JP5047169B2 - Molecular sieve SSZ-56 composition and its synthesis - Google Patents

Description

  The present invention relates to a novel crystalline molecular sieve SSZ-56, a method for producing SSZ-56 using N, N-diethyl-2-methyldecahydroquinolinium cation as a structure directing agent, and SSZ. -56 for example as a catalyst for hydrocarbon conversion reactions.

  Crystalline molecular sieves and zeolites are particularly useful in applications such as hydrocarbon conversion, gas drying, and separation because of their unique sieve properties as well as their catalytic properties. While many different crystalline molecular sieves have been disclosed, there continues to be a need for new zeolites with desirable properties for gas separation and drying, hydrocarbon and chemical conversion, and other applications. New zeolites may have certain new internal pore structures that give improved selectivity in these ways.

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

  The present invention relates to a series of crystalline molecular sieve series having unique properties, referred to herein as “molecular sieve SSZ-56” or simply “SSZ-56”. SSZ-56 is preferably in the form of its silicate, aluminosilicate, titanosilicate, vanadosilicate, or borosilicate. The term “silicate” refers to a molecular sieve including a molecular sieve having a high molar ratio of silicon oxide to aluminum oxide, preferably greater than 100, and consisting entirely of silicon oxide. As used herein, the term “aluminosilicate” refers to a molecular sieve that includes both aluminum oxide and silicon oxide, and the term “borosilicate” refers to a molecular sieve that includes both boron and silicon oxides.

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

  Further, according to the present invention, the molar ratio of (1) silicon oxide to (2) oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, vanadium oxide, and mixtures thereof is from about 15. Large, after calcination, a molecular sieve having the X-ray diffraction lines of Table 2 below is given. It should be noted that the molar ratio of the first oxide to the second oxide can be infinite, i.e. the second oxide may not be present in the molecular sieve. In that case, the molecular sieve is entirely a silica molecular sieve.

The present invention further provides such a molecular sieve having the following composition expressed in molar ratio in the as-synthesized anhydrous state:
_{YO 2 / W c O d 15} -∞ ( infinity)
M ₂ / _n / YO ₂ 0-0.03
Q / YO ₂ 0.02-0.05
Where Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium, or mixtures thereof; c is 1 or 2; d is c equal to 1 (ie, W Is tetravalent), or d is 3 or 5 when c is 2 (ie, d is 3 when W is trivalent, or 5 when W is pentavalent). M is an alkali metal cation, alkaline earth metal cation, or mixtures thereof; n is the valence of M (ie, 1 or 2); Q is a trans-fused ring N, N -Diethyl-2-methyldecahydroquinolinium cation A.

In accordance with the present invention, a molecular sieve having a molar ratio of silicon oxide to an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, vanadium oxide, and mixtures thereof is greater than about 200 ° C. A molecular sieve produced by heat treatment at a temperature of about 800 ° C. is also provided, and the molecular sieve produced in this way has the X-ray diffraction lines of Table 2. The present invention also encompasses molecular sieves thus produced that are primarily in the hydrogen form, which is produced by ion exchange with an acid or ammonium salt solution followed by a second calcination. The If the molecular sieve is synthesized with a sufficiently large SDA cation to sodium ion ratio, calcination alone will suffice. In order to increase catalyst activity, the SSZ-56 molecular sieve should be primarily in its hydrogen ion form. As used herein, “predominantly hydrogen ion type” means that after calcination, at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions.

  In accordance with the present invention, includes (1) a first oxide comprising silicon oxide, and (2) a second oxide comprising boron oxide, aluminum oxide, gallium oxide, iron oxide, titanium oxide, vanadium oxide, and mixtures thereof. A method for producing a crystalline material, wherein the molar ratio of the first oxide to the second oxide is greater than about 15, wherein the raw material of the oxide and the trans-fused ring N, N-diethyl-2-methyldecahydroxy Also provided is a method comprising contacting a structure directing agent comprising a norinium cation under crystallization conditions.

  The present invention provides a hydrocarbon conversion process comprising contacting a hydrocarbonaceous feed with a catalyst comprising the molecular sieve of the present invention under hydrocarbon conversion conditions. The molecular sieve can be primarily in the hydrogen form. It can be substantially non-acidic. The present invention provides that the molecular sieve has a molar ratio of oxide selected from (1) silicon oxide to (2) aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, and mixtures thereof. Larger, including such methods after calcination, having the X-ray diffraction lines of Table 2 below.

  Furthermore, the present invention also provides a hydrocracking process comprising contacting the catalyst comprising the molecular sieve of the present invention, preferably a molecular sieve primarily in the hydrogen form, with a hydrocarbon feedstock under hydrocracking conditions.

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

  The present invention provides a waxy hydrocarbon feed comprising contacting a catalyst comprising the molecular sieve of the invention, preferably in predominantly hydrogen form, with a waxy hydrocarbon feed under isomerization dewaxing conditions. Also included is a method for improving the viscosity index of the dewaxed product.

The present invention further comprises a method for producing _{C20 +} lubricating oil from a _{C20 +} olefin feed comprising isomerizing said olefin feed under isomerization conditions over a catalyst comprising the molecular sieve of the present invention. Includes manufacturing methods. The molecular sieve may be mainly in the hydrogen form. The catalyst may comprise at least one Group VIII metal.

  In accordance with the present invention, a process for catalytically dewaxing a hydrocarbon oil feedstock containing linear and slightly branched chain hydrocarbons boiling at a temperature greater than about 350 ° F. (177 ° C.) according to the present invention, Preferably, the catalyst comprising a molecular sieve, mainly in hydrogen form, and the hydrocarbon oil feedstock are contacted at a hydrogen pressure of about 15 to 3000 psi (0.103 to 20.7 MPa) in the presence of added hydrogen gas. There is also provided a catalytic dewaxing process comprising: 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 zeolite which is more shape selective than the molecular sieve of the first layer. The first layer may contain at least one Group VIII metal.

  The present invention includes hydrocracking a hydrocarbonaceous feedstock in a hydrocracking zone to obtain an effluent containing hydrocracked oil, the effluent containing the hydrocracked oil, Catalytic dewaxing in the presence of added hydrogen gas at a temperature of at least about 400 ° F. (204 ° C.) and a pressure of about 15 psig to about 3000 psig gauge (0.103-20.7 MPa) using a catalyst comprising a molecular sieve. And a method for producing a lubricating oil. The molecular sieve can be mainly of the hydrogen type. The catalyst can comprise at least one Group VIII metal.

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

  The present invention provides a hydrocarbonaceous feedstock comprising linear and slightly branched hydrocarbons having a boiling range above about 40 ° C. and below about 200 ° C., with the molecular sieve of the present invention, the molecular sieve being a basic metal. A product having an increased aromatic content by increasing the octane number of the hydrocarbon feedstock, comprising contacting the catalyst comprising a molecular sieve that has been rendered substantially non-acidic by neutralization with an aromatic conversion condition. A method of manufacturing is also included. The present invention also provides such a method where the molecular sieve includes a Group VIII metal component.

  In accordance with the present invention, a catalytic cracking comprising contacting a hydrocarbon feedstock in the reaction zone with a catalyst comprising the molecular sieve of the present invention, preferably a molecular sieve that is primarily in the hydrogen form, without adding hydrogen under catalytic cracking conditions. Law is also given. The present invention also includes such a catalytic cracking method when the catalyst further contains pore-containing crystalline cracking components.

The present invention further provides a feed having linear and slightly branched C _{4 to} C ₇ hydrocarbons under isomerization conditions with a catalyst comprising the molecular sieve of the present invention, preferably a molecular sieve that is predominantly in the hydrogen form. An isomerization process is provided for isomerizing C _{4 to} C ₇ hydrocarbons, including contacting. The molecular sieve can be impregnated with at least one Group VIII metal, preferably platinum. The catalyst can be calcined at an elevated temperature in a steam / air mixture after impregnation with the Group VIII metal.

The present invention, a C ₂ -C ₂₀ olefins, in an at least partially liquid phase conditions at least a molar excess of the aromatic hydrocarbon and the alkylation conditions, the molecular sieves of the present invention, preferably predominantly become hydrogen form Also provided is a process for alkylating aromatic hydrocarbons comprising the presence and contacting of a catalyst comprising a molecular sieve. Olefin can be a C ₂ -C ₄ olefins, aromatic hydrocarbons and olefins are each from about 4: can 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, there is provided a catalyst comprising an aromatic hydrocarbon and a polyalkylaromatic hydrocarbon, at least partly in liquid phase, the molecular sieve of the present invention, preferably mainly in the hydrogen form. A method is provided for transalkylating aromatic hydrocarbons comprising present and contacting at transalkylation conditions. Aromatic hydrocarbons and polyalkyl aromatic hydrocarbons 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 there is provided a process for converting paraffin to aromatic comprising contacting paraffin with a catalyst comprising the molecular sieve of the present invention under conditions to convert the paraffin to aromatic. , Gallium, zinc, or a compound of gallium or zinc.

  In accordance with the present invention, there is also provided a process for isomerizing an olefin comprising contacting the olefin with a catalyst comprising the molecular sieve of the present invention under conditions that cause isomerization of the olefin.

Further in accordance with the present invention, in a method for isomerizing an isomerization feed comprising a mixture of aromatic C ₈ stream or xylene isomers and ethylbenzene xylene isomers, the molecular sieve of the present invention the feed at isomerization conditions An anisotropy process is provided that results in a near-equilibrium ortho-, meta-, and para-xylene ratio comprising contacting with a catalyst comprising

  The present invention further provides a process for oligomerizing olefins comprising contacting the olefin feed with a catalyst comprising the molecular sieve of the present invention at oligomerization conditions.

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

Furthermore, according to the present invention, a method for producing a high molecular weight hydrocarbon from a low molecular weight hydrocarbon,
(A) a catalyst capable of introducing a low molecular weight hydrocarbon-containing gas into the reaction region, and converting the low molecular weight hydrocarbon into a high molecular weight hydrocarbon in the region, and a metal or metal compound and C ₂₊ hydrocarbon Contacting with synthesis conditions; and (b) removing a high molecular weight hydrocarbon-containing stream from the reaction zone;
A manufacturing method is provided.

According to the present invention, a catalyst composition for promoting the polymerization of 1-olefin,
(A) (1) Oxide pair of first tetravalent element (2) Trivalent element, pentavalent element, second tetravalent element different from the first tetravalent element, or an oxide of a mixture thereof A molecular sieve having a molar ratio greater than about 15 and having, after calcination, the X-ray diffraction lines of Table 2; and
Also provided is a catalyst composition comprising:

  The oxide (1) is silicon oxide and the oxide (2) can be an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, and indium oxide.

The present invention further provides a 1-olefin monomer,
(A) (1) Oxide pair of first tetravalent element (2) Trivalent element, pentavalent element, second tetravalent element different from the first tetravalent element, or an oxide of a mixture thereof A molecular sieve having a molar ratio greater than about 15 and having, after calcination, the X-ray diffraction lines of Table 2; and
A method for polymerizing 1-olefins comprising contacting a catalytically effective amount of the catalyst composition with a polymerization condition comprising a temperature and pressure suitable to initiate and promote the polymerization reaction.

  The oxide (1) is silicon oxide and the oxide (2) can be an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, and indium oxide.

  The present invention further includes a method of hydrogenating a hydrocarbon feed containing unsaturated hydrocarbons, wherein the feed and hydrogen are contacted with a catalyst comprising the molecular sieve of the invention under conditions that cause hydrogenation. Give a hydrogenation method. The catalyst may comprise a metal, salt, complex, in which case the metal is a group consisting of platinum, palladium, rhodium, iridium, or combinations thereof, or nickel, molybdenum, cobalt, tungsten, titanium. , Chromium, vanadium, rhenium, manganese, and combinations thereof.

  The present invention also provides a method for hydrotreating a hydrocarbon feedstock comprising contacting the hydrocarbon feedstock with a hydrotreating catalyst, the catalyst comprising the molecular sieve of the present invention and hydrogen under hydrotreating conditions. It is done.

  In accordance with the present invention, a method for reducing nitrogen oxides contained in a gas stream comprises contacting the gas stream with a molecular sieve, wherein the molecular sieve comprises (1) an oxide of a first tetravalent element The molar ratio of the oxide of (2) trivalent element, pentavalent element, second tetravalent element different from the first tetravalent element, or a mixture thereof is greater than about 15, and after calcination, Table 2 A nitrogen oxide reduction method having the following X-ray diffraction lines is provided. A method of reducing nitrogen oxides contained in a gas stream comprising contacting the gas stream with a molecular sieve, wherein the molecular sieve comprises (1) silicon oxide versus (2) aluminum oxide, gallium oxide, Nitrogen oxide reduction method wherein the molar ratio of the oxide selected from iron oxide, boron oxide, titanium oxide, indium oxide, and mixtures thereof is greater than about 15 and has the X-ray diffraction lines of Table 2 after calcination Is given. Molecular sieves are metals or metal ions that can catalyze the reduction of nitrogen oxides (eg, cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium, or mixtures thereof) And the process can be carried out in the presence of a stoichiometric excess of oxygen. In a preferred embodiment, the gas flow is an exhaust gas flow of an internal combustion engine.

