the gas phase or liquid phase with a catalyst containing SSZ-63.

The zeolite may have its original cation attached to it replaced with various other cations by techniques well known in the art. Typical cations include hydrogen, ammonium, and metal cations, and mixtures thereof. With regard to substituting metal cations, certain preferences are made of metals [eg, rare earth metals, manganese, calcium as well as Group II metals (eg, zinc) of the periodic table, and Group VIII of the periodic table ( For example, nickel)] cations. One of the most important requirements is that the zeolite has a fairly low aromatization activity (ie, in that case the amount of aromatic hydrocarbons produced is about 20% by weight or less). That is. This means that the acid activity (α value) as measured by the ability of the zeolite to decompose n-hexane is controlled from about 0.1 to about 120, preferably from about 0.1 to about 100. This is achieved by using the zeolites made.
The α value is defined by standard tests known in the art, for example, as shown in US Pat. No. 3,960,978, issued June 1, 1976 to Givens et al. The That US patent is hereby incorporated by reference in its entirety. Such zeolites can be obtained, if desired, by steaming used in the conversion process; or by any other method that may occur to those skilled in the art.

Condensation of alcohols A hydrocarbon product having a boiling point of gasoline by condensing a lower aliphatic alcohol having 1 to 10 carbon atoms, which contains a mixed aliphatic hydrocarbon and aromatic hydrocarbon SSZ-63 can be used to make a hydrocarbon product. The method disclosed in US Pat. No. 3,894,107 issued July 8, 1975 to Butter et al. Describes the working conditions used in this method. This US patent is hereby incorporated by reference in its entirety.
The catalyst may be in hydrogen form; or base exchanged or impregnated to contain ammonium or metal cation complement, preferably in the range of about 0.05 to 5% by weight. Have been. The metal cations that can be present include any of the Group I-VIII metals of the periodic table. However, in any case for a Group IA metal, the cation content appears to be high enough to make the catalyst virtually inactive, and the exchange seems to be high enough to eliminate all acidity. . There may be other methods involving the treatment of oxygen treated substrates, where a basic catalyst is desirable.

Hydrocarbon quality improvement smaller molecular weight of methane, SSZ-63; and, a metal or metal compound hydrocarbons lower molecular weight can be converted to hydrocarbons higher molecular weight; be contacted with the catalyst containing Can form higher molecular weight hydrocarbons from smaller molecular weight hydrocarbons. Examples of such reactions include the conversion of methane to C ₂₊ hydrocarbons (eg, ethylene or benzene, or both). Examples of useful metals and metal compounds include lanthanide and / or actinide metals or metal compounds.
These reactions; the metal or metal compound used; and the conditions under which the reaction can be carried out are described in U.S. Pat. No. 4,734,537, issued March 29, 1988 to Devries et al. No. 4,939,311 issued to Washcheck et al. On July 3, 1990; No. 4,962,261 issued to Abrevaya et al. On October 9, 1990; No. 5,095,161 issued to Abribaya et al. On March 10, 1992; No. 5,105,044 issued to Han et al. On April 14, 1992; No. 5,105,046 issued to Washcheck on April 14, 1993; No. 5,238,898 issued to Han et al. On August 24, 1993; No. 5,321,185 issued to Van der Vaart et al. On June 14, 994; and issued to Choudhary et al. On August 9, 1994 No. 5,336,825. Each of these US patent specifications is hereby incorporated by reference in its entirety.

