CA2613399C - Molecular sieve ssz-56 composition of matter and synthesis thereof - Google Patents

Abstract

The present invention relates to new crystalline molecular sieve SSZ-56 prepared using a trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium cation as a structure-directing agent, methods for synthesizing SSZ-56 and processes employing SSZ-56 in a catalyst.

Description

2 AND SYNTHESIS THEREOF

3 BACKGROUND OF THE INVENTION

4 Field of the Invention 6 The present invention relates to new crystalline molecular sieve SSZ-7 56, a method for preparing SSZ-56 using a trans-fused ring N,N-diethyl-2-8 methyldecahydroquinolinium cation as a structure directing agent and the use 9 of SSZ-56 in catalysts for, e.g., hydrocarbon conversion reactions.
State of the Art 11 Because of their unique sieving characteristics, as well as their 12 catalytic properties, crystalline molecular sieves and zeolites are especially 13 useful in applications such as hydrocarbon conversion, gas drying and 14 separation. Although many different crystalline molecular sieves have been disclosed, there is a continuing need for new zeolites with desirable properties 16 for gas separation and drying, hydrocarbon and chemical conversions, and 17 other applications. New zeolites may contain novel internal pore 18 architectures, providing enhanced selectivities in these processes.
19 Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and 21 alumina. Crystalline borosilicates are usually prepared under similar reaction 22 conditions except that boron is used in place of aluminum. By varying the 23 synthesis conditions and the composition of the reaction mixture, different 24 zeolites can often be formed.
SUMMARY OF THE INVENTION
26 The present invention is directed to a family of crystalline molecular 27 sieves with unique properties, referred to herein as "molecular sieve SSZ-56"
28 or simply "SSZ-56". Preferably, SSZ-56 is in its silicate, aluminosilicate, 29 titanosilicate, vanadosilicate or borosilicate form. The term "silicate"
refers to a molecular sieve having a high mole ratio of silicon oxide relative to 31 aluminum oxide, preferably a mole ratio greater than 100, including molecular 32 sieves comprised entirely of silicon oxide. As used herein, the term 33 "aluminosilicate" refers to a molecular sieve containing both aluminum oxide 1 and silicon oxide and the term "borosilicate" refers to a molecular sieve 2 containing oxides of both boron and silicon.
3 In accordance with this invention, there is provided a molecular sieve 4 having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second 6 tetravalent element different from said first tetravalent element or mixture 7 thereof and having, after calcination, the X-ray diffraction lines of Table 2.
8 Further, in accordance with this invention, there is provided a molecular 9 sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, 11 titanium oxide, vanadium oxide and mixtures thereof and having, after 12 calcination, the X-ray diffraction lines of Table 2 below. It should be noted 13 that the mole ratio of the first oxide to the second oxide can be infinity, i.e., 14 there is no second oxide in the molecular sieve. In these cases, the molecular sieve is an all-silica molecular sieve.
16 The present invention further provides such a molecular sieve having a 17 composition, as synthesized and in the anhydrous state, in terms of mole 18 ratios as follows:

YO2/W,,Od 15 - infinity 21 M2/n/YO2 0 - 0.03 22 Q/Y02 0.02-0.05 24 wherein Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; c is 1 or 2; d is 2 when c is 1 (i.e., W is 26 tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when 27 W is pentavalent); M is an alkali metal cation, alkaline earth metal cation or 28 mixtures thereof; n is the valence of M (i.e., 1 or 2); and Q is a trans-fused 29 ring N,N-diethyl-2-methyldecahydroquinolinium cation A.
H
Et N_~,Me H Et A

1 In accordance with this invention, there is also provided a 2 molecular sieve prepared by thermally treating a molecular sieve having a 3 mole ratio of silicon oxide to an oxide selected from aluminum oxide, gallium 4 oxide, iron oxide, boron oxide, titanium oxide, vanadium oxide and mixtures thereof greater than about 15 at a temperature of from about 200 C to about 6 800 C, the thus-prepared molecular sieve having the X-ray diffraction lines of 7 Table 2. The present invention also includes this thus-prepared molecular 8 sieve which is predominantly in the hydrogen form, which hydrogen form is 9 prepared by ion exchanging with an acid or with a solution of an ammonium salt followed by a second calcination. If the molecular sieve is synthesized 11 with a high enough ratio of SDA cation to sodium ion, calcination alone may 12 be sufficient. For high catalytic activity, the SSZ-56 molecular sieve should be 13 predominantly in its hydrogen ion form. As used herein, "predominantly in the 14 hydrogen form" means that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions and/or rare earth ions.
16 Also provided in accordance with the present invention is a method of 17 preparing a crystalline material comprising (1) a first oxide comprising silicon 18 oxide and (2) a second oxide comprising boron oxide, aluminum oxide, 19 gallium oxide, iron oxide, titanium oxide, vanadium oxide and mixtures thereof and having a mole ratio of the first oxide to the second oxide greater than 21 about 15, said method comprising contacting under crystallization conditions 22 sources of said oxides and a structure directing agent comprising a trans-23 fused ring N,N-diethyl-2-methyldecahydroquinolinium cation.
24 In accordance with the present invention there,is provided a process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed 26 at hydrocarbon converting conditions with a catalyst comprising the molecular 27 sieve of this invention. The molecular sieve may be predominantly in the 28 hydrogen form. It may also be substantially free of acidity. The invention 29 includes such a process wherein the molecular sieve has a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum 31 oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and 32 mixtures thereof, and has, after calcination, the X-ray diffraction lines of Table 33 2.