  The present invention is a method for treating a cold start engine exhaust gas stream containing hydrocarbons and other contaminants, wherein the engine exhaust gas stream is passed over a molecular sieve bed that preferentially adsorbs hydrocarbons over water, and the first exhaust. Providing a gas stream, flowing the first exhaust gas stream over the catalyst, converting all residual hydrocarbons and contaminants contained in the first exhaust gas stream into harmless products, and treating the exhaust Providing a gas stream and releasing the treated exhaust gas stream into the atmosphere, wherein the molecular sieve bed comprises (1) an oxide of a first tetravalent element and (2) a trivalent element, pentavalent The molar ratio of the oxide of the element, the second tetravalent element different from the first tetravalent element, or a mixture thereof is greater than about 15, and has the X-ray diffraction lines of Table 2 after calcination An exhaust gas flow treatment method is provided.

  Further, according to the present invention, in the method for treating an exhaust gas from a cold start engine described above, the molecular sieve is (1) silicon oxide vs. (2) aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, and their An exhaust gas treatment method is provided wherein the molar ratio of the oxide selected from the mixture is greater than about 15 and, after calcination, has the X-ray diffraction lines of Table 2. The invention further provides such a method when the engine is an internal combustion engine, including an automobile engine, which can supply hydrocarbonaceous fuel. The present invention also provides such a method when the molecular sieve is deposited with a metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof.

Detailed Description of the Invention The present invention includes a series of crystalline molecular sieves, referred to herein as "molecular sieve SSZ-56" or simply "SSZ-56". In preparing SSZ-56, N, N-diethyl-2-methyldecahydroquinolinium cation (trans fused ring isomer) is used as a structure directing agent, also known as a crystallization template ( SDA). An SDA useful for making SSZ-56 has the following structure:

The SDA cation is accompanied by an anion (X ⁻ ), which can be any anion that is not detrimental to the formation of molecular sieves. Representative anions include, for example, halogen ions such as fluoride ions, chloride ions, bromide ions, and iodide ions, hydroxide ions, acetate ions, sulfate ions, tetrafluoroborate ions, carboxylate ions, Etc. are included. Most preferred are hydroxide ions.

SSZ-56 is prepared from a reaction mixture having the composition shown in Table A below.

Reaction mixture
Typically in the range preferred range _{YO 2 / W a O b>} 15 30-60
OH− / YO ₂ 0.10−0.50 0.20−0.30
Q _/ YO 2 0.05-0.50 0.10-0.30
_{M 2 / n / YO 2 0-0.40} 0.10-0.25
H ₂ O _/ YO ₂ 20-80 30-45
Where Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium, or a mixture thereof; a is 1 or 2, and b is 1 (ie, W Is tetravalent), b is 3, when a is 2 (ie, W is trivalent); M is an alkali metal cation, alkaline earth metal cation, or their N is the valence of M (ie 1 or 2); and Q is the trans-fused ring N, N-diethyl-2-methyldecahydroquinolinium cation.

In fact, SSZ-56 is
(A) a source of oxide capable of forming a crystalline molecular sieve and a trans-fused ring N, N-diethyl-2-methyldecahydroquinolinium having an anionic counterion that is not detrimental to the formation of SSZ-56 Preparing an aqueous solution containing cations;
(B) maintaining the aqueous solution under conditions sufficient to form SSZ-56 crystals; and (c) recovering SSZ-56 crystals.
Is produced by a method including

  Thus, SSZ-56 includes crystalline material and SDA combined with metal and non-metal oxides bonded in tetrahedral coordination by covalent oxygen atoms to form a cross-linked three-dimensional crystal structure. be able to. Typical sources of silicon oxide include silicates, silica hydrogels, silicic acid, fumed silica, colloidal silica, tetraalkylorthosilicates, and silica hydroxides. Boron can be added in a form corresponding to its silicon counter ion, such as boric acid.

  The raw zeolite reactant can provide a boric acid source. In most cases, the raw zeolite is also a silica source. A deboronated raw material zeolite may be used as a raw material for silica, for example, by adding additional silicon using the conventional raw materials listed above. The use of raw zeolite reactants for the process of the present invention is described in US Pat. No. 5,225, published July 6, 1993 entitled “Method of Making Molecular Sieves” by Nakagawa. 179, the description of which is hereby incorporated by reference.

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

  The reaction mixture is maintained at an elevated temperature until SSZ-56 crystals are formed. Hydrothermal crystallization is usually carried out at a temperature of 100 ° C. to 200 ° C., preferably 135 ° C. to 160 ° C. under naturally occurring pressure. The crystallization time is typically longer than 1 day, preferably from about 3 days to about 20 days.

  The molecular sieve is preferably produced using gentle stirring and agitation.

  During the hydrothermal crystallization process, SSZ-56 crystals can be spontaneously nucleated from the reaction mixture. Using SSZ-56 crystals as seed material can be advantageous in reducing the time required to cause complete crystallization. Furthermore, seed addition can increase the purity of the resulting product by promoting nucleation and / or formation of SSZ-56 over the undesirable phase. When used as seeds, SSZ-56 crystals are added in an amount of 0.1 to 10% of the weight of the first tetravalent element oxide, eg, silica used in the reaction mixture.

  Once 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-56 crystals. The drying step can be performed at atmospheric pressure or in a vacuum.

As-produced SSZ-56 has a silicon oxide to boron oxide molar ratio greater than about 15 and, after calcination, has the X-ray diffraction lines of Table 2 below. Further, SSZ-56 as-synthesized (ie, before removing SDA from SSZ-56) has the composition shown in Table B below, expressed in molar ratio, in the anhydrous state:
Table B
As-synthesized SSZ-56
_{YO 2 / W c O d 15} -∞ ( infinity)
M ₂ / _n / YO ₂ 0-0.03
Q / YO ₂ 0.02-0.05
Where Y, W, M, n, and Q are as defined above, c is 1 or 2, and d is 2 when c is 1 (ie, W is tetravalent). Yes, or d is 3 or 5 when c is 2 (ie, d is 3 when W is trivalent, or 5 when W is pentavalent).

SSZ-56 can all be silica. SSZ-56 is produced as a borosilicate, and if desired, the boron is then removed by treating the borosilicate SSZ-56 with acetic acid at an elevated temperature [Jones et al., Chem. Mater. , As described in 2001,13,1041-1050], those of all silica type SSZ-56 _(i.e., it is possible to YO _{2 /} W c _{O d} is the production of ∞ (infinity)].

  If desired, SSZ-56 can be prepared as a borosilicate, and then boron can be removed and replaced with metal atoms by techniques known in the art as described above. In this manner, aluminum, gallium, iron, titanium, vanadium, and mixtures thereof can be added.

  SSZ-56 is thought to be composed of a new framework structure, or topology, characterized by its X-ray diffraction image. As synthesized, SSZ-56 has a crystal structure with a powder X-ray diffraction image showing the characteristic lines shown in Table 1, and is therefore distinguished from other molecular sieves.

（ａ） ±０．１０
（ｂ） 与えられたＸ線像は、相対強度スケールに基づいており、この場合、Ｘ線像の最も強い線には１００の値を付け、Ｗ（弱）は２０より小さく、Ｍ（中程度）は２０〜４０、Ｓ（強）は４０〜６０、ＶＳ（非常に強）は６０より大きい値が付けられている。

(A) ± 0.10
(B) The given X-ray image is based on a relative intensity scale, where the strongest line of the X-ray image is given a value of 100, W (weak) is less than 20 and M (medium) ) Is 20-40, S (strong) is 40-60, and VS (very strong) is greater than 60.

Table 1A below shows the powder X-ray diffraction lines including actual relative intensities for as-synthesized SSZ-56:

After calcination, the SSZ-56 molecular sieve has a crystal structure with a powder X-ray diffraction image including the characteristic lines shown in Table 2.

^（ａ） ±０．１０
Table 2A below shows the powder X-ray diffraction lines including actual relative intensities for calcined SSZ-56.

^(A) ± 0.10

  Powder X-ray diffraction images were determined by standard methods. The radiation was copper K-α / doublet. The height and position of the peak can be read from the relative intensity of the peak as a function of 2θ (θ is the Bragg angle) and the interplanar spacing d (Å) corresponding to the recorded line can be calculated.

  The variation in scattering angle (2θ) measurement due to instrument error and individual sample differences was estimated to be ± 0.10 °.

  The X-ray diffraction images of Table I are representative of SSZ-56 molecular sieves “as synthesized” or “as manufactured”. Slight variations in the diffraction pattern can be caused by variations in the silica to boron molar ratio of a particular sample due to changes in the lattice constant. In addition, a sufficiently small crystal will affect the shape and intensity of the peak, and will broaden the peak considerably.

Representative peaks from the X-ray diffraction image of calcined SSZ-56 are shown in Table 2. Calcination can result in fluctuations in the peak intensity as well as a slight shift of the diffraction pattern as compared to an image of the “as-manufactured” material. Molecular sieves produced by exchanging metals or other cations present in a molecular sieve with various other cations (eg, H ⁺ or NH ₄ ⁺ ) produce essentially the same diffraction pattern, In some cases, slight variations in the interplanar spacing and the relative intensity of the peak may occur. Despite these slight variations, the basic crystal lattice remains unchanged by these treatments.

  Crystalline SSZ-56 can be used as-synthesized, but it may be preferable to thermally treat (calcinate). 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 agent such as EDTA or dilute acid solution to increase the silica to alumina molar ratio. The molecular sieve can also be steamed. Steam treatment helps stabilize the crystal lattice against being eroded by acid.

  Molecular sieves should be in close combination with hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals such as palladium or platinum, and hydrogenation / dehydrogenation functions are desired. Can be used for applications.

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 methods [eg, published July 7, 1964 by Plank et al. U.S. Pat. No. 3,140,249 issued to U.S. Pat. No. 3,140,251 issued on 7 July 1964 by Planck et al. And 7 Jul. 1964 by Planck et al. See published U.S. Pat. No. 3,140,253. Typical substitution cations include metal cations, such as rare earth , Group IA, Group IIA, and Group VIII metals, and mixtures thereof. Among the replacement 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-56. SSZ-56 can also be impregnated with metal, or the metal can be physically well mixed with SSZ-56 using standard methods known in the art.

  A typical ion exchange method involves contacting a synthetic molecular sieve with a solution containing a salt of the desired replacement cation (s). Many types of salts can be used, but chlorides and other halides, acetates, nitrates, and sulfates are particularly preferred. The molecular sieve is usually calcined prior to the ion exchange procedure to remove organic material present in the grooves and on the surface. This is because this results in more effective ion exchange. Typical examples of the ion exchange method are US Pat. No. 3,140,249 published on July 7, 1964 by Planck et al., US Patent published on July 7, 1964 by Planck et al. Described in many types of patents, including US Pat. No. 3,140,251 and US Pat. No. 3,140,253 issued July 7, 1964 to Planck et al.

  After contact with the desired replacement cation salt solution, 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 in an 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, and the catalytically active product particularly useful in hydrocarbon conversion Can be generated.

  Regardless of the cations present in the synthesized form of SSZ-56, the spatial arrangement of the atoms forming the basic crystal lattice of the molecular sieve remains essentially unchanged.

  SSZ-56 can be formed in many different physical forms. Generally speaking, the molecular sieve passes through a 2 mesh (Tyler) sieve and is in the form of a powder, granule, molded product, such as an extrudate having a particle size sufficient to remain on the 400 mesh (Tyler) sieve. Can be. When the catalyst is formed by extrusion using an organic binder or the like, SSZ-56 can be extruded and then dried, or dried or partially dried and then extruded.

  SSZ-56 can be composited with other materials that are durable to the temperatures and other conditions used in the organic conversion process. Such matrix materials include active and inert materials and synthetic or natural zeolites as well as inorganic materials such as clays, silica, and metal oxides. Examples of such materials and the manner in which they can be used are described in US Pat. No. 4,910,006 published May 20, 1990 by Zones et al., And 1994 5 by Nakagawa. U.S. Pat. No. 5,316,753, published 31 May, both of which are hereby incorporated by reference in their entirety.