SSZ-63 can be used to perform catalytic reduction of nitrogen oxides in the gas stream. The gas stream typically also contains oxygen, often in its stoichiometric excess. SSZ-63 may also contain a metal or metal ion that can catalyze the reduction of nitrogen oxides in or on SSZ-63. Examples of such metals or metal ions include copper, cobalt, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium, and mixtures thereof.
One example of such a process for the catalytic reduction of nitrogen oxides in the presence of zeolite is disclosed in US Pat. No. 4,297,328 issued Oct. 27, 1981 to Ritscher et al. Has been. This US patent specification is hereby incorporated by reference. Catalytic methods there are combustion of carbon monoxide and hydrocarbons; and catalytic reduction of nitrogen oxides contained in a gas stream (eg, exhaust gas from an internal combustion engine). The zeolite being used is sufficiently ion-exchanged, doped or loaded with metal so that an effective amount of catalytic copper or copper ions is provided within or on the zeolite. In addition, the process is performed in an excess of oxidant (eg, oxygen).

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

カチオンと結合しているアニオン（Ｘ⁻）は、ゼオライトの形成に有害でないアニオンであれば如何なるものでもよい。典型的なアニオンには、ハロゲン（例えば、フッ化物、塩化物、臭化物及びヨウ化物）、水酸化物、酢酸塩、硫酸塩、テトラフルオロホウ酸塩、カルボン酸塩、等が包含される。最も好ましいアニオンは、水酸化物である。 Example 1
Synthesis of template reagent A (N-cyclodecyl-N-methyl-pyrrolidinium cation)

The anion (X ⁻ ) bonded to the cation may be any anion that is not harmful to the formation of zeolite. Typical anions include halogens (eg, fluoride, chloride, bromide and iodide), hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like. The most preferred anion is a hydroxide.

The N-cyclodecyl-N-methyl-pyrrolidinium cation of the template reagent (SDA) was synthesized according to the method described below (see Scheme 1). To a solution of cyclodecanone (25 g; 0.16 mol) in 320 ml of anhydrous hexane in a three-necked round bottom flask equipped with a reflux condenser and a mechanical stirrer, 34 g (0.48 mol) of pyrrolidine and 48 g (0.4 mol) of anhydrous magnesium sulfate was added. The resulting mixture was stirred while refluxing for 5 days with heating. The mixture was filtered through a glass funnel. The filtrate was concentrated under reduced pressure by a rotary evaporator to produce 32 g (96%) of the expected enamine (1-cyclodec-1-enyl-pyrrolidine) as a reddish oily substance. ¹ H-NMR and ¹³ C-NMR spectrum confirmed the desired product. The enamine was reduced by catalytic hydrogenation in ethanol in the presence of 10% Pd supported on activated carbon at 55 psi hydrogen pressure in ethanol to give a quantitative yield of the corresponding amine (N-cyclodecyl-pyrrolidine). did.

Quaternization of N-cyclodecyl-pyrrolidine with methyl iodide (synthesis of N-cyclodecyl-N-methyl-pyrrolidinium iodide)
To a solution of 30 g (0.14 mol) N-cyclodecyl-pyrrolidine in 250 ml absolute alcohol in a 1 liter reaction flask was added 30 g (0.21 mol) methyl iodide. The reaction mixture was mechanically stirred at room temperature for 48 hours. Then 0.5 molar equivalent of methyl iodide was added and the mixture was then heated to reflux and refluxed for 30 minutes. The reaction mixture was then cooled and concentrated under reduced pressure on a rotary evaporator to give the product as a pale yellow solid. The product was purified by dissolving in acetone; then precipitating by adding diethyl ether. Recrystallization yielded 46 g (93%) of pure N-cyclodecyl-N-methyl-pyrrolidinium iodide. ¹ H-NMR and ¹³ C-NMR for the product were typical.

Ion exchange (synthesis of N-cyclodecyl hydroxide-N-methyl-pyrrolidinium hydroxide)
N-cyclodecyl-N-methyl-pyrrolidinium iodide (45 g; 0.128 mol) was dissolved in 150 ml of water in a 500 ml plastic bottle. To the solution was added 160 mg of ion exchange resin —OH [BIO RAD® AH1-X8] and the mixture was stirred at room temperature overnight. The mixture was filtered and the solid was washed with an additional 85 ml of water. The reaction gave 0.12 mol of SDA (N-cyclodecyl-N-methyl-pyrrolidinium hydroxide) as indicated by titration analysis with 0.1N HCl.