1 Further provided by the present invention is a hydrocracking process 2 comprising contacting a hydrocarbon feedstock under hydrocracking 3 conditions with a catalyst comprising the molecular sieve of this invention, 4 preferably predominantly in the hydrogen form.
This invention also includes a dewaxing process comprising contacting 6 a hydrocarbon feedstock under dewaxing conditions with a catalyst 7 comprising the molecular sieve of this invention, preferably predominantly in 8 the hydrogen form.
9 The present invention also includes a process for improving the viscosity index of a dewaxed product of waxy hydrocarbon feeds comprising 11 contacting the waxy hydrocarbon feed under isomerization dewaxing 12 conditions with a catalyst comprising the molecular sieve of this invention, 13 preferably predominantly in the hydrogen form.
14 The present invention further includes a process for producing a C20+
lube oil from a C20+ olefin feed comprising isomerizing said olefin feed under 16 isomerization conditions over a catalyst comprising the molecular sieve of this 17 invention. The molecular sieve may be predominantly in the hydrogen form.
18 The catalyst may contain at least one Group VIII metal.
19 In accordance with this invention, there is also provided a process for catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350 F
21 (177 C) and containing straight chain and slightly branched chain 22 hydrocarbons comprising contacting said hydrocarbon oil feedstock in the 23 presence of added hydrogen gas at a hydrogen pressure of about 15-3000 psi 24 (0.103 - 20.7 MPa) with a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form. The catalyst may 26 contain at least one Group VIII metal. The catalyst may be a layered catalyst 27 comprising a first layer comprising the molecular sieve of this invention, and a 28 second layer comprising an aluminosilicate zeolite which is more shape 29 selective than the molecular sieve of said first layer. The first layer may contain at least one Group VIII metal.
31 Also included in the present invention is a process for preparing a 32 lubricating oil which comprises hydrocracking in a hydrocracking zone a 33 hydrocarbonaceous feedstock to obtain an effluent comprising a 1 hydrocracked oil, and catalytically dewaxing said effluent comprising 2 hydrocracked oil at a temperature of at least about 400 F (204 C) and at a 3 pressure of from about 15 psig to about 3000 psig (0.103 - 20.7 Mpa 4 gauge)in the presence of added hydrogen gas with a catalyst comprising the molecular sieve of this invention. The molecular sieve may be predominantly 6 in the hydrogen form. The catalyst may contain at least one Group VIII
metal.
7 Further included in this invention is a process for isomerization 8 dewaxing a raffinate comprising contacting said raffinate in the presence of 9 added hydrogen with a catalyst comprising the molecular sieve of this invention. The raffinate may be bright stock, and the molecular sieve may be 11 predominantly in the hydrogen form. The catalyst may contain at least one 12 Group VIII metal.
13 Also included in this invention is a process for increasing the octane of 14 a hydrocarbon feedstock to produce a product having an increased aromatics content comprising contacting a hydrocarbonaceous feedstock which 16 comprises normal and slightly branched hydrocarbons having a boiling range 17 above about 40 C and less than about 200 C, under aromatic conversion 18 conditions with a catalyst comprising the molecular sieve of this invention 19 made substantially free of acidity by neutralizing said molecular sieve with a basic metal. Also provided in this invention is such a process wherein the 21 molecular sieve contains a Group VIII metal component.
22 Also provided by the present invention is a catalytic cracking process 23 comprising contacting a hydrocarbon feedstock in a reaction zone under 24 catalytic cracking conditions in the absence of added hydrogen with a catalyst comprising the molecular sieve of this invention, preferably predominantly in 26 the hydrogen form. Also included in this invention is such a catalytic cracking 27 process wherein the catalyst additionally comprises a large pore crystalline 28 cracking component.
29 This invention further provides an isomerization process for isomerizing C4 to C7 hydrocarbons, comprising contacting a feed having normal and 31 slightly branched C4 to C7 hydrocarbons under isomerizing conditions with a 32 catalyst comprising the molecular sieve of this invention, preferably 33 predominantly in the hydrogen form. The molecular sieve may be

5 1 impregnated with at least one Group VIII metal, preferably platinum. The 2 catalyst may be calcined in a steam/air mixture at an elevated temperature 3 after impregnation of the Group VIII metal.
4 Also provided by the present invention is a process for alkylating an aromatic hydrocarbon which comprises contacting under alkylation conditions

6 at least a molar excess of an aromatic hydrocarbon with a C2 to C20 olefin

7 under at least partial liquid phase conditions and in the presence of a catalyst

8 comprising the molecular sieve of this invention, preferably predominantly in

9 the hydrogen form. The olefin may be a C2 to C4 olefin, and the aromatic hydrocarbon and olefin may be present in a molar ratio of about 4:1 to about 11 20:1, respectively. The aromatic hydrocarbon may be selected from the 12 group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, 13 naphthalene derivatives, dimethylnaphthalene or mixtures thereof.
14 Further provided in accordance with this invention is a process for transalkylating an aromatic hydrocarbon which comprises contacting under 16 transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic 17 hydrocarbon under at least partial liquid phase conditions and in the presence 18 of a catalyst comprising the molecular sieve of this invention, preferably 19 predominantly in the hydrogen form. The aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon may be present in a molar ratio of from about 21 1:1 to about 25:1, respectively.
22 The aromatic hydrocarbon may be selected from the group consisting 23 of benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the 24 polyalkyl aromatic hydrocarbon may be a dialkylbenzene.
Further provided by this invention is a process to convert paraffins to 26 aromatics which comprises contacting paraffins under conditions which cause 27 paraffins to convert to aromatics with a catalyst comprising the molecular 28 sieve of this invention, said catalyst comprising gallium, zinc, or a compound 29 of gallium or zinc.
In accordance with this invention there is also provided a process for 31 isomerizing olefins comprising contacting said olefin under conditions which 32 cause isomerization of the olefin with a catalyst comprising the molecular 33 sieve of this invention.