  SSZ-56 is a variety of hydrocarbon conversion reactions for reducing nitrogen oxides in gas streams, such as hydrocracking, dewaxing, isomerization, etc., and for treating cold start engine exhaust gas streams. Useful as a catalyst for

Hydrocarbon conversion process SSZ-56 zeolite is useful in hydrocarbon conversion reactions. The hydrocarbon conversion reaction is a chemical method using a catalyst that changes a carbon-containing compound to a different carbon-containing compound. Examples of hydrocarbon conversion reactions where SSZ-56 is expected to be useful include hydrocracking, dewaxing, catalytic cracking, olefin and aromatic formation reactions. These catalysts include n-paraffin and naphthene isomerization, polymerization and oligomerization of olefinic or acetylenic compounds such as isobutylene and 1-butene, polymerization of 1-olefins (eg ethylene), modification, polyalkyl substitution Other petroleum reformers such as isomerization of aromatics (eg m-xylene) and disproportionation of aromatics (eg toluene) to give a mixture of benzene, xylene and higher methylbenzenes, and oxidation reactions It is also expected to be useful for hydrocarbon conversion reactions. Also included are rearrangement reactions to produce various naphthalene derivatives, and formation of high molecular weight hydrocarbons from low molecular weight hydrocarbons (eg, methane upgrading).

  The SSZ-56 catalyst has high selectivity and can give a large proportion of the desired product over the total product under hydrocarbon conversion conditions.

In order to increase the catalyst activity, SSZ-56 zeolite is preferably mainly in the hydrogen ion type. Generally, a zeolite is converted to its hydrogen form by ammonium exchange and then calcination. If the zeolite is synthesized with a sufficiently large SDA cation to sodium ion ratio, calcination alone will suffice. After calcination, preferably at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions. As used herein, “mainly hydrogen type” means that at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions after calcination.

  SSZ-56 zeolite can be used to process hydrocarbonaceous feedstocks. Hydrocarbon feedstock contains carbon compounds and many different such as unused petroleum fraction, recycled petroleum fraction, shale oil, liquefied coal, tar sand oil, synthetic paraffin from NAO, recycled plastic feedstock Any carbon-containing feedstock that can be obtained from any raw material and is generally susceptible to reactions catalyzed by zeolites. Depending on the type of process that the hydrocarbonaceous feed undergoes, the feed may or may not contain metal, which may be rich or low in nitrogen or sulfur impurities. However, it can be appreciated that the lower the feed metal, nitrogen, and sulfur content, the more generally the treatment will be more effective (the catalyst will be more active).

  The conversion of the hydrocarbonaceous feed may be done in any convenient manner, depending on the type of process desired, for example in a fluidized bed, moving bed or fixed bed reactor. 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, denitration, and desulfurization reactions.

  The following table shows typical reaction conditions that can be used when a catalyst comprising SSZ-56 is used in the hydrocarbon conversion reaction of the present invention. Preferred conditions are indicated in parentheses.

^１ 数百気圧
^２ 気相反応
^３ 炭化水素分圧
^４ 液相反応
^５ ＷＨＳＶ

¹ hundred barometric pressure
^Two gas phase reaction
³ Hydrocarbon partial pressure
^4- liquid phase reaction
⁵ WHSV

  Other reaction conditions and parameters are given below.

Hydrocracking, preferably using a catalyst comprising mainly hydrogen-type SSZ-56 and a hydrogenation accelerator, heavy oil residue feedstock, cyclic feedstock, and other hydrocracked feedstock are described in US Pat. Hydrocracking can be performed using the processing conditions and catalyst components described in US Pat. No. 4,910,006 and US Pat. No. 5,316,753.

  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. The hydrogenation catalyst comprises at least one of the group consisting of platinum, palladium, rhodium, iridium, ruthenium, and mixtures thereof, or at least one of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof. It is preferably selected from the group consisting of a group of metals, salts, and complexes thereof. Reference to catalytically active metal (s) includes elemental state or some form of such metal (s) such as oxides, sulfides, halides, carboxylates, etc. And The hydrogenation catalyst is present in an amount effective to provide the hydrogenation function of the hydrocracking catalyst, preferably in an amount ranging from 0.05 to 25% by weight.

Dewaxing, preferably primarily in hydrogen form, SSZ-56 can be used to dewax hydrocarbonaceous feeds by selectively removing linear paraffins. Typically, contacting the waxy feed with SSZ-56 at isomerization dewaxing conditions improves the viscosity index of the dewaxed product (compared to the waxy feed).

  Catalytic dewaxing conditions are highly dependent on the feed used and the desired pour point. It is preferred that hydrogen be present in the reaction zone during the catalytic dewaxing process. The hydrogen to feed ratio is typically about 500 to about 30,000 SCF / bbl (standard cubic feet / barrel) [0.089 to 5.34 SCM / l (standard cubic meters / liter)], preferably about 1000 to About 20,000 SCF / bbl [0.178 to 3.56 SCM / l]. In general, hydrogen will be separated from the product and recycled to the reaction zone. Typical feedstocks include light gas oils, heavy gas oils, and reduced crude oils boiling at temperatures above about 350 ° F. (177 ° C.).

  A typical dewaxing process involves boiling a hydrocarbon oil feedstock containing linear and slightly branched hydrocarbons at temperatures above about 350 ° F. (177 ° C.), SSZ-56 and at least one type. Catalytic dewaxing by contact with a catalyst comprising a Group VIII metal at a hydrogen pressure of about 15 to 3000 psi (0.103 to 20.7 Mpa) in the presence of added hydrogen gas.

  The SSZ-56 hydrodewaxing catalyst can optionally include a type of hydrogenation component commonly used in dewaxing catalysts. For examples of these hydrogenation components, see the aforementioned US Pat. No. 4,910,006 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 also be operated in a manner that increases isomerization dewaxing at the expense of cracking reactions.

  The feed may be hydrocracked and then dewaxed. This type of two-step process and typical hydrocracking conditions are described in U.S. Pat. No. 4,921,594, published May 1, 1990 by Miller (this is for reference only). Is included here).

  SSZ-56 can also be used as a dewaxing catalyst in the form of a layered catalyst. That is, the catalyst includes a first layer that includes zeolite SSZ-56 and at least one Group VIII metal, and a second layer that includes an aluminosilicate zeolite that is more shape selective than zeolite SSZ-56. The use of a layered catalyst is described in U.S. Pat. No. 5,149,421 published Sep. 22, 1992 by Miller, which is hereby incorporated by reference in its entirety. Yes. The layered body may comprise a bed of SSZ-56 layered with a non-zeolite component designed for hydrocracking or hydrofinishing.

  SSZ-56 describes raffinate, including bright stock, in U.S. Pat. No. 4,181,598 issued on 1 January 1980 to Gillespie et al. Can also be used for dewaxing under conditions such as those described in

  It is often desirable to produce a more stable dewaxed product using mild hydrogenation (sometimes referred to as hydrofinishing). The hydrofinishing step can be performed before or after the dewaxing step, preferably after. The hydrofinishing is typically performed at a temperature in the range of about 190 ° C. to about 340 ° C., at a pressure of about 400 psig to about 3000 psig (2.76 to 20.7 Mpa gauge) at a space of about 0.1-20. At a rate (LHSV) and a hydrogen recycle rate of about 400-1500 SCF / bbl (about 0.071-0.27 SCM / l). The hydrogenation catalyst used must have sufficient activity not only to hydrogenate olefins, diolefins and colored objects that may be present, but also to reduce the aromatic content. Suitable hydrogenation catalysts are described in U.S. Pat. No. 4,921,594 issued May 1, 1990 to Miller, which is hereby incorporated by reference in its entirety. . The hydrofinishing process is advantageous for producing a product (eg, a lubricating oil) with acceptable stability. This is because dewaxed products made from hydrocracked feedstocks tend to be unstable to air and light and tend to form sludge naturally and quickly.

A lubricating oil can be produced using SSZ-56. For example, a _{C20 +} lubricating oil can be produced by isomerizing a _{C20 +} olefin feed over a catalyst comprising hydrogen type SSZ-56 and at least one Group VIII metal. Alternatively, the hydrocarbonaceous feedstock is hydrocracked in the hydrocracking zone to obtain an effluent containing hydrocracked oil, the effluent at a temperature of at least about 400 ° F. (204 ° C.), Catalytic dewaxing with a catalyst comprising hydrogen-type SSZ-56 and at least one Group VIII metal in the presence of added hydrogen gas at a pressure of about 15 psig to about 3000 psig (0.103-20.7 Mpa gauge) Thus, a lubricating oil can be produced.

Aromatic forming SSZ-56 can be used to convert light straight run naphtha and similar mixtures to highly aromatic mixtures. For example, linear and slightly branched hydrocarbons, preferably those having a boiling range above about 40 ° C. and below about 200 ° C., products having a substantially higher octane aromatic content. Can be converted by contacting the hydrocarbon feed with an SSZ-56 containing catalyst. SSZ-56 containing catalysts can also be used to convert heavier feeds to BTX or valuable naphthalene derivatives.

  The conversion catalyst preferably comprises a Group VIII metal compound so that it has sufficient activity for commercial use. As used herein, a Group VIII metal compound refers to 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 together with Group VIII metal compounds, preferably noble metal compounds. The most preferred metal is platinum. The amount of Group VIII metal present in the conversion catalyst is within the normal range used for the reforming catalyst, about 0.05 to 2.0% by weight, preferably 0.2 to 0.8% by weight. Should be.

  In order to selectively produce aromatics in useful amounts, the conversion catalyst should be substantially free of acidity by neutralizing the zeolite with a basic metal, such as an alkali metal compound. It is essential. Methods for making a catalyst non-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 can be made substantially acidic only at very high silica: alumina molar ratios.

The catalytic cracking hydrocarbon cracking raw material is preferably mainly hydrogen type SSZ-56, and can be catalytically cracked without hydrogen.

When SSZ-56 is used as a catalytic cracking catalyst in the absence of hydrogen, it can be any conventional cracking catalyst such as any aluminosilicate that has been used as a component of the cracking catalyst. Can be used together. Typically these are atmospheric pore crystalline aluminosilicates. Examples of these conventional cracking catalysts are described in the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753. When a conventional cracking catalyst (TC) component is used, the relative weight ratio of TC to SSZ-56 is generally about 1:10 to about 500: 1, desirably 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 zeolites and / or conventional cracking components may be further ion exchanged with rare earth ions to improve selectivity.

  The cracking catalyst is 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 catalysts of the present invention are highly active and highly selective for the isomerization of C _{4 to} C ₇ hydrocarbons. Active means that the catalyst can work at a relatively low temperature, which is thermodynamically favorable to highly branched paraffins. Thus, the catalyst can produce a high octane product. High selectivity means that a relatively large liquid yield can be achieved when the catalyst is operated at a high octane number.

The process of the present invention involves contacting an isomerization catalyst, i.e., a catalyst comprising hydrogen-type SSZ-56, with a hydrocarbon feed at isomerization conditions. The feed is a light straight cut having a boiling point in the range of 30 ° F to 250 ° F (-1 ° C to 121 ° C), preferably 60 ° F to 200 ° F (16 ° C to 93 ° C). Is preferred. Preferably the hydrocarbon feed for the process is, C ₄ -C ₇ straight and slightly branched low octane hydrocarbons substantial amount, more preferably from C ₅ and C ₆ hydrocarbons.

The isomerization reaction is preferably performed in the presence of hydrogen. Preferably, hydrogen is added to give a hydrogen to hydrocarbon ratio (H ₂ / HC) of H ₂ / HC of 0.5 to 10, more preferably 1 to 8 H ₂ / HC. For a further description of the isomerization process conditions, see the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753.

  A low sulfur feed is particularly preferred in the process of the present invention. The sulfur content of the feed is preferably less than 10 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm. In the case of feeds that have not yet been reduced in sulfur content, hydrogenation catalysts that are resistant to sulfur poisoning can reach acceptable levels by hydrogenating the feed in the pre-saturated region. it can. For more detailed discussion of 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 content and water content of the feed. Suitable catalysts and methods for these purposes are known to those skilled in the art.

  After the period of operation, the catalyst may be deactivated by sulfur or coke. For a more detailed discussion of this sulfur and coke removal and catalyst regeneration method, see the aforementioned US Pat. No. 4,910,006 and US Pat. No. 5,316,753.

  The conversion catalyst preferably comprises a Group VIII metal compound and 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, 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 about 0.05 to 2.0% by weight, preferably 0.2 to 0.8% by weight, within the normal use range for isomerization catalysts. Good.

Alkylation and alkyl exchange SSZ-56 can be used in methods for alkylation or alkyl exchange of aromatic hydrocarbons. The method of an aromatic hydrocarbon and C ₂ -C ₁₆ olefin alkylating agent or a polyalkyl aromatic hydrocarbon transalkylation agent, at least partially liquid phase conditions, in the presence of a catalyst comprising SSZ-56 Including contacting.

  SSZ-56 can also be used to remove benzene from gasoline by alkylating benzene and removing the alkylated product from gasoline as described above.

For high catalyst activity, SSZ-56 zeolite should 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 to 20, preferably 2 to 2, such as ethylene, propylene, butene-1, trans-butene-2, and cis-butene-2, or mixtures thereof. It is an olefin having 4 carbon atoms. Penten may be desirable. Preferred olefins are ethylene and propylene. Longer chain α-olefins can be used as well.