(Example 2)
Synthesis of Borosilicate SSZ-63 In a 23 cc Teflon (registered trademark) liner, 4.9 g of a 0.61 molar aqueous solution of N-cyclodecyl-N-methyl-pyrrolidinium hydroxide (SDA 3 mmol) and 1 molar aqueous solution of NaOH 1 .2 g (1.2 mmol NaOH) and 5.9 g deionized water were charged. To this mixture was added 0.06 g of sodium borate decahydrate (0.157 mmol of Na ₂ B ₄ O ₇ · 10H ₂ O; about 0.315 mmol of B ₂ O ₃ ) until completely dissolved. Stir. To this solution, 0.9 g of CABO-SIL M-5® fumed silica (about 14.7 mmol of SiO ₂ ) was added and mixed well by hand. The resulting gel was heated at about 160 ° C. in an oven with the lid removed and placed in a Parr steel autoclave and rotated at about 43 rpm. The reaction was monitored by periodically monitoring the pH of the gel; expecting crystal growth using a scanning electron microscope (SEM). Immediately after crystallization was complete, after heating for 12 days under the conditions described above, the starting reaction gel became a clear liquid layer and a finely divided sediment. The mixture was filtered through a glass funnel. The collected solid was washed thoroughly with water and then with acetone (about 20 ml) to remove any organic residues. The solid was air dried overnight and then dried in an oven at 120 ° C. for 1 hour. The reaction gave 0.85 g of SSZ-63. The authenticity of SSZ-63 was determined by its unique XRD pattern and transmission electron microscopy analysis.

(Example 3)
Conversion of Borosilicate SSZ-63 to Aluminosilicate SSZ-63 Synthesized as described in Example 2 above and calcined borosilicate SSZ-63 as shown in Example 17 below, was suspended in a 1 molar solution [1 mole of _{Al (NO 3) 3 · 9H} 2 O solution 15ml / zeolite 1 g] of aluminum nitrate nonahydrate. The suspension was heated at reflux for 48 hours. The mixture was then filtered and the collected solid was washed thoroughly with water and then air dried overnight. The solid was further dried in an oven at 120 ° C. for 2 hours.

Example 4
Synthesis of Germanosilicate SSZ-63 In a 23 cc Teflon (registered trademark) liner, a 0.61 molar aqueous solution of N-cyclodecyl-N-methyl-pyrrolidinium hydroxide 4.85 g (SDA 3 mmol) and a 1 molar aqueous solution of NaOH 1 .25 g (NaOH 1.25 mmol) and deionized water 5.8 g were charged. To this mixture was added 0.25 g (2.39 mmol) of GeO ₂ and stirred until completely dissolved. To this solution was added 0.7 g of CAB-O-SIL M-5® (about 11.4 mmol of SiO ₂ ) and mixed well by hand. The resulting gel was heated at about 160 ° C. in an oven with the lid removed, placed in a pearl steel autoclave and rotated at about 43 rpm. The reaction was monitored by periodically monitoring the pH of the gel; expecting crystal growth using a scanning electron microscope (SEM). Immediately after crystallization was complete, after heating for 6 days, the starting reaction gel became a clear liquid layer and a fine sediment. The mixture was filtered through a glass funnel. The collected solid was washed thoroughly with water and then with acetone (about 20 ml) to remove any organic residues. The solid was air dried overnight and then dried in an oven at 120 ° C. for 1 hour. The reaction gave 0.73 g of SSZ-63.

(Examples 5 to 16)
Changing the _SiO 2 _/ B 2 _{O 3} ratio of the synthesis starting synthesis gel of borosilicate SSZ-63, was synthesized SSZ-63. This was accomplished by changing the SiO ₂ / B ₂ O ₃ ratio of the starting gel, although all were kept the same using the synthesis conditions described in Example 2. This means that the amount of sodium borate decahydrate added in each experiment, while keeping the amount of CAB-O-SIL M-5® (a source of SiO ₂ ) constant. Went by changing. Consequently, changing the amount of sodium borate decahydrate changed the SiO ₂ / Na ratio in these starting gels. The table below shows the SiO ₂ / B ₂ O ₃ ratio, the SiO ₂ / Na ratio, and the observed product for each experiment.