1 Further provided in accordance with this invention is a process for 2 isomerizing an isomerization feed comprising an aromatic C8 stream of xylene 3 isomers or mixtures of xylene isomers and ethylbenzene, wherein a more 4 nearly equilibrium ratio of ortho-, meta- and para-xylenes is obtained, said process comprising contacting said feed under isomerization conditions with a 6 catalyst comprising the molecular sieve of this invention.
7 The present invention further provides a process for oligomerizing 8 olefins comprising contacting an olefin feed under oligomerization conditions 9 with a catalyst comprising the molecular sieve of this invention.
This invention also provides a process for converting oxygenated 11 hydrocarbons comprising contacting said oxygenated hydrocarbon with a 12 catalyst comprising the molecular sieve of this invention under conditions to 13 produce liquid products. The oxygenated hydrocarbon may be a lower 14 alcohol.
Further provided in accordance with the present invention is a process 16 for the production of higher molecular weight hydrocarbons from lower 17 molecular weight hydrocarbons comprising the steps of:
18 (a) introducing into a reaction zone a lower molecular weight 19 hydrocarbon-containing gas and contacting said gas in said zone under C2+ hydrocarbon synthesis conditions with the catalyst and a metal or 21 metal compound capable of converting the lower molecular weight 22 hydrocarbon to a higher molecular weight hydrocarbon; and 23 (b) withdrawing from said reaction zone a higher molecular weight 24 hydrocarbon-containing stream.
Also provided in accordance with this invention is a catalyst 26 composition for promoting polymerization of 1-olefins, said composition 27 comprising 29 (A) a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, 31 pentavalent element, second tetravalent element which is different from said 32 first tetravalent element or mixture thereof and having, after calcination, the 33 X-ray diffraction lines of Table 2; and 2 (B) an organotitanium or organochromium compound.
3 Oxide (1) may be silicon oxide, and oxide (2) may be an oxide selected 4 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide.
6 The present invention further provides a for polymerizing 1-olefins, 7 which process comprises contacting 1-olefin monomer with a catalytically 8 effective amount of a catalyst composition comprising (A) a molecular sieve having a mole ratio greater than about 15 of (1) an 11 oxide of a first tetravalent element to (2) an oxide of a trivalent element, 12 pentavalent element, second tetravalent element which is different from 13 said first tetravalent element or mixture thereof and having, after 14 calcination, the X-ray diffraction lines of Table 2; and 16 (B) an organotitanium or organochromium compound 18 under polymerization conditions which include a temperature and pressure 19 suitable for initiating and promoting the polymerization reaction.
Oxide (1) may be silicon oxide, and oxide (2) may be an oxide selected 21 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, 22 indium oxide.
23 The present invention further provides a process for hydrogenating a 24 hydrocarbon feed containing unsaturated hydrocarbons, the process comprising contacting the feed and hydrogen under conditions which cause 26 hydrogenation with a catalyst comprising the molecular sieve of this invention.
27 The catalyst can also contain metals, salts or complexes wherein the metal is 28 selected from the group consisting of platinum, palladium, rhodium, iridium or 29 combinations thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, rhenium, manganese and 31 combinations thereof.
32 In accordance with this invention, there is also provided a process for 33 hydrotreating a hydrocarbon feedstock comprising contacting the feedstock 1 with a hydrotreating catalyst and hydrogen under hydrotreating conditions, 2 wherein the catalyst comprises the molecular sieve of this invention.
3 In accordance with this invention, there is provided a process for the 4 reduction of oxides of nitrogen contained in a gas stream wherein said process comprises contacting the gas stream with a molecular sieve, the 6 molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a 7 first tetravalent element to (2) an oxide of a trivalent element, pentavalent 8 element, second tetravalent element different from said first tetravalent 9 element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2. There is also provided a process for the reduction of oxides 11 of nitrogen contained in a gas stream wherein said process comprises 12 contacting the gas stream with a molecular sieve, the molecular sieve having 13 a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected 14 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray 16 diffraction lines of Table 2. The molecular sieve may contain a metal or metal 17 ions (such as cobalt, copper, platinum, iron, chromium, manganese, nickel, 18 zinc, lanthanum, palladium, rhodium or mixtures thereof) capable of catalyzing 19 the reduction of the oxides of nitrogen, and the process may be conducted in the presence of a stoichiometric excess of oxygen. In a preferred 21 embodiment, the gas stream is the exhaust stream of an internal combustion 22 engine.
23 The present invention provides a process for treating a cold-start 24 engine exhaust gas stream containing hydrocarbons and other pollutants consisting of flowing said engine exhaust gas stream over a molecular sieve 26 bed which preferentially adsorbs the hydrocarbons over water to provide a 27 first exhaust stream, and flowing the first exhaust gas stream over a catalyst 28 to convert any residual hydrocarbons and other pollutants contained in the 29 first exhaust gas stream to innocuous products and provide a treated exhaust stream and discharging the treated exhaust stream into the atmosphere, the 31 molecular sieve bed characterized in that it comprises a molecular sieve 32 having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent 33 element to (2) an oxide of a trivalent element, pentavalent element, second 34 tetravalent element which is different from said first tetravalent element or 1 mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2 2.
3 Further provided in accordance with this invention is the above process 4 for treatment of cold-start engine exhaust wherein the molecular sieve has a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from 6 aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium 7 oxide and mixtures thereof, and having, after calcination, the X-ray diffraction 8 lines of Table 2. The present invention further provides such a process wherein 9 the engine is an internal combustion engine, including automobile engines, which can be fueled by a hydrocarbonaceous fuel. Also provided by the present 11 invention is such a process wherein the molecular sieve has deposited on it a 12 metal selected from the group consisting of platinum, palladium, rhodium, 13 ruthenium, and mixtures thereof.
14 According to another aspect, there is provided a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to 16 (2) an oxide of a trivalent element, pentavalent element, second tetravalent 17 element which is different from said first tetravalent element or mixture thereof 18 and having, after calcination, the X-ray diffraction lines of Table 2.
19 According to a further aspect, there is provided a molecular sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected 21 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, 22 indium oxide and mixtures thereof, and having, after calcination, the X-ray 23 diffraction lines of Table 2.
24 According to another aspect, there is provided a process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon 26 converting conditions with a catalyst comprising a molecular sieve having a mole 27 ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an 28 oxide of a trivalent element, pentavalent element, second tetravalent element 29 which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.
31 According to a further aspect, there is provided a process for converting 32 oxygenated hydrocarbons comprising contacting said oxygenated hydrocarbon 33 under conditions to produce liquid products with a catalyst comprising a 34 molecular sieve having a mole ratio greater than about 15 of an oxide of a first tetravalent element to an oxide of a second tetravalent element which is different 1 from said first tetravalent element, trivalent element, pentavalent element or 2 mixture thereof and having, after calcination, the X-ray diffraction lines of Table 3 2.
4 According to another aspect, there is provided a catalyst composition for promoting polymerization of 1-olefins, said composition comprising:
6 (A) a molecular sieve having a mole ratio greater than about 15 of (1) an 7 oxide of a first tetravalent element to (2) an oxide of a trivalent element, 8 pentavalent element, second tetravalent element which is different from said first 9 tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2; and 11 (B) an organotitanium or organochromium compound.
12 According to a further aspect, there is provided a process for 13 hydrotreating a hydrocarbon feedstock comprising contacting the feedstock with 14 a hydrotreating catalyst and hydrogen under hydrotreating conditions, wherein the catalyst comprises a molecular sieve having a mole ratio greater than about 16 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent 17 element, pentavalent element, second tetravalent element which is different from 18 said first tetravalent element or mixture thereof and having, after calcination, the 19 X-ray diffraction lines of Table 2.
According to another aspect, there is provided a process for 21 hydrotreating a hydrocarbon feedstock comprising contacting the feedstock with 22 a hydrotreating catalyst and hydrogen under hydrotreating conditions, wherein 23 the catalyst comprises a molecular sieve having a mole ratio greater than about 24 15 of (1) an silicon oxide (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, 26 and having, after calcination, the X-ray diffraction lines of Table 2.
27 According to a further aspect, there is provided a process for converting 28 hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon 29 converting conditions with a catalyst comprising a molecular sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from 31 aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium 32 oxide and mixtures thereof, and having, after calcination, the X-ray diffraction 33 lines of Table 2.
34 According to another aspect, there is provided a process for the reduction of oxides of nitrogen contained in a gas stream wherein said process comprises 10a 1 contacting the gas stream with a molecular sieve, the molecular sieve having a 2 mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to 3 (2) an oxide of a trivalent element, pentavalent element, second tetravalent 4 element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.
6 According to a further aspect, there is provided a process for the 7 reduction of oxides of nitrogen contained in a gas stream wherein said process 8 comprises contacting the gas stream with a molecular sieve, the molecular sieve 9 having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium 11 oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray 12 diffraction lines of Table 2.
13 According to another aspect, there is provided a process for treating a 14 cold-start engine exhaust gas stream containing hydrocarbons and other pollutants consisting of flowing said engine exhaust gas stream over a molecular 16 sieve bed which preferentially adsorbs the hydrocarbons over water to provide a 17 first exhaust stream, and flowing the first exhaust gas stream over a catalyst to 18 convert any residual hydrocarbons and other pollutants contained in the first 19 exhaust gas stream to innocuous products and provide a treated exhaust stream and discharging the treated exhaust stream into the atmosphere, the molecular 21 sieve bed characterized in that it comprises a molecular sieve having a mole 22 ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an 23 oxide of a trivalent element, pentavalent element, second tetravalent element 24 which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.