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

  When the process performed is alkylation, the reaction conditions are as follows. The aromatic hydrocarbon feed should be present in stoichiometric excess. The molar ratio of aromatic to olefin is preferably greater than 4: 1 to prevent premature catalyst fouling. 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 should be sufficient to maintain the liquid phase at least partially to retard catalyst contamination. 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 may be in the range of 10 seconds to 10 hours, but is usually 5 minutes to 1 hour. The weight space hourly speed (WHSV) in grams of aromatic hydrocarbons and olefins per gram of catalyst per hour (WHSV) is generally in the range of about 0.5-50.

  When the process performed is transalkylation, the molar ratio of aromatic hydrocarbons will generally be in the range of about 1: 1 to 25: 1, preferably about 2: 1 to 20: 1. The reaction temperature will 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 should be sufficient to maintain at least a partial liquid phase, typically about 50 psig to 1000 psig (0.345 to 6.89 Mpa gauge), preferably 300 psig to 600 psig (2.07-4). .14 Mpa gauge). The weight space velocity will be in the range of about 0.1-10. U.S. Pat. No. 5,082,990, published by Hsieh et al., Published January 21, 1992, describes such a method and is hereby incorporated by reference.

Paraffin to aromatic conversion SSZ-56 can be used to convert light gaseous C ₂ -C ₆ paraffins to higher molecular weight hydrocarbons including aromatic compounds. The zeolite preferably comprises a catalytic metal or metal oxide, in which case the metal is selected from the group consisting of groups IB, IIB, VIII, or 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-56 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 linear olefin, more preferably linear butene. As used herein, normal butene refers to all forms of linear butene, such as 1-butene, cis-2-butene, and trans-2-butene. Typically, hydrocarbons other than linear butene, or other C _4-6 linear olefins will be present in the feed stream. These other hydrocarbons may include, for example, alkanes, other olefins, aromatics, hydrogen, and inert gases.

  The feed stream will typically be effluent from a fluid catalytic cracking unit or a methyl-t-butyl ether unit. The fluid catalytic cracker effluent typically contains about 40-60% by weight of linear butene. The methyl-t-butyl ether unit effluent typically contains 40-100% by weight linear butene. The feed stream preferably contains at least about 40% by weight linear butene, more preferably at least about 65% by weight linear butene. The terms isoolefin and methyl branched isoolefin are used interchangeably herein.

  This process is carried out under isomerization conditions. The hydrocarbon feed is contacted with a catalyst containing SSZ-56 in the gas phase. This process is generally about 625 ° F to about 950 ° F (329 ° C to 510 ° C) for butenes, preferably about 700 ° F to about 900 ° F (371 ° C to 482 ° C), for pentene and hexene. It can be conducted at a temperature of about 350 ° F to about 650 ° F (177 ° C to 343 ° C). The pressure is from reduced pressure to about 200 psig (1.38 Mpa gauge), preferably about 15 psig to about 200 psig (0.103 to 1.38 Mpa gauge), more preferably about 1 psig to about 150 psig (0.00689 to 1.03 Mpa gauge). Is in range.

The liquid hourly space velocity during contact is generally from about 0.1 to about 50 hr- ¹ , preferably from about 0.1 to about 20 hr- ¹ , more preferably from about 0.2 to about 10 based on the hydrocarbon feed. Hour- ¹ , most preferably about 1 to about 5 hour- ¹ . The hydrogen / hydrocarbon molar ratio is maintained from about 0 to about 30 or more. Hydrogen can be added directly to the feed stream or directly to the isomerization zone. The reaction is preferably substantially free of water and is typically less than about 2% by weight based on the feed. This process 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 be moved up or down. The mol% conversion, for example the conversion of linear butene to isobutene, is at least 10, preferably at least 25, most preferably at least 35.

Xylene Isomerization SSZ-56 may isomerize more than one type of xylene isomers of C ₈ aromatic feed in ortho at a ratio close to the equilibrium value -, meta -, and para - also useful in a method of obtaining a xylene is there. In particular, xylene isomerization is used in connection with another method of producing para-xylene. For example, para mixed C ₈ aromatics stream - a portion of the xylene may be recovered by crystallization and centrifugation. The mother liquor from the crystallizer is then reacted under xylene isomerization conditions to restore ortho-, meta-, and para-xylene to near equilibrium ratios. 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 combined stream is distilled to remove heavy and light by-products. The resulting C ₈ aromatics stream, then sent to the crystallizer to repeat the process.

  Optionally, gas phase isomerization is performed in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (eg, ethylbenzene). When hydrogen is used, the catalyst will contain about 0.1 to 2.0% by weight of a hydrogenation / dehydrogenation component selected from the Group VIII metal component of the periodic table, particularly platinum or nickel. By Group VIII metal component is meant these metals and compounds such as their oxides and sulfides.

  Optionally, the isomerization feed can contain 10-90% by weight of a diluent such as toluene, trimethylbenzene, naphthene, or paraffin.

It is expected that oligomerized SSZ-56 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 the process are medium to heavy olefins that are useful for both fuel, ie gasoline or gasoline blending feedstock, and chemicals.

  The oligomerization process involves contacting the olefin feed with a catalyst comprising SSZ-56 in the gas phase or liquid phase.

Zeolite can initially replace the cation associated with it with many other types of cations according to techniques well known in the art. Typical cations will include hydrogen, ammonium, metal cations, and mixtures thereof. Among the metal cations for substitution, in addition to rare earth metals, manganese and calcium, cations of metals of Group II of the periodic table such as zinc and metals such as Group VIII of the periodic table such as nickel are particularly preferable. One important requirement is that the aromatization activity of the zeolite is rather low, i.e. the amount of aromatics produced is about 20% by weight or less. This is to use a zeolite with a controlled acidic activity [α value] of about 0.1 to about 120, preferably about 0.1 to about 100, as measured by its ability to decompose n-hexane. Is achieved.

  Alpha values are shown, for example, in US Pat. No. 3,960,978 issued to Gives et al., published June 1, 1976, which is hereby incorporated by reference in its entirety. As defined by standard tests known in the art. If necessary, such zeolites can be obtained by steam treatment, by use in a conversion step, or by other methods that would occur to those skilled in the art.

Alcohol condensation SSZ-56 can be used to condense lower aliphatic alcohols having 1 to 10 carbon atoms to gasoline boiling hydrocarbon products, including mixed aliphatic and aromatic hydrocarbons. The method described in U.S. Pat. No. 3,894,107, published on 8 July 1975 by Butter et al., Which is hereby incorporated by reference in its entirety, includes Describes the process conditions used in the method.

  The catalyst may be in hydrogen form, or preferably in the range of about 0.05 to 5% by weight, base exchanged or impregnated to contain ammonium or metal cation replenishment. Metal cations that can be present include any of Group I-VIII metals of the periodic table. However, in the case of Group IA metals, the cation content should not be so high that it effectively deactivates the catalyst, or the exchange is all acid excluded. It should not be like that. If a basic catalyst is desired, there may be other steps involving treatment of the oxygenated material.

By contacting a methane -enhanced low molecular weight hydrocarbon with a catalyst containing a metal or metal compound that can convert SSZ-56 and low molecular weight hydrocarbons to high molecular weight hydrocarbons, Hydrogen can be formed. 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 performed are described in US Pat. No. 4,734,537, published 29 March 1988 by Devries et al. No. 4,939,311 published on July 3, 1990 by Washech et al .; No. 4,962,261 published on October 9, 1990 by Abrevaya et al .; Abbraya et al. No. 5,095,161 published on March 10, 1992; No. 5,105,044 published on April 14, 1992 by Han et al .; 1992 by Washet Check No. 5,105,046 published on May 14; August 24, 1993 by Han et al. Published No. 5,238,898; No. 5,321,185 published 14 June 1994 by van der Vaart; and 8 1994 by Choudhary et al. No. 5,336,825, each of which is hereby incorporated by reference in its entirety, published on Monday.

1-Olefin Polymerization The molecular sieve of the present invention can be used as a catalyst for 1-olefin polymerization, for example, ethylene polymerization. To form an olefin polymerization catalyst, a molecular sieve as previously described is reacted with a special type of organometallic compound. Organometallic compounds useful for forming the polymerization catalyst include trivalent and tetravalent organotitanium and organochromium compounds having an alkyl moiety and optionally a halo moiety. In the context of the present invention, the term “alkyl” includes alkaryl groups such as linear and branched alkyl, cycloalkyl, and benzyl.

  Examples of trivalent and tetravalent organochromium and organotitanium compounds are disclosed in US Pat. No. 4,376,722 published March 15, 1983 by Chester et al., March 22, 1983 by Chester et al. Issued on May 1, 1984 by Chester et al. And published on July 2, 1985 by Chester et al. U.S. Pat. No. 4,526,942. The description of said patent is hereby incorporated herein by reference in its entirety.

Examples of organometallic compounds used to form the polymerization catalyst have the general formula:
MY _n X _m-n
Wherein M is a metal selected from titanium and chromium; Y is alkyl; X is halogen (eg, Cl or Br); n is 1 to 4; m is equal to n Or 3 or 4).
Although the compound corresponding to is included, it is not limited to them.

Examples of organotitanium and organochromium compounds encompassed by such a formula include the formula, CrY ₄ , CrY ₃ , CrY ₃ X, CrY ₂ X, CrY ₂ X ₂ , CrYX ₂ , CrYX ₃ , TiY ₄ , TiY ₃ , TiY ₃ X, TiY ₂ X, TiY ₂ X ₂ , TiYX ₂ , TiYX _{3 wherein} X can be Cl or Br, Y is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2-ethylbutyl, octyl, 2-ethylhexyl, 2,2-diethylbutyl, 2-isopropyl-3-methylbutyl, etc., for example, cyclohexylmethyl , 2-cyclohexylethyl, 3-cyclohexylpropyl, 4 Cyclohexylalkyl, such as cyclohexylbutyl, and corresponding alkyl-substituted cyclohexyl radicals such as, for example, (4-methylcyclohexyl) methyl, neophyll, ie, β, β-dimethyl-phenethyl, benzyl, ethylbenzyl, and p-isopropyl Which can be benzyl]. Preferred examples of Y include C _1-5 alkyl, especially butyl.

  The organotitanium and organochromium materials used in the catalyst can be produced by techniques well known in the art. See, for example, the aforementioned patent by Chester et al.

  The organic titanium or organic chromium compound can be combined with the molecular sieve of the present invention to form an olefin polymerization catalyst, for example, by reacting the organometallic compound with the molecular sieve. In general, such reactions are conducted in the same reaction medium used to produce the organometallic compound, under conditions that promote the formation of such reaction products. The molecular sieve can simply be added to the reaction mixture after the formation of the organometallic compound is complete. The molecular sieve is added in an amount sufficient to provide about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight of organometallic compound per 100 parts by weight of molecular sieve in the reaction medium.

  During the reaction between the organometallic compound and the molecular sieve, the temperature of the reaction medium is also maintained at a level that is low enough to ensure the stability of the organometallic reactant. For example, temperatures in the range of about −150 ° C. to 50 ° C., preferably about −80 ° C. to 0 ° C. can be used effectively. A reaction time of about 0.01 to 10 hours, more preferably about 0.1 to 1 hour can be used to react the organotitanium or organochromium compound with the molecular sieve.

  When the reaction is complete, the catalyst material so formed can be recovered and dried by evaporating the reaction medium solvent in a nitrogen atmosphere. Alternatively, the olefin polymerization reaction can be carried out in the same solvent-based reaction medium used to form the catalyst.

  The polymerization catalyst can be used to catalyze the polymerization of 1-olefins. The polymer produced using the catalyst of the present invention is usually a solid polymer of at least one mono-1-olefin having 2 to 8 carbon atoms per molecule. These polymers are usually solid ethylene homopolymers or copolymers of ethylene and another mono-1-olefin having 3 to 8 carbon atoms per molecule. Examples of the copolymer include copolymers such as ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, and ethylene / 1-octene. The major part of such a copolymer is derived from ethylene and generally consists of about 80-99, preferably 95-99 mol% ethylene. These polymers are well suited for extrusion, blow molding, injection molding, and the like.

  The polymerization reaction is effective as a catalyst for monomers (one or many), for example, ethylene alone or one or more other olefins, substantially without the presence of catalyst poisons such as moisture and air. This can be done by contacting with a sufficient amount of supported organometallic catalyst at a temperature and pressure sufficient to initiate the polymerization reaction. If desired, an inert organic solvent is used as a diluent and if the polymerization reaction is carried out with the reactants in a liquid phase, eg, particulate (slurry) or solution process, it is used to facilitate handling of the material. You can also. The reaction is in the absence of a solvent, but can be carried out using gas phase reactants in a fluid bed configuration in the presence of an inert gas such as nitrogen if desired.