(Example 17)
Calcination of SSZ-63 The material from Example 3 is calcined in the following manner. A thin bed of material is heated in a muffle furnace from room temperature to 120 ° C. at a rate of 1 ° C./min and held at 120 ° C. for 3 hours. The temperature is then ramped to 540 ° C. at the same rate and held at this temperature for 5 hours. The temperature is then raised to 594 ° C. and held at that temperature for an additional 5 hours. During the heating, a 50/50 mixture of air and nitrogen is passed over the SSZ-63 at a rate of 20 standard cubic feet per minute.

(Example 18)
Using NH ₄ exchanged NH ₄ NO ₃ , an ion exchange of the calcined SSZ-63 material (prepared in Example 2 and calcined in Example 17) was performed to convert the SSZ-63 to its Na ^Convert from ⁺ form to NH ₄ ⁺ form and finally to H ⁺ form. The same mass of NH ₄ NO ₃ and SSZ-63 is slurried with water in a [water] to [SSZ-63] ratio of 25-50: 1. The exchange solution is heated at 95 ° C. for 2 hours and then filtered. This procedure can be repeated up to 3 times. After the final exchange, the SSZ-63 is washed several times with water and then dried. This NH ₄ ⁺ form of SSZ-63 can then be converted to the H ⁺ form by calcination (as described in Example 17) to 540 ° C.

(Example 19)
Determination of the constraining index (after treatment according to Examples 17, 3 and 18) Hydrogen type SSZ-63 of Example 2 was pelletized with 2-3 KPSI and ground, passed through a 20-40 mesh; Calcinate more than 50 g in air at about 540 ° C. for 4 hours; then cool in a desiccator. 0.50 g is packed into a 3/8 inch stainless steel tube with alundum on both sides of the molecular sieve. A Lindberg furnace is used to heat the reactor tube. Helium is introduced into the reactor tube at 10 cc / min at atmospheric pressure. The reactor is heated to about 315 ° C. and a 50/50 (w / w) feed of n-hexane and 3-methylpentane is directed into the reactor at a rate of 8 μl / min. The feedstock is delivered by a Brownlee pump. Direct continuous sampling into the gas chromatograph begins 10 minutes after directing the feedstock. The constraint index value is calculated from gas chromatography data using methods known in the art. SSZ-63 has a constraint index of 1.1 after 10 minutes at 315 ° C., and the feed conversion is 87.7%. The constraint index decreased with time on stream (0.6 at 100 minutes). This suggests that SSZ-63 is a coarse pore molecular sieve.

(Example 20)
n-Hexadecane Hydrocracking Samples of SSZ-63 prepared in Example 2 were treated as in Examples 17, 3 and 18. The sample was then slurried with water and the pH of the slurry was adjusted to a pH of about 10 with dilute ammonium hydroxide. A Pd (NH ₃ ) ₄ (NO ₃ ) ₂ solution at a concentration that would give 0.5 wt% Pd by dry weight of the molecular sieve sample was added to the slurry. The slurry was stirred at 100 ° C. for 48 hours. After cooling, the slurry was filtered through a glass frit, washed with deionized water, and then dried at 100 ° C. The catalyst was then gradually calcined in air to 482 ° C. and then held at that temperature for 3 hours.
The calcined catalyst was pelletized and pulverized on a Carver Press to produce particles in the 20/40 mesh size range. The sized catalyst (0.5 g) was packed into a 1/4 inch outer diameter tubular reactor in a micro unit to perform n-hexadecane hydroconversion. . The table below shows the experimental conditions and the product data of the hydrocracking test for n-hexadecane. After testing the catalyst for n-hexadecane, the catalyst was titrated with a solution of butylamine in hexane. The conversion and product data in the titrated state were again evaluated at elevated temperatures. The results shown in the table below show that the SSZ-63 is useful as a hydrocracking catalyst.