27 The present invention comprises a family of crystalline molecular sieves 28 designated herein "molecular sieve SSZ-56" or simply "SSZ-56". In preparing 29 SSZ-56, a N,N-diethyl-2-methyldecahydroquinolinium cation (the trans-fused ring isomer) is used as a structure directing agent ("SDA"), also known as a 31 crystallization template. The SDA useful for making SSZ-56 has the following 32 structure:

10b t-'Et N
2 H X Et 3 The SDA cation is associated with an anion (X) which may be any anion 4 that is not detrimental to the formation of the molecular sieve.
Representative anions include halogen, e.g., fluoride, chloride, bromide and 10c 1 iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like.
2 Hydroxide is the most preferred anion.
3 SSZ-56 is prepared from a reaction mixture having the composition 4 shown in Table A below.
TABLE A
6 Reaction Mixture 7 Typical Preferred 8 YO2/WaOb 15 30 - 60 9 OH-1Y02 0.10-0.50 0.20-0.30 Q/Y02 0.05-0.50 0.10-0.30 11 M21/YO2 0-0.40 0.10-0.25 14 where Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; a is 1 or 2, b is 2 when a is 1 (i.e., W is 16 tetravalent); b is 3 when a is 2 (i.e., W is trivalent); M is an alkali metal cation, 17 alkaline earth metal cation or mixtures thereof; n is the valence of M
(i.e., 1 or 18 2); and Q is a trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium 19 cation;.
In practice, SSZ-56 is prepared by a process comprising:
21 (a) preparing an aqueous solution containing sources of 22 oxides capable of forming a crystalline molecular sieve and a trans-fused ring 23 N,N-diethyl-2-methyldecahydroquinolinium cation having an anionic 24 counterion which is not detrimental to the formation of SSZ-56;
(b) maintaining the aqueous solution under conditions 26 sufficient to form crystals of SSZ-56; and 27 (c) recovering the crystals of SSZ-56.
28 Accordingly, SSZ-56 may comprise the crystalline material and the 29 SDA in combination with metallic and non-metallic oxides bonded in tetrahedral coordination through shared oxygen atoms to form a cross-linked 31 three dimensional crystal structure. Typical sources of silicon oxide 32 include silicates, silica hydrogel, silicic acid, fumed silica, colloidal silica, 33 tetra-alkyl orthosilicates, and silica hydroxides. Boron can be added in forms 34 corresponding to its silicon counterpart, such as boric acid.