  The polymerization reaction is conducted at temperatures from about 30 ° C. to about 200 ° C. or higher depending on the operating pressure, the pressure of the olefin monomer, the particular catalyst used and its concentration. Of course, the operating temperature selected will also depend on the desired polymer melt index. This is because it is certain that temperature is a factor that regulates the molecular weight of the polymer. Preferably, the temperature used is from about 30 ° C. to about 100 ° C. for conventional slurry or “particle formation” processes, or from 100 ° C. to 150 ° C. for “solution formation” processes. In the fluidized bed process, temperatures from about 70 ° C to 110 ° C can be used.

  The pressure used in the polymerization reaction may be a pressure sufficient to initiate polymerization of the monomer (one or many) to a high molecular weight polymer. Therefore, an inert gas can be used as a diluent to provide a range from reduced pressure to about 30,000 psig or higher to ultrahigh pressure. A preferred pressure is from atmospheric pressure (0 psig) to about 1000 psig. As a general rule, a pressure of 20 to 800 psig is most preferred.

  The selection of the inert organic solvent medium used in the solution or slurry process aspect of the present invention is not very strict, but the solvent is inert to the supported organometallic catalyst and the olefin polymer produced and the reaction used. Should be stable at temperature. However, the inert organic solvent medium need not serve as a solvent for the polymer produced. Among the inert organic solvents that can be applied for such purposes are saturated aliphatics having about 3 to 12 carbon atoms per molecule such as hexane, heptane, pentane, isooctane, purified kerosene, etc. Saturated alicyclic hydrocarbons having about 5 to 12 carbon atoms per molecule such as hydrocarbons, cyclohexane, cyclopentane, dimethylcyclopentane, methylcyclohexane, and the like, and benzene, toluene, xylene, etc. Mention may be made of aromatic hydrocarbons having about 6 to 12 carbon atoms per molecule. Particularly preferred solvent media are cyclohexane, pentane, hexane, and heptane.

  Hydrogen can be introduced into the polymerization reaction zone to reduce the molecular weight of the polymer produced (ie, provide a much higher melt index, MI). The hydrogen partial pressure when using hydrogen can be in the range of 5-100 psig, preferably 25-75 psig. The melt index of the polymers produced in accordance with the present invention can range from about 0.1 to about 70 or more.

  A more detailed description of suitable polymerization conditions, including examples of granular, solution, and fluid bed polymerization configurations, can be found in US Pat. No. 3,709,853, published Jan. 9, 1973 by Karapinka, Karol. (Karol) et al., U.S. Pat. No. 4,086,408, published Apr. 25, 1978. Both of these patents are hereby incorporated by reference.

Hydrotreating SSZ-56 is useful as a hydrotreating catalyst. During hydroprocessing, oxygen, sulfur, and nitrogen present in the hydrocarbonaceous feed are reduced to low levels. If aromatics and olefins are present in the feed, the double bonds they have will also be saturated. In some cases, the hydroprocessing catalyst and hydroprocessing conditions minimize cracking reactions that can reduce the yield of the most desulfurized product (typically a product useful as a fuel). Selected as

Hydroprocessing conditions include 400-900 ° F. (204-482 ° C.), preferably 650-850 ° F. (343-454 ° C.) reaction temperature; 500-5000 psig (3.5-34.6 Mpa), preferably Is 1000 to 3000 psig (7.0 to 20.8 MPa) pressure; 0.5 hour ^{−1 to} 20 hour ⁻¹ (v / v) feed rate (LHSV); and 300 to 300 per barrel of liquid hydrocarbon feed. it is typical that include total hydrogen consumption 2000scf of _{H 2 (H 2} for liquid hydrocarbon feed 1 m ³ per 53.4~356m ^3). The hydrotreating catalyst will typically be a complex of a Group VI metal or compound thereof and a Group VIII metal or compound thereof supported on the molecular sieve of the present invention. Such hydroprocessing catalysts are typically pre-sulfided.

  Catalysts useful for hydrotreating hydrocarbon feeds are described in US Pat. No. 4,347,121 published May 31, 1982 by Mayer et al., And 1989 by Chester et al. U.S. Pat. No. 4,810,357, published March 7, 1980, both of which are hereby incorporated by reference in their entirety. Suitable catalysts include noble metals from Group VIII such as Fe, Co, Ni, Pt, or Pd and / or Group VI metals such as Cr, Mo, Sn, or W. Examples of combinations of Group VIII and Group VI metals include Ni-Mo or Ni-Sn. Other suitable catalysts were published in US Pat. No. 4,157,294 published June 5, 1979 by Iwao et al. And published on September 9, 1975 by Fischer et al. U.S. Pat. No. 3,904,513. U.S. Pat. No. 3,852,207 issued December 3, 1974 by Strangeland et al. Describes suitable noble metal catalysts and mild hydrotreating conditions. The contents of these patents are incorporated herein for reference.

  The amount of hydrogenation component (s) in the catalyst is about 0.5% to about 10% by weight of Group VIII, calculated as metal oxide (s) per 100 parts by weight of the total catalyst. Suitably it is in the range of the component (s) and 5% to about 25% by weight of the Group VI metal component (s). In this case, weight percent is based on the weight of the catalyst prior to sulfidation. The hydrogenation component (s) in the catalyst may be in an oxidized state and / or a sulfurized state.

Hydrogenated SSZ-56 can be used as a catalyst to catalyze the hydrogenation of hydrocarbon feeds containing unsaturated hydrocarbons. Unsaturated hydrocarbons can include olefins, dienes, polyenes, aromatic compounds, and the like.

  Hydrogenation is accomplished by contacting a hydrocarbon feed containing unsaturated hydrocarbons with hydrogen in the presence of a catalyst containing SSZ-56. The catalyst can also include one or more metals from Group VIB and Group VIII, including their salts, complexes, and solutions. References to these catalytically active metals include those in the elemental state or some form of such metals (one or many) such as oxides, sulfides, halides, carboxylates, etc. And Examples of such metals include the group consisting of platinum, palladium, rhodium, iridium, or combinations thereof, or nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, rhenium, manganese, and their Included are metals, salts, or complexes selected from the group consisting of combinations.

  The hydrogenation component of the catalyst (i.e. the metal) is present in an amount effective to provide the hydrogenation function of the catalyst, preferably in the range of 0.05 to 25% by weight.

  Hydrogenation conditions such as temperature, pressure, space velocity, contact time, etc. are well known in the art.

Reduction of nitrogen oxides in a gas stream SSZ-56 can also be used to catalytically reduce nitrogen oxides in a gas stream. Typically, the gas stream also contains oxygen, often containing a stoichiometric excess. SSZ-56 may also contain a metal or metal ion that can catalyze the reduction of nitrogen oxides in or on it. Examples of such metals or metal ions include cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium, and mixtures thereof.

  An example of such a process for the catalytic reduction of nitrogen oxides in the presence of zeolite is described in US Pat. No. 4,297,328 published Oct. 27, 1981 by Ritscher et al. Are included here for reference). The contact process there is the combustion of carbon monoxide and hydrocarbons and the catalytic reduction of nitrogen oxides contained in a gas stream such as exhaust gas from an internal combustion engine. The zeolite used is ion exchanged, doped or deposited with sufficient metal to provide an effective amount of catalytic copper metal or copper ions in or on the zeolite. Furthermore, the process is carried out in an excess of oxidant, for example oxygen.

Gaseous waste products resulting from combustion of hydrocarbonaceous fuels such as cold start exhaust gasoline and fuel oil contain carbon monoxide, hydrocarbons, and nitrogen oxides as products of combustion or incomplete combustion, and Give serious health problems in relation to pollution. Exhaust gases from other carbonaceous fuel combustion related mechanisms such as stationary engines, industrial furnaces, etc. cause substantial air pollution, and exhaust gases from automobile engines are the main source of pollution. Because of these health issues, the Environmental Protection Agency (EPA) has issued strict regulations on the amount of carbon monoxide, hydrocarbons, and nitrogen oxides emitted by automobiles. The implementation of these regulations has resulted in the use of catalytic converters to reduce the amount of pollutants emitted from automobiles.

  To achieve simultaneous conversion of carbon monoxide, hydrocarbons, and nitrogen oxide contaminants, a catalyst may be used with an air-to-fuel ratio control means that functions to respond to feedback signals from oxygen sensors in the engine exhaust system. It is getting done. These ternary control catalysts work well after they reach an operating temperature of about 300 ° C., but at lower temperatures they cannot convert substantial amounts of contaminants. This means that when an engine, in particular an automobile engine, is started, its three-component control catalyst cannot convert hydrocarbons and other pollutants into harmless compounds.

  Adsorption beds have been used to adsorb hydrocarbons during the cold start part of the engine. Although the method would typically be used in the case of hydrocarbon fuels, the present invention can also be used to treat exhaust gas streams from alcohol fuel engines. The adsorbent bed is typically placed immediately before the catalyst. That is, the exhaust gas stream first flows through the adsorption bed and then through the catalyst. The adsorption bed mainly adsorbs hydrocarbons rather than water under the conditions present in the exhaust gas stream. After a certain amount of time, the adsorption bed reaches a temperature (typically about 150 ° C.) at which the bed can no longer remove hydrocarbons from the exhaust gas stream. That is, instead of adsorbing hydrocarbons, they are actually desorbed from the adsorption bed. This regenerates the adsorbent bed so that it can adsorb hydrocarbons during the next cold start.

  In the prior art, several documents have been submitted dealing with the use of an adsorbent bed to minimize hydrocarbon emissions during engine cold start operations. One such document is US Pat. No. 3,699,683, where an adsorbent bed is placed after both the reduction catalyst and the oxidation catalyst. The patentee passes the gas stream through the reduction catalyst when the exhaust gas stream is below 200 ° C., then through the oxidation catalyst, and finally through the adsorbent bed, thereby adsorbing hydrocarbons in the adsorbent bed. It is disclosed. When the temperature is higher than 200 ° C., the gas stream released from the oxidation catalyst is divided into a large part and a small part, the majority is discharged directly into the atmosphere, and the small part is passed through the adsorbent bed to remove unburned hydrocarbons. Desorbed and then the resulting small portion of this exhaust gas stream containing unburned hydrocarbons desorbed is passed to the engine where they are burned.

  Another document is US Pat. No. 2,942,932, which teaches a method for oxidizing carbon monoxide and hydrocarbons contained in an exhaust gas stream. The process disclosed in this patent flows an exhaust gas stream below 800 ° F. to an adsorption zone where carbon monoxide and hydrocarbons are adsorbed and then the resulting stream from this adsorption zone is sent to the oxidation zone. Consists of. When the temperature of the exhaust gas stream reaches about 800 ° F., the exhaust gas stream is no longer passed through the adsorption zone and is sent directly to the oxidation zone with excess air.

  US Pat. No. 5,078,979, published on 7 January 1992 by Dunne, which is hereby incorporated by reference in its entirety, uses a molecular sieve adsorbent bed. And treating the exhaust gas flow from the engine to prevent cold start emissions. Examples of molecular sieves include faujasite, clinoptilolite, mordenite, chabazite), silicalite, zeolite Y, ultrastable zeolite Y, and ZSM-5. included.

  Canadian Patent 1,205,980 describes a method for reducing waste emissions from alcohol-fueled vehicles. This method consists of sending a cold engine starting exhaust gas to a bed of zeolite particles and then over an oxidation catalyst, which is then released into the atmosphere. As the exhaust gas stream becomes warm, it is continuously passed through the adsorption bed and then the oxidation bed.

  As already mentioned, the present invention relates generally to a method for treating an engine exhaust gas stream, and more particularly to a method for minimizing emissions during a cold start operation of an engine. The engine consists of an internal combustion or external combustion engine that generates an exhaust gas stream containing toxic components or pollutants including unburned or pyrolyzed hydrocarbons or similar organics. Other toxic components that are normally present in exhaust gases include nitrogen oxides and carbon monoxide. The engine may be supplied with a hydrocarbonaceous fuel. The term “carbonaceous fuel” as used herein and in the appended claims includes hydrocarbons, alcohols, and mixtures thereof. Examples of hydrocarbons that can be used as engine fuel are the hydrocarbon mixtures that make up gasoline or diesel fuel. Alcohols that can be used as engine fuel include ethanol and methanol. Alcohol mixtures and mixtures of alcohols and hydrocarbons can also be used. The engine may be a jet engine, a gas turbine, an internal combustion engine, such as an automobile, truck or bus engine, a diesel engine, and the like. The method of the present invention is particularly suitable for a hydrocarbon, alcohol, or hydrocarbon-alcohol mixture internal combustion engine mounted on an automobile. For simplicity in illustrating the present invention, the description as fuel will use hydrocarbons. The use of hydrocarbons in the following description should not be considered as limiting the present invention to hydrocarbon fuel engines.