(Example 21)
The argon adsorption analysis SSZ-63 has a micropore volume of 0.22 cc / g based on the argon adsorption isotherm at 87.6 K displayed on the ASAP 2010 instrument based on Micrometries. Have. The low pressure dose was 3.00 cm ³ / g, giving an equilibration interval of 15 seconds. The Saito Foley adaptation of the Horvath-Kawazoe mathematical expression [Microporous Materials, 1995, 3, 531] and the conventional t plot t (t) t plot method t . Mathematical representation of density functional theory (DFT) and parameters developed by Olivier for activated carbon slits [Porous Mater. , 1995, 2, 9] were used to analyze the argon adsorption isotherm. Similar measurements were made with nitrogen using a Digisorb system.

It is a powder X-ray-diffraction pattern of calcined SSZ-63.

Claims (68)

  [Oxide (2) of [first tetravalent element oxide (1)] versus [trivalent element; pentavalent element; second tetravalent element different from first tetravalent element; or a mixture thereof] ] And a molecular sieve having the X-ray diffraction lines of Table II after calcination.   [Oxide (1) selected from the group consisting of silicon oxide, germanium oxide, and mixtures thereof] versus [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 in Table II after the molar ratio of oxide (2)] selected from is greater than about 15 and after calcination.   The molecular sieve according to claim 2, wherein the oxide contains silicon oxide and aluminum oxide.   The molecular sieve according to claim 2, wherein the oxide contains silicon oxide and boron oxide.   The molecular sieve according to claim 2, wherein the oxide contains silicon oxide and germanium oxide.   The molecular sieve according to claim 2, wherein the oxide contains silicon oxide.   The molecular sieve according to claim 1, wherein the molecular sieve is predominantly hydrogen type.   The molecular sieve of claim 1 which is substantially non-acidic.   The molecular sieve according to claim 2, wherein the molecular sieve is predominantly hydrogen type.   The molecular sieve according to claim 2 which is not substantially acidic. As-synthesized and anhydrous, with the following molar ratio:
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; when c is 1, d is 2, or 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 a valence of M; and Q is a N-cyclodecyl-N-methyl-pyrrolidinium cation).   The molecular sieve according to claim 11, 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 Y is a mixture of germanium and silicon, and the molar ratio of YO ₂ / W _c O _d is ∞.   An oxide (1) of a first tetravalent element oxide and a trivalent element; a pentavalent element; a second tetravalent element different from the first tetravalent element; or a mixture thereof. And a method of producing a crystalline material having a molar ratio of [first oxide] to [second oxide] greater than 15, comprising: The said manufacturing method including making the source of the said various oxides and the template reagent containing N-cyclodecyl-N-methyl- pyrrolidinium cation contact.   The method of claim 15, wherein the first tetravalent element is selected from the group consisting of silicon, germanium, and combinations thereof.   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 or the second tetravalent element is selected from the group consisting of aluminum, boron, titanium, and combinations thereof.   The method of claim 16, wherein the first tetravalent element is silicon.   16. The method of claim 15, wherein the crystalline material has the X-ray diffraction lines of Table II after calcination. The method of claim 15, wherein the crystalline material has a BEA ^* crystal structure.   A method for converting hydrocarbons comprising: [first tetravalent element oxide] versus [second tetravalent element different from first tetravalent element; trivalent element; pentavalent element; And a mixture containing the zeolite having the X-ray diffraction lines of Table II after the calcination and a hydrocarbon feedstock, The conversion method as described above, comprising contacting under conditions for conversion.   23. The method of claim 22, wherein the zeolite is not substantially acidic.   23. The process of claim 22, wherein the process is a hydrocracking process comprising contacting the catalyst with a hydrocarbon feedstock under hydrocracking conditions.   