1 A source zeolite reagent may provide a source of boron. In most 2 cases, the source zeolite also provides a source of silica. The source zeolite 3 in its deboronated form may also be used as a source of silica, with additional 4 silicon added using, for example, the conventional sources listed above. Use of a source zeolite reagent for the present process is more completely 6 described in U.S. Patent No. 5,225,179, issued July 6, 1993 to Nakagawa 7 entitled "Method of Making Molecular Sieves", the disclosure of which is 8 incorporated herein by reference.
9 Typically, an alkali metal hydroxide and/or an alkaline earth metal hydroxide, such as the hydroxide of sodium, potassium, lithium, cesium, 11 rubidium, calcium, and magnesium, is used in the reaction mixture; however, 12 this component can be omitted so long as the equivalent basicity is 13 maintained. The SDA may be used to provide hydroxide ion. Thus, it may be 14 beneficial to ion exchange, for example, the halide to hydroxide ion, thereby reducing or eliminating the alkali metal hydroxide quantity required. The alkali 16 metal cation or alkaline earth cation may be part of the as-synthesized 17 crystalline oxide material, in order to balance valence electron charges 18 therein.
19 The reaction mixture is maintained at an elevated temperature until the crystals of the SSZ-56 are formed. The hydrothermal crystallization is usually 21 conducted under autogenous pressure, at a temperature between 100 C and 22 200 C, preferably between 135 C and 160 C. The crystallization period is 23 typically greater than 1 day and preferably from about 3 days to about 24 20 days.
Preferably, the molecular sieve is prepared using mild stirring or 26 agitation.
27 During the hydrothermal crystallization step, the SSZ-56 crystals can 28 be allowed to nucleate spontaneously from the reaction mixture. The use of 29 SSZ-56 crystals as seed material can be advantageous in decreasing the time necessary for complete crystallization to occur. In addition, seeding can lead 31 to an increased purity of the product obtained by promoting the nucleation 32 and/or formation of SSZ-56 over any undesired phases. When used as 33 seeds, SSZ-56 crystals are added in an amount between 0.1 and 10% of the 1 weight of first tetravalent element oxide, e.g. silica, used in the reaction 2 mixture.
3 Once the molecular sieve crystals have formed, the solid product is 4 separated from the reaction mixture by standard mechanical separation techniques such as filtration. The crystals are water-washed and then dried, 6 e.g., at 900C to 150 C for from 8 to 24 hours, to obtain the as-synthesized 7 SSZ-56 crystals. The drying step can be performed at atmospheric pressure 8 or under vacuum.
9 SSZ-56 as prepared has a mole ratio of silicon oxide to boron oxide greater than about 15; and has, after calcination, the X-ray diffraction lines of 11 Table 2 below. SSZ-56 further has a composition, as synthesized (i.e., prior 12 to removal of the SDA from the SSZ-56) and in the anhydrous state, in terms 13 of mole ratios, shown in Table B below.

As-Synthesized SSZ-56 16 YO2/WcOd 15 - infinity' 17 M21n/YO2 0 - 0.03 18 Q/Y02 0.02-0.05 where Y, W, M, n, and Q are as defined above and c is 1 or 2; d is 2 when c is 21 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W
is 22 trivalent or 5 when W is pentavalent).
23 SSZ-56 can be an all-silica. SSZ-56 is made as a borosilicate and then 24 the boron can be removed, if desired, by treating the borosilicate SSZ-56 with acetic acid at elevated temperature (as described in Jones et al., Chem.
26 Mater., 2001, 13, 1041-1050) to produce an all-silica version of SSZ-56 (i.e., 27 YO2/WcOd is ).
28 If desired, SSZ-56 can be made as a borosilicate and then the boron 29 can be removed as described above and replaced with metal atoms by techniques known in the art. Aluminum, gallium, iron, titanium, vanadium and 31 mixtures thereof can be added in this manner.
32 It is believed that SSZ-56 is comprised of a new framework structure or 33 topology which is characterized by its X-ray diffraction pattern. SSZ-56, 1 as-synthesized, has a crystalline structure whose X-ray powder diffraction 2 pattern exhibit the characteristic lines shown in Table 1 and is thereby 3 distinguished from other molecular sieves.

X-ray data for the as-synthesized Boron-SSZ-56 20(a) d Relative Intensity (b) 6.58 13.43 M
7.43 11.88 M
7.93 11.14 S
8.41 10.51 M
13.22 6.69 M
13.93 5.95 M
14.86 5.95 M
22.59 3.93 VS
23.26 3.82 VS
24.03 3.70 S
6 (a) 0.10 7 (b) The X-ray patterns provided are based on a relative intensity 8 scale in which the strongest line in the X-ray pattern is assigned 9 a value of 100: W(weak) is less than 20; M(medium) is between 20 and 40; S(strong) is between 40 and 60; VS(very strong) is 11 greater than 60.

12 Table 1A below shows the X-ray powder diffraction lines for as-13 synthesized SSZ-56 including actual relative intensities.

As-Synthesized SSZ-56 I/lo x100 20(a) d Relative Intensity 6.58 13.42 36.3 7.43 11.88 25.2 7.93 11.14 58.5 8.41 10.51 30.9 8.84 10.00 18.0 9.5 9.30 4.9 11.04 8.00 11.1 11.29 7.83 4.5 11.56 7.64 12.6 12.15 7.27 18.7 13.22 6.70 34.3 No X100 20(a) d Relative Intensity 13.93 6.35 21.6 14.86 5.96 20.4 15.94 5.56 5.7 17.02 5.20 10.8 17.45 5.07 8.2 17.77 4.99 5.8 18.04 4.91 13.6 18.79 4.72 8.4 19.72 4.50 2.1 19.90 4.46 2.2 20.11 4.41 4.4 20.42 4.35 8.8 21.22 4.18 19.8 21.57 4.12 3.2 22.58 3.93 73.1 23.26 3.82 100.0 24.03 3.70 48.9 25.04 3.55 5.7 25.32 3.51 4.1 25.49 3.49 3.5 25.99 3.42 12.9 26.58 3.35 10.2 26.86 3.32 7.2 28.33 3.15 6.6 28.86 3.09 13.3 29.41, 3.03 3.5 29.68 3.00 5.1 30.07 2.97 9.4 31.07 2.88 2.2 32.08 2.79 5.9 32.82 2.73 2.7 34.13 2.62 4.9 34.97 2.56 3.4 37.49 2.39 2.9 1 (a) 0.10 2 After calcination, the SSZ-56 molecular sieves have a crystalline 3 structure whose X-ray powder diffraction pattern include the characteristic 4 lines shown in Table 2:

6 X-ray data for calcined SSZ-56 20 d Relative Intensity 6.54 13.51 VS
7.36 11.97 VS
7.89 11.20 VS

8.35 10.58 VS
8.81 10.03 S
13.16 6.72 M
14.83 5.96 M
22.48 3.95 VS
23.24 3.82 VS
23.99 3.70 S
1 (a) 0.10 2 Table 2A below shows the X-ray powder diffraction lines for calcined 3 SSZ-56 including actual relative intensities.

Calcined SSZ-56 I/lo 100 20(a) d Relative Intensity 6.54 13.51 70.0 7.38 11.97 69.3 7.89 11.20 85.2 8.35 10.58 68.7 8.81 10.03 43.2 11.23 7.87 14.7 11.52 7.68 5.6 12.09 7.31 9.9 13.16 6.72 23.3 13.89 6.37 11.1 14.42 6.14 9.3 14.83 5.97 38.5 15.89 5.57 8.1 16.95 5.22 6.0 17.41 5.09 5.4 17.75 5.00 6.7 17.96 4.93 6.3 18.75 4.73 7.7 19.05 4.66 3.3 20.00 4.44 7.5 20.36 4.36 5.0 21.15 4.19 16.9 21.55 4.12 4.5 22.48 3.95 63.0 23.24 3.82 100.0 23.99 3.71 44.8 25.15 3.54 4.4 25.41 3.50 2.6 25.96 3.43 15.6 26.51 3.36 10.2 26.83 3.32 6.5 28.19 3.16 10.6 I/lo x 100 20(a) d Relative Intensity 28.80 3.10 15.7 29.28 3.05 2.7 30.02 2.97 11.3 30.98 2.88 3.0 31.99 2.80 5.5 32.72 2.73 4.3 34.04 2.63 5.9 34.42 2.60 2.6 34.70 2.58 4.1 35.34 2.54 2.1 36.05 2.49 2.7 37.41 2.40 2.8 39.76 2.26 1.8 1 (a) 0.10 2 The X-ray powder diffraction patterns were determined by standard 3 techniques. The radiation was the K-alpha/doublet of copper. The peak 4 heights and the positions, as a function of 20 where 0 is the Bragg angle, were read from the relative intensities of the peaks, and d, the interplanar spacing 6 in Angstroms corresponding to the recorded lines, can be calculated.
7 The variation in the scattering angle (two theta) measurements, due to 8 instrument error and to differences between individual samples, is estimated 9 at 0.10 degrees.
The X-ray diffraction pattern of Table 1 is representative of "as-11 synthesized" or "as-made" SSZ-56 molecular sieves. Minor variations in the 12 diffraction pattern can result from variations in the silica-to-boron mole ratio of 13 the particular sample due to changes in lattice constants. In addition, 14 sufficiently small crystals will affect the shape and intensity of peaks, leading to significant peak broadening.
16 Representative peaks from the X-ray diffraction pattern of calcined 17 SSZ-56 are shown in Table 2. Calcination can also result in changes in the 18 intensities of the peaks as compared to patterns of the "as-made" material, as 19 well as minor shifts in the diffraction pattern. The molecular sieve produced by exchanging the metal or other cations present in the molecular sieve with 21 various other cations (such as H+ or NH4') yields essentially the same .22 diffraction pattern, although again, there may be minor shifts in the interplanar 23 spacing and variations in the relative intensities of the peaks.
Notwithstanding 1 these minor perturbations, the basic crystal lattice remains unchanged by 2 these treatments.
3 Crystalline SSZ-56 can be used as-synthesized, but preferably will be 4 thermally treated (calcined). Usually, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any 6 desired metal ion. The molecular sieve can be leached with chelating agents, 7 e.g., EDTA or dilute acid solutions, to increase the silica to alumina mole ratio.
8 The molecular sieve can also be steamed; steaming helps stabilize the 9 crystalline lattice to attack from acids.
The molecular sieve can be used in intimate combination with 11 hydrogenating components, such as tungsten, vanadium, molybdenum, 12 rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as 13 palladium or platinum, for those applications in which a hydrogenation-14 dehydrogenation function is desired.
Metals may also be introduced into the molecular sieve by replacing 16 some of the cations in the molecular sieve with metal cations via standard ion 17 exchange techniques (see, for example, U.S. Patent Nos. 3,140,249 issued 18 July 7, 1964 to Plank et al.; 3,140,251 issued July 7, 1964 to Plank et al.; and 19 3,140,253 issued July 7, 1964 to Plank et al.). Typical replacing cations can include metal cations, e.g., rare earth, Group IA, Group IIA and Group VIII
21 metals, as well as their mixtures. Of the replacing metallic cations, cations of 22 metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and 23 Fe are particularly preferred.
24 The hydrogen, ammonium, and metal components can be ion-exchanged into the SSZ-56. The SSZ-56 can also be impregnated with 26 the metals, or the metals can be physically and intimately admixed with the 27 SSZ-56 using standard methods known to the art.
28 Typical ion-exchange techniques involve contacting the synthetic 29 molecular sieve with a solution containing a salt of the desired replacing cation or cations. Although a wide variety of salts can be employed, chlorides 31 and other halides, acetates, nitrates, and sulfates are particularly preferred.
32 The molecular sieve is usually calcined prior to the ion-exchange procedure to 33 remove the organic matter present in the channels and on the surface, since 34 this results in a more effective ion exchange. Representative ion exchange 1 techniques are disclosed in a wide variety of patents including U.S. Patent 2 Nos. 3,140,249 issued on July 7, 1964 to Plank et al.; 3,140,251 issued on 3 July 7, 1964 to Plank et al.; and 3,140,253 issued on July 7, 1964 to Plank 4 et al.
Following contact with the salt solution of the desired replacing cation, 6 the molecular sieve is typically washed with water and dried at temperatures 7 ranging from 65 C to about 200 C. After washing, the molecular sieve can be 8 calcined in air or inert gas at temperatures ranging from about 200 C to about 9 800 C for periods of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially useful in hydrocarbon conversion 11 processes.