  When the engine is started, not only relatively high concentrations of hydrocarbons but also other contaminants are produced in the engine exhaust gas stream. As used herein, pollutants collectively refer to any unburned fuel components and combustion by-products found in the exhaust gas stream. For example, if the fuel is a hydrocarbon fuel, hydrocarbons, nitrogen oxides, carbon monoxide, and other combustion byproducts will be found in the engine exhaust gas stream. The temperature of this engine exhaust gas stream is relatively cold, generally below 500 ° C, typically in the range of 200-400 ° C. This engine exhaust flow has the above characteristics during the initial operation of the engine, typically for the first 30-120 seconds after starting the cold engine. The engine exhaust stream will typically contain about 500-1000 ppm hydrocarbon by volume.

  The engine exhaust gas stream to be treated is passed over a molecular sieve bed containing molecular sieve SSZ-56 to produce a first exhaust stream. The molecular sieve SSZ-56 is described below. The first exhaust stream released from the molecular sieve bed is then flowed over the catalyst to convert the contaminants contained in the first exhaust stream into harmless components, giving a treated exhaust stream that is To release. It will be appreciated that the treated exhaust stream can be passed through a muffler or other silencer well known in the art prior to release to the atmosphere.

  Catalysts used to convert pollutants to innocuous components are commonly referred to in the art as ternary controlled catalysts. Because it oxidizes all residual hydrocarbons present in the first exhaust stream to carbon dioxide and water, oxidizes all residual carbon monoxide to carbon dioxide, and converts all residual nitrogen oxides to nitrogen and oxygen. This is because the reduction can be performed simultaneously. In some cases, for example, when alcohol is used as the fuel, the catalyst may not need to convert nitrogen oxides to nitrogen and oxygen. In this case, the catalyst is called an oxidation catalyst. Due to the relatively low temperature of the engine exhaust stream and the first exhaust stream, this catalyst does not function with very high efficiency and therefore requires a molecular sieve bed.

  When the molecular sieve bed reaches a sufficient temperature, typically about 150-200 ° C, contaminants adsorbed on the bed begin to desorb and are carried over the catalyst by the first exhaust stream. At this point, the catalyst has reached its operating temperature and can therefore be completely converted into non-hazardous components.

  The adsorbent bed used in the present invention can be conveniently used in particulate form, or the adsorbent may be attached to an integral solid carrier. If a particulate form is desired, the adsorbent can be formed into shapes such as globules, pellets, granules, rings, spheres, and the like. When using a monolithic form, it is usually most convenient to use the adsorbent as a thin film or coating attached to an inert carrier material that provides structural support to the adsorbent. The inert carrier material can be any refractory material such as a ceramic or metallic material. It is desirable that the carrier material does not react with the adsorbent and is not degraded by the gas to which it is exposed. Examples of suitable ceramic materials include sillimanite, petalite, cordierite, mullite, zircon, zircon mullite, spoutumene, alumina titanate, and the like. In addition, metal materials that fall within the scope of the present invention include metals as described in US Pat. No. 3,920,583 that are oxidation resistant or otherwise can withstand high temperatures. And alloys.

  The carrier material can best be used in any rigid unitary shape that provides a plurality of holes or grooves extending in the direction of gas flow. The shape is preferably a honeycomb structure. The honeycomb structure can advantageously be used as a unitary form or as an array of multiple modules. The honeycomb structure is usually oriented such that the gas flows generally in the same direction as the chamber or groove of the honeycomb structure. See US Pat. Nos. 3,785,998 and 3,767,453 for a more detailed discussion of monolithic structures.

  The molecular sieve is attached to the carrier in any convenient manner well known in the art. A preferred method includes preparing a slurry using molecular sieves and coating the monolithic honeycomb carrier with the slurry. The slurry can be prepared by means known in the art such as combining an appropriate amount of molecular sieve and binder with water. This mixture is then mixed using means such as sonication, grinding, and the like. Using this slurry, the integral honeycomb structure is immersed in the slurry and drained or blown to remove excess slurry from the groove and heated to about 100 ° C. to coat the honeycomb structure. . If the desired loading of the molecular sieve has not been achieved, the above method can be repeated as many times as necessary to achieve the desired loading.

  Instead of attaching the molecular sieve to the unitary honeycomb structure, the molecular sieve can be formed into the unitary honeycomb structure by means known in the art.

  The adsorbent may optionally contain one or more catalytic metals dispersed thereon. Metals that can be dispersed on the adsorbent are noble metals consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof. The desired noble metal can be deposited on the adsorbent serving as a support in any suitable manner well known in the art. An example of a method for dispersing a noble metal on an adsorbent carrier is to impregnate an adsorbent carrier with an aqueous solution of a decomposable compound of a desired noble metal (one or many kinds), and then drying the adsorbent on which the noble metal compound is dispersed. And then calcining in air at a temperature of about 400 ° C. to about 500 ° C. for about 1 to about 4 hours. A decomposable compound means a compound that gives a metal or metal oxide when heated in air. Examples of degradable compounds that can be used are described in US Pat. No. 4,791,091, hereby incorporated by reference. Preferred degradable components are chloroplatinic acid, rhodium trichloride, chloropalladic acid, hexachloroiridate (VI) acid, and hexachlororuruthenate. The noble metal is preferably present in an amount ranging from about 0.01 to about 4% by weight of the adsorbent support. In particular, for platinum and palladium, the range is 0.1 to 4% by weight, while for rhodium and ruthenium, the range is about 0.01 to 2% by weight.

  These catalytic metals can oxidize hydrocarbons and carbon monoxide and reduce the nitrogen oxide component to innocuous products. Thus, the adsorbent bed can act as both an adsorbent and a catalyst.

  The catalyst used in the present invention is selected from any three-component control catalyst or oxidation catalyst well known in the art. Examples of such catalysts are described in U.S. Pat. Nos. 4,528,279, 4,791,091, 4,760,044, 4,868,148, and all incorporated herein by reference. No. 4,868,149. Preferred catalysts well known in the art are those containing platinum and rhodium, and optionally palladium, while oxidation catalysts usually do not contain rhodium. The oxidation catalyst usually contains platinum and / or palladium metal. These catalysts may contain promoters and stabilizers such as barium, cerium, lanthanum, nickel, and iron. Noble metal promoters and stabilizers are usually deposited on a support such as alumina, silica, titania, zirconia, aluminosilicate, and mixtures thereof, with alumina being preferred. The catalyst can be conveniently used in particulate form, or the catalyst complex can be attached to an integral solid carrier, with an integral carrier being preferred. Particulate and unitary forms of the catalyst are produced as described above for the adsorbent.

  The following examples demonstrate the invention and are not limiting.

Example 1
Synthesis of the directing agent N, N-diethyl-2-methyldecahydroquinolinium hydroxide The parent amine 2-methyldecahydroquinoline was obtained by hydrogenation of 2-methylquinoline (quinaldine) as described below. In a 1000 ml stainless steel hydrogenation vessel, 200 g (1.4 mol) 2-methylquinoline (quinaldine) purchased from Aldrich Chemical Company and 300 ml glacial acetic acid, 10 g PtO ₂ , and 15 ml Concentrated H ₂ SO ₄ was introduced. The mixture was purged with nitrogen twice (pressurizing the vessel with nitrogen to 1000 psi and evacuating). The reaction vessel was then pressurized with hydrogen gas to 1500 psi and stirred at 50 ° C. overnight. The pressure dropped overnight and the vessel was pressurized back to 1500 psi (with H ₂ gas) and stirred until no pressure drop was observed anymore. When the reaction was complete, the mixture was filtered and the filtrate was treated with 50 wt% aqueous sodium hydride solution until the pH was ~ 9. The treated filtrate was diluted with 1000 ml diethyl ether. The organic layer was separated, washed with water and brine and dried over anhydrous MgSO ₄ . By concentrating in vacuo (using a rotary evaporator), a pair of isomers (cis and trans fused ring isomers, both isomers with methyl groups in the equatorial position) 1.1: A transcondensation of 0.9: gave cis-condensed isomer ratio in 97% yield of amine (208 g) Product authenticity was determined by spectral data analysis including NMR, IR, and GCMS spectroscopy. In principle, there are four similar isomers, but only two isomers were formed.

  N-ethyl-2-methyldecahydroquinolinium hydroiodide was prepared according to the method described below. To a solution of 100 g (0.65 mol) of 2-methyldecahydroquinoline (trans and cis) in 350 ml of acetonitrile was added 111 g (0.72 mol) of ethyl iodide. The mixture was stirred at room temperature for 96 hours (using an overhead stirrer). Then another 1/2 molar equivalent of ethyl iodide was added and the mixture was heated to reflux for 6 hours. The reaction mixture was concentrated on a rotary evaporator at reduced pressure and the resulting solid was rinsed with 500 ml of ethyl ether to remove any unreacted amine and excess iodide. This reaction gave two types of N-ethyl-2-methyl-decahydroquinolinium hydroiodide (mono-ethyl derivative) and a small amount of a quaternized derivative mixture. The product is isolated several times by recrystallization with isopropyl alcohol, and is converted into pure trans-fused ring N-ethyl-2-methyl-decahydroquinolinium hydroiodide and pure cis-fused ring N-ethyl-2-methyl. -Decahydroquinolinium hydroiodide was provided (see formula below).

N, N-diethyl-2-methyldecahydroquinolinium iodide was prepared according to the procedure shown below. The procedure below is typical for preparing N, N-diethyl-2-methyl-decahydro-quinolinium iodide. The resulting trans-fused ring N-ethyl-2-methyl-decahydroquinolinium hydroiodide (28 g, 0.09 mol) was added to a solution of acetonitrile (150 ml) and KHCO ₃ (14 g, 0.14 mol). Added. To this solution was added 30 g (0.19 mol) of ethyl iodide and the resulting mixture was stirred (using an overhead stirrer) at room temperature for 72 hours. Further, one or more molar equivalents of ethyl iodide were added and the reaction was heated to reflux and stirred at reflux temperature for 6 hours. Heating was stopped and the reaction was further stirred at room temperature overnight. The reaction was terminated by removing excess ethyl iodide and solvent at reduced pressure on a rotary evaporator. The resulting solid was suspended in 500 ml of chloroform, thereby dissolving the desired product, leaving unnecessary KHCO ₃ and its salt by-products. The solution was filtered and the filtrate was dried over anhydrous MgSO ₄ . Filtration and concentration on a rotary evaporator at reduced pressure gave the desired N, N-diethyl-2-methyl-decahydroquinolinium iodide as a light tan solid. This solid was further purified by recrystallization from isopropyl alcohol. The reaction gave 26.8 g (87% yield). The procedure described above produced the cis-fused ring isomer, N, N-diethyl-2-methyl-decahydro-quinolinium iodide. Trans-fused ring derivative A (see Scheme 1 below) is a templating agent (SDA) useful for producing SSZ-56, N, N-diethyl-2-methyldecahydroquinolinium hydroxide.

  The hydroxide form of the N, N-diethyl-2-methyl-decahydro-quinolinium cation was prepared by ion exchange as described in the procedure below. To a solution of 20 g (0.06 mol) of N, N-diethyl-2-methyldecahydro-quinolinium iodide in 80 ml of water, 80 g of OH ion exchange resin [BIORAD® AGI-X8] was added and the resulting mixture was gently stirred for several hours at room temperature. The mixture was filtered and the ion exchange resin was rinsed with an additional 30 ml of water (to ensure removal of all cations from the resin). The rinse and original filtrate were combined and titration analysis of a small sample of the filtrate with 0.1N HCl showed an OH ion concentration of 0.5M (0.055 moles of cation). Scheme 1 below depicts the synthesis of the template agent.

  Four isomers are possible from this synthesis (drawn below), but two isomers were produced: trans-condensed equatorial methyl A and cis-condensed equatorial methyl B;

Example 2
Synthesis of borosilicate SSZ-56 from calcined boron BETA zeolite N, N-diethyl-2-methyldecahydroquinolinium hydroxide (trans fused ring isomer) in 23 cc Teflon liner ) 0.5M solution 3 g (1.5 mM), NaOH 1.0 N aqueous solution 0.5 g (0.5 mM), 4.5 g deionized water, and 0.65 g calcined boron BETA zeolite were all mixed. The Teflon liner was capped, placed in a Parr reactor and heated to 150 ° C. while rotating in an oven at about 43 rpm. The progress of the reaction was checked by monitoring the gel pH and looking for crystal formation using a scanning electron microscope (SEM) at intervals of 3-6 days. Usually the reaction was complete after heating for 18-24 days (at 160 ° C. the crystallization time achieved was much shorter). The final pH at the end of the reaction ranged from 10.8 to 11.6. When crystallization was complete (by SEM analysis), the reaction mixture (usually a white fine powder precipitate with a clear liquid) was filtered. The collected solid was rinsed several times with deionized water (˜1000 ml), then air dried overnight and then dried in an oven at 120 ° C. for 15-20 minutes. This reaction produced 0.55-0.6 g of pure boron SSZ-56 as determined by XRD analysis.