23. The process of claim 22, wherein the process is a dewaxing process comprising contacting the catalyst with a hydrocarbon feed under dewaxing conditions.   A method for improving the viscosity index of a dewaxed product made with a waxy hydrocarbon feedstock comprising contacting a catalyst with a waxy hydrocarbon feedstock under isomerization dewaxing conditions. 23. The method of claim 22, which is an improvement method. _23. A process for producing _{C20 +} lubricating oil from a _{C20 +} olefin feedstock, wherein the process comprises isomerizing the olefin feedstock under catalytic isomerization conditions. The method described.   28. The method of claim 27, wherein the catalyst further contains at least one Group VIII metal.   A process for catalytic dewaxing of hydrocarbon oil feedstocks boiling above about 350 ° F. and containing linear and slightly branched chain hydrocarbons, under the dewaxing conditions, 23. The process of claim 22, wherein said catalytic dewaxing process comprises contacting said hydrocarbon oil feedstock with a catalyst at a hydrogen pressure of about 15 to 3000 psi in the presence of.   30. The method of claim 29, wherein the catalyst further contains at least one Group VIII metal.   The catalyst comprises: a first layer containing a zeolite and at least one Group VIII metal; and a second layer containing an aluminosilicate zeolite that is much more shape selective than the first layer zeolite. 30. A process according to claim 29 comprising a layered catalyst containing. A method for producing a lubricating oil, 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. and about 15 psig to about 3000 psig in the presence of added hydrogen gas; Dewaxing the effluent containing the hydrocracked oil with a catalyst at a pressure of
23. The method of claim 22, wherein the method comprises:   33. The method of claim 32, wherein the catalyst further comprises at least one Group VIII metal.   23. A method for isomerization dewaxing of a raffinate, the method comprising contacting the raffinate with a catalyst in the presence of added hydrogen gas under isomerization dewaxing conditions. the method of.   35. The method of claim 34, wherein the catalyst further contains at least one Group VIII metal.   35. The method of claim 34, wherein the raffinate is bright stock.   A method for increasing the octane number of a hydrocarbon feedstock to produce a product having an increased aromatic hydrocarbon content, having a boiling range above about 40 ° C and below about 200 ° C. 23. The process of claim 22, wherein the process comprises contacting a slightly branched hydrocarbon with a catalyst under conditions of conversion to an aromatic hydrocarbon.   38. The method of claim 37, wherein the zeolite is not substantially acidic.   38. The method of claim 37, wherein the zeolite contains a Group VIII metal component.   23. A process according to claim 22 which is a catalytic cracking process comprising contacting a hydrocarbon feedstock with a catalyst under catalytic cracking conditions in the reaction zone and in the absence of added hydrogen gas.   41. The method of claim 40, wherein the catalyst further comprises a coarse pore crystalline cracking component. A isomerization process for isomerizing C ₄ -C ₇ hydrocarbons under isomerization conditions, contacting the feedstock with a C ₄ -C ₇ hydrocarbons linear or slightly branched as a catalyst 23. The method of claim 22, wherein the isomerization method comprises:   43. The method of claim 42, wherein the zeolite is impregnated with at least one Group VIII metal.   43. The method of claim 42, wherein the catalyst is impregnated with a Group VIII metal and then calcined at a high temperature in a steam / air mixture.   44. The method of claim 43, wherein the Group VIII metal is platinum. A method for alkylating aromatic hydrocarbons, wherein at least a molar excess of aromatic hydrocarbons is removed from C ₂ to under alkylation conditions, at least partially under liquid phase conditions, and in the presence of a catalyst. is the above method comprising contacting a C ₂₀ olefin, a method according to claim 22. Olefins are _C 2 -C ₄ olefin, A method according to claim 46.   48. The method of claim 47, wherein the aromatic hydrocarbon and olefin are each present in a molar ratio of about 4: 1 to about 20: 1.   48. The method of claim 47, wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene, or mixtures thereof.   