12 Regardless of the cations present in the synthesized form of SSZ-56, 13 the spatial arrangement of the atoms which form the basic crystal lattice of the 14 molecular sieve remains essentially unchanged.
SSZ-56 can be formed into a wide variety of physical shapes.
16 Generally speaking, the molecular sieve can be in the form of a powder, a 17 granule, or a molded product, such as extrudate having a particle size 18 sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 19 400-mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion with an organic binder, the SSZ-56 can be extruded before drying, 21 or, dried or partially dried and then extruded.
22 SSZ-56 can be composited with other materials resistant to the 23 temperatures and other conditions employed in organic conversion 24 processes. Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as 26 clays, silica and metal oxides. Examples of such materials and the manner in 27 which they can be, used are disclosed in U.S. Patent No. 4,910,006, issued 28 May 20, 1990 to Zones et al., and U.S. Patent No. 5,316,753, issued May 31, 29 1994 to Nakagawa..
31 SSZ-56 is useful in catalysts for a variety of hydrocarbon conversion 32 reactions such as hydrocracking, dewaxing, isomerization and the like, for the 1 reduction of oxides of nitrogen in a gas stream, and for treating a cold-start 2 engine exhaust stream.
3 Hydrocarbon Conversion Processes 4 SSZ-56 zeolites are useful in hydrocarbon conversion reactions.
Hydrocarbon conversion reactions are chemical and catalytic processes in 6 which carbon containing compounds are changed to different carbon 7 containing compounds. Examples of hydrocarbon conversion reactions in 8 which SSZ-56 are expected to be useful include hydrocracking, dewaxing, 9 catalytic cracking and olefin and aromatics formation reactions. The catalysts are also expected to be useful in other petroleum refining and hydrocarbon 11 conversion reactions such as isomerizing n-paraffins and naphthenes, 12 polymerizing and oligomerizing olefinic or acetylenic compounds such as 13 isobutylene and butene-1, polymerization of 1-olefins (e.g., ethylene), 14 reforming, isomerizing polyalkyl substituted aromatics (e.g., m-xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, 16 xylenes and higher methylbenzenes and oxidation reactions. Also included 17 are rearrangement reactions to make various naphthalene derivatives, and 18 forming higher molecular weight hydrocarbons from lower molecular weight 19 hydrocarbons (e.g., methane upgrading).
The SSZ-56 catalysts may have high selectivity, and under 21 hydrocarbon conversion conditions can provide a high percentage of desired 22 products relative to total products.
23 For high catalytic activity, the SSZ-56 zeolite should be predominantly 24 in its hydrogen ion form. Generally, the zeolite is converted to its hydrogen form by ammonium exchange followed by calcination. If the zeolite is 26 synthesized with a high enough ratio of SDA cation to sodium ion, calcination 27 alone may be sufficient. It is preferred that, after calcination, at least 80% of 28 the cation sites are occupied by hydrogen ions and/or rare earth ions. As 29 used herein, "predominantly in the hydrogen form" means that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions 31 and/or rare earth ions.
32 SSZ-56 zeolites can be used in processing hydrocarbonaceous 33 feedstocks. Hydrocarbonaceous feedstocks contain carbon compounds and 34 can be from many different sources, such as virgin petroleum fractions, 1 recycle petroleum fractions, shale oil, liquefied coal, tar sand oil, synthetic 2 paraffins from NAO, recycled plastic feedstocks and, in general, can be any 3 carbon containing feedstock susceptible to zeolitic catalytic reactions.
4 Depending on the type of processing the hydrocarbonaceous feed is to undergo, the feed can contain metal or be free of metals, it can also have high 6 or low nitrogen or sulfur impurities. It can be appreciated, however, that in 7 general processing will be more efficient (and the catalyst more active) the 8 lower the metal, nitrogen, and sulfur content of the feedstock.
9 The conversion of hydrocarbonaceous feeds can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed 11 reactors depending on the types of process desired. The formulation of the 12 catalyst particles will vary depending on the conversion process and method 13 of operation.
14 Other reactions which can be performed using the catalyst of this invention containing a metal, e.g., a Group VIII metal such platinum, include 16 hydrogenation-dehydrogenation reactions, denitrogenation and desulfurization 17 reactions.
18 The following table indicates typical reaction conditions which may be 19 employed when using catalysts comprising SSZ-56 in the hydrocarbon conversion reactions of this invention. Preferred conditions are indicated in 21 parentheses.

Process Temp., C Pressure LHSV
Hydrocracking 175-485 0.5-350 bar 0.1-30 Dewaxing 200-475 15-3000 psig, 0.1-20 (250-450) 0.103-20.7 Mpa (0.2-10) gauge (200-3000, 1.38-20.7 Mpa gauge) Aromatics 400-600 atm.-10 bar 0.1-15 formation (480-550) Cat. Cracking 127-885 subatm.-1 0.5-50 (atm.-5 atm.) Oligomerization 232-649 0.1-50 .2,3 0.2-50

10-2324 0.05-205 (27-204)4 (0.1-10)5 Paraffins to 100-700 0-1000 psig 0.5-40 aromatics Condensation of 260-538 0.5-1000 psig, 0.5-50 alcohols 0.00345-6.89 Mpa gauge Isomerization 93-538 50-1000 psig, 1-10 (204-315) 0.345-6.89 Mpa (1-4) gauge Xylene 260-593 0.5-50 atm. 0.1-100 isomerization (315-566)2 (1-5 atm)2 (0.5-50)5 38-3714 1-200 atm.4 0.5-50 2 1 Several hundred atmospheres 3 2 Gas phase reaction 4 3 Hydrocarbon partial pressure 4 Liquid phase reaction 7 Other reaction conditions and parameters are provided below.