Example 3
Preparation of particle-added borosilicate SSZ-56 3 g of a 0.5 M solution of N, N-diethyl-2-methyldecahydroquinolinium hydroxide (trans fused ring isomer) in a 23 cc Teflon liner. 1.5 mM), 0.5 g (0.5 mM) 1.0 N aqueous solution of NaOH, 4.5 g deionized water, and 0.65 g calcined boron BETA zeolite, and 0.03 g SSZ-56 (described above). In the same manner). The Teflon liner was capped, placed in a pearl reactor and heated to 150 ° C. while rotating in an oven at about 43 rpm. The progress of the reaction was checked by monitoring the gel pH and looking for crystal formation using a scanning electron microscope (SEM) at 3 day intervals. Crystallization was complete after 6 days of heating (SEM analysis). The final pH at the end of the reaction was usually 11.2. When crystallization is complete, the reaction mixture is filtered and the collected solid is rinsed with deionized water (˜1000 ml), then air dried overnight and then dried in an oven at 120 ° C. for 15-20 minutes. . This reaction produced 0.6 g of pure boron SSZ-56. The identity and properties of the material were determined by XRD analysis.

Example 4
Direct synthesis of borosilicate SSZ-56 from sodium borate decahydrate as a boron source and CAB-O-SIL M-5 as a silicon source in a 23 cc Teflon liner in water 6 g (3 mM) of a 0.5 M solution of N, N-diethyl-2-methyldecahydroquinolinium oxide (trans fused ring isomer), 1.2 g (1.2 mM) of a 1.0 N aqueous solution of NaOH, 4.8 g Deionized water and 0.065 g sodium borate decahydrate were mixed and stirred until the sodium borate was completely dissolved. Then added cab-O-Sil _{M-5 (~98% SiO 2} ) of 0.9 g, it was mixed thoroughly. The resulting gel was capped, placed in a pearl reactor and heated to 160 ° C. while rotating in an oven at about 43 rpm. The progress of the reaction was checked by monitoring the pH of the gel and looking for crystal formation using a scanning electron microscope (SEM) at 6 day intervals. Usually, the reaction was complete after heating for 18-24 days. The final pH at the end of the reaction ranged from 11.5 to 12.3. When crystallization was complete (by SEM analysis), the reaction mixture, a clear liquid and a white fine powdery precipitate, was filtered. The collected solid was rinsed several times with deionized water (˜1000 ml), then air dried overnight and then dried in an oven at 120 ° C. for 15 minutes. This reaction usually produces 0.75-0.9 g of pure boron SSZ-56.

Example 5
Synthesis of particle-added borosilicate SSZ-56 from sodium borate decahydrate as a boron source and cab o sil M-5 as a silicon source in a 23 cc Teflon liner in N, N-diethyl hydroxide 6 g (3 mM) of a 0.5 M solution of 2-methyldecahydroquinolinium (trans fused ring isomer), 1.2 g (1.2 mM) of a 1.0 N aqueous solution of NaOH, 4.8 g of deionized water, and 0 0.062 g of sodium borate decahydrate was mixed and stirred until the sodium borate was completely dissolved. Then added cab-O-Sil _{M-5 (~98% SiO 2} ) and 0.04g of B-SSZ-56 prepared with as the example 4 0.9 g, thoroughly mixed did. The resulting gel was capped, placed in a pearl reactor and heated to 160 ° C. while rotating in an oven at about 43 rpm. The progress of the reaction was checked by monitoring the gel pH and looking for crystal formation using a scanning electron microscope (SEM) at intervals of 3-5 days. The reaction was complete after heating for 7 days. The final pH at the end of the reaction was about 12.2. When crystallization was complete (by SEM analysis), the reaction mixture, a clear liquid and a white fine powdery precipitate, was filtered. The collected solid was rinsed several times with deionized water (˜1000 ml), then air dried overnight and then dried in an oven at 120 ° C. for 15 minutes. This reaction produced 0.88 g of pure boron SSZ-56.

Example 6
The template agent molecules (structure directing agent: SDA) were removed from the zeolite SSZ-56 by the calcination method described under calcination of SSZ-56 to achieve release of its grooves and cavities. A sample of as-prepared SSZ-56 synthesized by the procedure of Examples 2, 3, 4, or 5 discussed above is made into a thin bed of SSZ-56 in a calcining dish and placed in a muffle furnace. It was calcined by heating from room temperature to 595 ° C in three steps. The sample was heated to 120 ° C. at a rate of 1 ° C./min and held for 2 hours. The temperature was then raised to 540 ° C. at a rate of 1 ° C./min and held for 5 hours. The temperature was then raised again to 595 ° C. at a rate of 1 ° C./min and held there for 5 hours. A stream of nitrogen with a slight air leak was passed over the zeolite at a rate of 20 standard ft ³ / min (0.57 standard m ³ / min) during the calcination process heating.

Example 7
Ammonium ion exchange of SSZ-56 Na ⁺ -type SSZ-56 prepared as in Example 2, 3, 4 or 5 and calcined as in Example 6 was converted to an aqueous solution of NH ₄ NO ₃ (typically the, of _{H 2} O 20 ml, was converted to the _NH ^{4 +} type SSZ-56 by heating for 2-3 hours at 90 ° C. in SSZ-56) of _NH 4 _NO 3 / 1g of 1g. The mixture was then filtered and this process was repeated as many times as desired (usually performed 2-3 times). After filtration, the resulting NH ₄ exchange product was washed with deionized water and air dried. This NH ₄ ⁺ form SSZ-56 can be converted to the H ⁺ form by calcination to 540 ° C. (stopped at the end of the second stage as described in Example 6 above).

Example 8
Preparation of Aluminosilicate SSZ-56 by Aluminum Exchange of Boron-SSZ-56 Aluminosilicate SSZ-56 was prepared by exchanging borosilicate SSZ-56 with aluminum nitrate according to the procedure described below. Calcined H ⁺ -type borosilicate SSZ-56 (prepared as in Example 2, 3, 4 or 5 and treated with ammonium nitrate as in Example 6 and calcined) was converted to aluminum nitrate. nine to 1 molar solution in hydrate by suspending the zeolite ^{(H +} / borosilicate SSZ-56) in _{(10ml Al (NO 3) 3} · 9H 2 O-1M solution of / 1g SSZ- 56), easily converted to aluminosilicate SSZ-56. The suspension was heated at reflux overnight. The resulting mixture was then filtered and the collected solid was rinsed thoroughly with deionized water and air dried overnight. The solid was further dried in an oven at 120 ° C. for 2 hours. This exchange can also be performed for Na ⁺ -type SSZ-56 (produced as in Examples 2, 3, 4, or 5 and calcined as in Example 6).

Example 9
Nitrogen adsorption (micropore volume analysis)
Synthesized as described above Example 2 and 4, the Na ⁺ and ^{H +} form SSZ-56 was then processed as in Example 6 and 7, the _{N 2} is used as the adsorbate, by a BET method specific surface area and micropore Volumetric analysis was performed. The zeolite had a micropore volume of 0.18 cc / g for the Na ⁺ form and 0.19 cc / g for the H ⁺ form and showed a significant void volume.

Example 10
Argon adsorption (micropore volume analysis)
A calcined sample of Na ⁺ type borosilicate SSZ-56 (synthesized as in Example 2 and calcined as in Example 6) was recorded on an ASAP 2010 facility from Micromerities 87. It had a micropore volume of 0.16 cc / g based on an argon adsorption isotherm of 5 ° K (−186 ° C.). The sample was first degassed at 400 ° C. for 16 hours, after which argon was adsorbed. The amount of low-pressure introduced was 2.00 cm ³ / g (STP). The maximum equilibration time used for one dose was 1 hour and the total operation time was 37 hours. The argon adsorption isotherm was analyzed using the Horvarth-Kawazoe-style Saito Foley modification (Microporous Materials, 3, 531 (1995)), and the conventional t-plot method [J. Catalysis, 4, 319 (1965)], parameters developed for activated carbon slits according to density functional theory (DFT) format and Olivier [Porous Mater. 2.9 (1995)].

Example 11
Constraint Index (Constrain Index) Hydrogen-type SSZ-56 synthesized as in Test Example 2 was calcined as in Examples 6 and 7, ammonium exchanged, and aluminum exchanged as in Example 8. The resulting aluminum exchanged SSZ-56 sample was then ammonium exchanged as in Example 7 and then calcined to 540 ° C. as in Example 6. H-Al-SSZ-56 was pelletized at 4 kpsi, pulverized, and granulated to 20-40 mesh. A 0.6 g sample of the granular material was calcined in air at about 540 ° C. for 4 hours, cooled in a desiccator and dried reliably. Next, 0.5 g was packed in a 3/8 inch stainless steel tube, and Alundum (registered trademark) was packed on both sides of the molecular sieve bed. The reaction tube was heated using a Lindburg furnace. Helium was introduced into the reaction tube at 10 cc / min and atmospheric pressure. The reactor was heated to about 315 ° C. and a 50/50 feed of n-hexane and 3-methylpentane was introduced into the reactor at a rate of 8 μl / min. The feed was pumped with a Brownlee pump. Sampling directly into the GC began 10 minutes after feed introduction. Constraint index (CI) values were calculated from GC data using methods known in the art. SSZ-56 had a CI of 0.76 and a conversion of 79% after 15 minutes of operation. This material was immediately contaminated, with a CI of 0.35 at 105 minutes and a conversion of 25.2%. CI tests have shown that this material is a very active catalyst material.

Example 12
1 g of a sample of the n-hexadecane hydrocracking test SSZ-56 (prepared as described for the binding index test of Example 11) was suspended in 10 g of deionized water. To this suspension was added a solution of Pd (NH ₃ ) ₄ (NO ₃ ) ₂ at a concentration that gave 0.5% by weight of Pd with respect to the dry weight of the molecular sieve sample. The pH of this solution was adjusted to a pH of 9.2 by dropwise addition of a 0.15N solution of ammonium hydroxide. The mixture was then heated at 75 ° C. in an oven for 48 hours. The mixture was then filtered through a glass frit, washed with deionized water and air dried. The collected Pd-SSZ-56 sample was slowly calcined in air to 482 ° C. and held there for 3 hours.

  The calcined Pd / SSZ-56 catalyst was pelletized with a Carver Press and pulverized to produce particles having a 20/40 mesh particle size. Particle size classified catalyst (0.5 g) was loaded into a 1/4 inch outer diameter tubular reactor in a micro unit for n-hexadecane hydroconversion. The table below gives experimental conditions and product data for the hydrocracking test for that n-hexadecane.

As the results shown in the table below indicate, SSZ-56 is a highly active isomerization selective catalyst that provides 96.5% nC ₁₆ conversion at 256 ° C.

Claims (82)

(1) Oxide of first tetravalent element to (2) Trivalent element, pentavalent element, second tetravalent element other than the first tetravalent element, or oxide molar ratio thereof A molecular sieve having an X-ray diffraction line of Table 2 after calcination.

(1) silicon oxide to (2) molar ratio of oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, and mixtures thereof is greater than 15, Molecular sieve having two X-ray diffraction lines.

  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. The molecular sieve according to claim 1 or 2, wherein after calcination, at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions . In the as-synthesized anhydrous state, expressed as a molar ratio, the following composition:
YO ₂ / _W c _O d 15- infinity M ₂ / _n / YO ₂ 0.01-0.03
Q / YO ₂ 0.02-0.05
[Wherein Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium, or a mixture thereof; c is 1 or 2; 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 the valence of M Q is a trans-fused ring N, N-diethyl-2-methyldecahydroquinolinium cation. ]
A molecular sieve having
A molecular sieve having the X-ray diffraction lines of Table 2 when calcined.

(1) a first oxide containing silicon oxide, and (2) a second oxide containing boron oxide, the molar ratio of the first oxide to the second oxide being greater than 15, A method for producing a crystalline material having two X-ray diffraction lines, comprising: a raw material for the oxide; and a structure directing agent containing a trans-fused ring N, N-diethyl-2-methyldecahydroquinolinium cation; Contacting with crystallization conditions.

The crystalline material is expressed in molar ratio:
YO ₂ / W _a O _b ≧ 15
OH− / YO ₂ 0.10-0.50
Q _/ YO 2 0.05-0.50
M ₂ / _n / YO ₂ 0.02-0.40
H ₂ O _/ YO ₂ 30-80
(Where Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium, or a mixture thereof; a is 1 or 2, and when a is 1, b is 2 and when a is 2, b is 3; M is an alkali metal cation, alkaline earth metal cation, or a mixture thereof; n is the valence of M; and Q Is a trans-fused ring N, N-diethyl-2-methyldecahydroquinolinium cation.)
A process according to claim 8 , wherein the process is prepared from a reaction mixture comprising: A hydrocarbonaceous feed, and (1) an oxide of a first tetravalent element, (2) a trivalent element, a pentavalent element, a second tetravalent element other than the first tetravalent element, or their A method for converting hydrocarbons comprising contacting a catalyst comprising a molecular sieve having an X-ray diffraction line in Table 2 after calcination and having a molar ratio of oxide in the mixture of greater than 15 under hydrocarbon conversion conditions.