A method for performing an alkyl exchange reaction of an aromatic hydrocarbon, wherein the aromatic hydrocarbon is converted to a polyalkyl aromatic under alkyl exchange reaction conditions, at least partially under liquid phase conditions, and in the presence of a catalyst. 23. The method of claim 22, wherein the method comprises contacting with a hydrocarbon.   51. The method of claim 50, wherein the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon are each present in a molar ratio of about 1: 1 to about 25: 1.   51. The method of claim 50, wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof.   51. The method of claim 50, wherein the polyalkyl aromatic hydrocarbon is a dialkyl benzene.   51. A process according to claim 22, 24, 25, 26, 27, 29, 32, 34, 40, 42, 46 or 50, wherein the zeolite is predominantly in the hydrogen form.   A method for the conversion of paraffins into aromatic hydrocarbons, comprising: a zeolite; and gallium, zinc, or a compound of gallium or zinc under conditions for converting paraffins into aromatic hydrocarbons; 23. The method of claim 22, wherein the conversion method comprises contacting paraffin.   23. The method of claim 22, wherein the method comprises contacting the olefin with a catalyst under conditions to isomerize the olefin. Isomerization containing the stream of aromatic streams in a by ortho-xylene hydrocarbons C _8, nearer the equilibrium ratio of the meta-xylene and para-xylene are obtained; xylene isomers; or xylene isomers and mixture of ethylbenzene 23. The method of claim 22, wherein the method is for isomerizing a feedstock, the method comprising contacting the feedstock with a catalyst under isomerization conditions.   23. The method of claim 22, wherein the method is for oligomerizing an olefin, the method comprising contacting the olefin feedstock with a catalyst under oligomerization conditions.   In a method for converting an oxygenated hydrocarbon, under conditions for producing a liquid product, an oxide of a first tetravalent element versus a second different from the first tetravalent element. The molar ratio of tetravalent element; trivalent element; pentavalent element; or mixtures thereof] is greater than about 15 and after calcination, the zeolite having the X-ray diffraction lines of Table II. The above-mentioned conversion method, comprising contacting the catalyst containing and the oxygenated hydrocarbon.   60. The method of claim 59, wherein the oxygenated hydrocarbon is a lower alcohol.   61. The method of claim 60, wherein the lower alcohol is methanol. A process for producing higher molecular weight hydrocarbons from smaller molecular weight hydrocarbons, comprising:
(A) introducing a gas containing a smaller molecular weight hydrocarbon into the reaction zone, and then in the zone under conditions of synthesis of C ₂₊ hydrocarbons; and the smaller molecular weight of said Contacting the gas with a metal or metal compound capable of converting hydrocarbons to higher molecular weight hydrocarbons; and (b) recovering a stream containing higher molecular weight hydrocarbons from the reaction zone. The method according to claim 22, wherein the production method comprises:   64. The method of claim 62, wherein the metal or metal compound comprises a lanthanide metal, a lanthanide metal compound, an actinide metal, or an actinide metal compound.   64. The method of claim 62, wherein the lower molecular weight hydrocarbon is methane.   In a method for reducing nitrogen oxides contained in a gas stream in the presence of oxygen, [first tetravalent element oxide (1)] vs. [trivalent element; pentavalent element; The second tetravalent element different from the valent element; or a mixture thereof; the oxide (2)] molar ratio is greater than about 15 and, after calcining, has the X-ray diffraction lines of Table II Said reduction method comprising contacting said gas stream with a zeolite containing zeolite.   66. The method of claim 65, wherein the zeolite contains a metal or metal ion that can catalyze the reduction of nitrogen oxides.   68. The method of claim 66, wherein the metal is copper, cobalt, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium, or mixtures thereof. 68. The method of claim 66, wherein the gas flow is an exhaust flow of an internal combustion engine.

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