The method of claim 10 , wherein the method is a hydrocracking method comprising contacting the catalyst and a hydrocarbon feedstock under hydrocracking conditions. The process of claim 10 , wherein the process is a dewaxing process comprising contacting the catalyst with a hydrocarbon feed at dewaxing conditions. It said method is a method for improving the the catalyst, the waxy hydrocarbon feed comprising contacting in an isomerization dewaxing conditions, the viscosity index of the dewaxed product of waxy hydrocarbon feed, wherein Item 11. The method according to Item 10 . The method according to claim 10, in the method on the catalyst, which comprises isomerizing at isomerization conditions to Oh olefin feed, a method for producing a C ₂₀₊ lubricant from C ₂₀₊ olefin feed. The method of claim 14 , wherein the catalyst further comprises at least one Group VIII metal. The method of claim 10 , wherein the catalyst further comprises at least one Group VIII metal. A layered catalyst in which the catalyst includes a first layer containing the molecular sieve and at least one Group VIII metal, and a second layer containing an aluminosilicate zeolite that is more shape selective than the molecular sieve of the first layer. The method of claim 10 , comprising: The method of claim 10 , wherein the method comprises:
Hydrocracking a hydrocarbonaceous feedstock in a hydrocracking zone to obtain a effluent comprising hydrocracked oil; and using the catalyst, the effluent comprising hydrocracked oil; Catalytic dewaxing in the presence of added hydrogen gas at a pressure of 15 psig to 3000 psig (0.103 to 20.7 MPa gauge) at a temperature of at least 400 ° F (204 ° C);
A method for producing a lubricating oil, comprising: The method of claim 18 , wherein the catalyst further comprises at least one Group VIII metal. 11. The method of claim 10 , wherein the method is a method of isomerizing and dewaxing a raffinate comprising contacting the raffinate and the catalyst in the presence of added hydrogen at isomerization and dewaxing conditions. 21. The method of claim 20 , wherein the catalyst further comprises at least one Group VIII metal. 21. The method of claim 20 , wherein the raffinate is bright stock. The method of claim 10 , wherein the molecular sieve comprises a Group VIII metal component. Said method, the hydrocarbon feedstock in the reaction zone, and the catalyst is a catalytic cracking process comprising contacting in the absence of added hydrogen at catalytic cracking conditions, method according to claim 10. 25. The method of claim 24 , wherein the catalyst further comprises an atmospheric pore crystalline decomposition component. The method of claim 10 , wherein the molecular sieve is impregnated with at least one Group VIII metal. 11. The method of claim 10 , wherein the catalyst is calcined at elevated temperature in a steam / air mixture after impregnation with the Group VIII metal. 27. The method of claim 26 , wherein the Group VIII metal is platinum. And the method C ₂ -C ₂₀ olefin, and at least a molar excess of the aromatic hydrocarbons, at alkylation conditions, the method comprising at least partially liquid phase conditions, is contacted in the presence the catalyst, aromatic The process according to claim 10 , which is a process for alkylating a group hydrocarbon. Wherein the olefin is a _C 2 -C ₄ olefin, A method according to claim 29. 32. The method of claim 30 , wherein the aromatic hydrocarbon and the olefin are each present in a molar ratio of 4: 1 to 20: 1. 31. The method of claim 30 , wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene, or mixtures thereof. The process comprises contacting an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon at least partially in a liquid phase condition in the presence of a catalyst and in an alkyl exchange condition to exchange the aromatic hydrocarbon. The method of claim 10 , which is a method. Said molecular sieve, after calcination, in which at least 80% of the cation sites is occupied by hydrogen ions and / or rare earth ions, claim 10,11～14,18,20,24,29, or 33 The method of any one of these. 34. The method of claim 33 , wherein the aromatic hydrocarbon and polyalkyl aromatic hydrocarbon are each present in a molar ratio of 1: 1 to 25: 1. 34. The method of claim 33 , wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof. 34. The method of claim 33 , wherein the polyalkyl aromatic hydrocarbon is a dialkylbenzene. The method comprises contacting paraffin with the molecular sieve and a catalyst containing gallium, zinc, or a compound of gallium or zinc under conditions for converting paraffin to aromatic, and converting paraffin to aromatic. The method of claim 10 , wherein: The method according to claim 10 , wherein the method comprises contacting the olefin with the catalyst under conditions that cause isomerization of the olefin, wherein the method isomerizes the olefin. In a method for the method of isomerizing the isomerization feed comprising a mixture of aromatic C ₈ stream or xylene isomers and ethylbenzene xylene isomers, contacting said feed with said catalyst and isomerization conditions 11. The process of claim 10 , wherein an ortho-, meta-, and para-xylene ratio is obtained that is closer to equilibrium. 11. The method of claim 10 , wherein the method comprises contacting an olefin feed with the catalyst at oligomerization conditions and is a method of oligomerizing an olefin. Mole of oxygenated hydrocarbon and oxide of first tetravalent element, second tetravalent element other than the first tetravalent element, trivalent element, pentavalent element, or a mixture thereof A process for converting oxygenated hydrocarbons, comprising contacting a catalyst comprising a molecular sieve having an X-ray diffraction line of Table 2 under conditions that produce a liquid product after calcination, the ratio being greater than 15.

43. The method of claim 42 , wherein the oxygenated hydrocarbon is a lower alcohol. 44. The method of claim 43 , wherein the lower alcohol is methanol. The method of claim 10 , wherein the method is a method of producing high molecular weight hydrocarbons from low molecular weight hydrocarbons,
(A) introducing a low molecular weight hydrocarbon-containing gas into the reaction zone, and converting the gas into a low molecular weight hydrocarbon into a high molecular weight hydrocarbon in the reaction zone and a metal or metal compound, and C ₂₊ contacting with hydrocarbon synthesis conditions; and (b) removing a high molecular weight hydrocarbon-containing stream from the reaction zone;
Including methods. 46. The method of claim 45 , wherein the metal or metal compound comprises a lanthanide or actinide metal or metal compound. 46. The method of claim 45 , wherein the low molecular weight hydrocarbon is methane. 1-a catalyst composition for promoting the polymerization of olefins,
(A) (1) Oxide of first tetravalent element (2) Trivalent element, pentavalent element, second tetravalent element other than the first tetravalent element, or oxide thereof A molecular sieve having an X-ray diffraction line of Table 2 after calcination; and (B) an organic titanium or organic chromium compound;
A catalyst composition comprising:

49. The oxide according to claim 48 , wherein the oxide (1) is silicon oxide and the oxide (2) is an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide. Method. The method comprises 1-olefin monomer,
(A) (1) Oxide of first tetravalent element (2) Trivalent element, pentavalent element, second tetravalent element other than the first tetravalent element, or oxide thereof A molecular sieve having an X-ray diffraction line of Table 2 after calcination; and (B) an organic titanium or organic chromium compound;
A method of polymerizing a 1-olefin comprising contacting a catalytically effective amount of a catalyst composition with a polymerization condition comprising a temperature and pressure suitable to initiate and promote the polymerization reaction, The method of claim 10 . 51. The oxide according to claim 50 , wherein the oxide (1) is silicon oxide and the oxide (2) is an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide. Method. 51. The method of claim 50 , wherein the 1-olefin monomer is ethylene. 52. The method of claim 51 , wherein the 1-olefin monomer is ethylene. 11. The method of claim 10 , wherein the method is a method of hydrogenating a hydrocarbon feed containing unsaturated hydrocarbons, wherein the feed and hydrogen are contacted with the catalyst under conditions that cause hydrogenation. A method comprising: The catalyst includes a metal, salt, or complex, and the metal is made of platinum, palladium, rhodium, iridium, or a combination thereof, or nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, 55. The method of claim 54 , selected from the group consisting of rhenium, manganese, and combinations thereof. Contacting a hydrocarbon feedstock with a hydrotreating catalyst and hydrogen under hydrotreating conditions, wherein said catalyst comprises (1) a first tetravalent element oxide pair (2) trivalent The molar ratio of the oxide of the element, pentavalent element, second tetravalent element other than the first tetravalent element, or a mixture thereof is greater than 15, and has the X-ray diffraction lines of Table 2 after calcination A method of hydrotreating a hydrocarbon feedstock comprising a molecular sieve.

57. The method of claim 56 , wherein the catalyst comprises a Group VIII metal or compound, a Group VI metal or compound, or combinations thereof. Contacting a hydrocarbon feedstock with a hydrotreating catalyst and hydrogen under hydrotreating conditions, wherein said catalyst comprises (1) silicon oxide vs. (2) aluminum oxide, gallium oxide, iron oxide, Hydrogenated hydrocarbon feedstock comprising a molecular sieve having an X-ray diffraction line of Table 2 after calcining, wherein the molar ratio of the oxide selected from boron oxide, titanium oxide, indium oxide, and mixtures thereof is greater than 15 How to process.

59. The method of claim 58 , wherein the oxide comprises silicon oxide and aluminum oxide. 59. The method of claim 58 , wherein the oxide comprises silicon oxide and boron oxide. 59. The method of claim 58 , wherein the oxide comprises silicon oxide. 59. The method of claim 58 , wherein the catalyst comprises a Group VIII metal or compound, a Group VI metal or compound, or combinations thereof. A molar ratio of a hydrocarbonaceous feed and an oxide selected from (1) silicon oxide to (2) aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, and mixtures thereof is from 15 A process for converting hydrocarbons comprising, after large calcination, contacting a catalyst comprising a molecular sieve having the X-ray diffraction lines of Table 2 under hydrocarbon conversion conditions.

A method for reducing nitrogen oxides contained in a gas stream comprising contacting said gas stream with a molecular sieve, wherein said molecular sieve comprises (1) an oxide pair of a first tetravalent element (2) The molar ratio of oxides of trivalent elements, pentavalent elements, second tetravalent elements other than the first tetravalent elements, or mixtures thereof is greater than 15, and after calcination, X in Table 2 Said method comprising line diffraction lines.

A method for reducing nitrogen oxides contained in a gas stream comprising contacting said gas stream with a molecular sieve, wherein said molecular sieve comprises (1) silicon oxide vs. (2) aluminum oxide, oxidation The method, wherein the molar ratio of an oxide selected from gallium, iron oxide, boron oxide, titanium oxide, indium oxide, and mixtures thereof is greater than 15 and has the X-ray diffraction lines of Table 2 after calcination.

66. The method according to claim 64 or 65 , which is performed in the presence of oxygen. 66. The method of claim 64 or 65 , wherein the molecular sieve comprises a metal or metal ion that can catalyze the reduction of nitrogen oxides. 68. The method of claim 67 , wherein the metal is cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium, or mixtures thereof. 66. A method according to claim 64 or 65 , wherein the gas stream is an exhaust gas stream of an internal combustion engine. 68. The method of claim 67 , wherein the gas stream is an exhaust gas stream of an internal combustion engine. A method of treating a cold start engine exhaust gas stream containing hydrocarbons and other contaminants, wherein the engine exhaust gas stream is flowed over a molecular sieve bed where hydrocarbons are preferentially adsorbed over water and the first exhaust A gas stream is obtained, the first exhaust gas stream is flowed over the catalyst, all residual hydrocarbons and contaminants contained in the first exhaust gas stream are converted into harmless products, and the treated exhaust Obtaining a gas stream and releasing the treated exhaust gas stream into the atmosphere, wherein the molecular sieve bed comprises (1) an oxide of a first tetravalent element, (2) a trivalent element, five The molar ratio of the oxide of the valence element, the second tetravalent element other than the first tetravalent element, or a mixture thereof is greater than 15, and after calcination, includes a molecular sieve having the X-ray diffraction lines of Table 2 And said method.

The molecular sieve has a molar ratio of oxide selected from (1) silicon oxide to (2) aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, and mixtures thereof, greater than 15; 72. The method of claim 71 , having the X-ray diffraction lines of Table 2 after calcination. 73. The method of claim 72 , wherein the oxide comprises silicon oxide and aluminum oxide. 73. The method of claim 72 , wherein the oxide comprises silicon oxide and boron oxide. 73. The method of claim 72 , wherein the oxide comprises silicon oxide. 72. The method of claim 71 , wherein the engine is an internal combustion engine. 77. The method of claim 76 , wherein the internal combustion engine is an automobile engine. 72. The method of claim 71 , wherein the engine is supplied with a hydrocarbonaceous fuel. 72. The method of claim 71 , wherein the molecular sieve has deposited thereon a metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof. 80. The method of claim 79 , wherein the metal is platinum. 80. The method of claim 79 , wherein the metal is palladium. 80. The method of claim 79 , wherein the metal is a mixture of platinum and palladium.