1 Uydrocracking 2 Using a catalyst which comprises SSZ-56, preferably predominantly in 3 the hydrogen form, and a hydrogenation promoter, heavy petroleum residual 4 feedstocks, cyclic stocks and other hydrocrackate charge stocks can be hydrocracked using the process conditions and catalyst components 6 disclosed in the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent 7 No. 5,316,753.
8 The hydrocracking catalysts contain an effective amount of at least one 9 hydrogenation component of the type commonly employed in hydrocracking catalysts. The hydrogenation component is generally selected from the group

11 of hydrogenation catalysts consisting of one or more metals of Group VIB
and

12 Group VIII, including the salts, complexes and solutions containing such.
The

13 hydrogenation catalyst is preferably selected from the group of metals, salts

14 and complexes thereof of the group consisting of at least one of platinum, palladium, rhodium, iridium, ruthenium and mixtures thereof or the group 16 consisting of at least one of nickel, molybdenum, cobalt, tungsten, titanium, 17 chromium and mixtures thereof. Reference to the catalytically active metal or 18 metals is intended to encompass such metal or metals in the elemental state 19 or in some form such as an oxide, sulfide, halide, carboxylate and the like.
The hydrogenation catalyst is present in an effective amount to provide the 21 hydrogenation function of the hydrocracking catalyst, and preferably in the 22 range of from 0.05 to 25% by weight.
23 Dewaxing 24 SSZ-56, preferably predominantly in the hydrogen form, can be used to dewax hydrocarbonaceous feeds by selectively removing straight chain 26 paraffins. Typically, the viscosity index of the dewaxed product is improved 27 (compared to the waxy feed) when the waxy feed is contacted with SSZ-56 28 under isomerization dewaxing conditions.
29 The catalytic dewaxing conditions are dependent in large measure on the feed used and upon the desired pour point. Hydrogen is preferably 31 present in the reaction zone during the catalytic dewaxing process. The 32 hydrogen to feed ratio is typically between about 500 and about 33 30,000 SCF/bbl (standard cubic feet per barrel) (0.089 to 5.34 SCM/liter 34 (standard cubic meters/liter)), preferably about 1000 to about 20,000 SCF/bbl 1 (0.178 to 3.56 SCM/liter). Generally, hydrogen will be separated from the 2 product and recycled to the reaction zone. Typical feedstocks include light 3 gas oil, heavy gas oils and reduced crudes boiling above about 350 F
4 (177 C). ' ' A typical dewaxing process is the catalytic dewaxing of a hydrocarbon 6 oil feedstock boiling above about 350 F (177 C) and containing straight chain 7 and slightly branched chain hydrocarbons by contacting the hydrocarbon oil 8 feedstock in the presence of added hydrogen gas at a hydrogen pressure of 9 about 15-3000 psi (0.103-20.7 Mpa) with a catalyst comprising SSZ-56 and at least one Group VIII metal.
11 The SSZ-56 hydrodewaxing catalyst may optionally contain a 12 hydrogenation component of the type commonly employed in dewaxing 13 catalysts. See the aforementioned U.S. Patent No. 4,910,006 and U.S.
14 Patent No. 5,316,753 for examples of these hydrogenation components.
The hydrogenation component is present in an effective amount to 16 provide an effective hydrodewaxing and hydroisomerization catalyst 17 preferably in the range of from about 0.05 to 5% by weight. The catalyst may 18 be run in such a mode to increase isomerization dewaxing at the expense of 19 cracking reactions.
The feed may be hydrocracked, followed by dewaxing. This type of 21 two stage process and typical hydrocracking conditions are described in U.S.
22 Patent No. 4,921,594, issued May 1, 1990 to Miller.

24 SSZ-56 may also be utilized as a dewaxing catalyst in the form of a layered catalyst. That is, the catalyst comprises a first layercomprising 26 zeolite SSZ-56 and at least one Group VIII metal, and a second layer 27 comprising an aluminosilicate zeolite which is more shape selective than 28 zeolite SSZ-56. The use of layered catalysts is disclosed in U.S. Patent 29 No. 5,149,421, issued September 22, 1992 to Miller. The layering may also include a bed of SSZ-56 layered with a non-zeolitic component designed for 31 either hydrocracking or hydrofinishing.

1 SSZ-56 may also be used to dewax raffinates, including bright stock, 2 under conditions such as those disclosed in U. S. Patent No. 4,181,598, issued 3 January 1, 1980 to Gillespie et al.
4 It is often desirable to use mild hydrogenation (sometimes referred to as hydrofinishing) to produce more stable dewaxed products. The hydrofinishing 6 step can be performed either before or after the dewaxing step, and preferably 7 after. Hydrofinishing is typically conducted at temperatures ranging from about 8 190 C to about 340 C at pressures from about 400 psig to about 3000 psig (2.76 9 to 20.7 Mpa gauge) at space velocities (LHSV) between about 0.1 and 20 and a hydrogen recycle rate of about 400 to 1500 SCF/bbl (0.071 to 0.27 SCM/liter).
11 The hydrogenation catalyst employed must be active enough not only to 12 hydrogenate the olefins, diolefins and color bodies which may be present, but 13 also to reduce the aromatic content. Suitable hydrogenation catalyst are 14 disclosed in U. S. Patent No. 4,921,594, issued May 1, 1990 to Miller. The hydrofinishing step is beneficial in preparing an acceptably stable product (e.g., a 16 lubricating oil) since dewaxed products prepared from hydrocracked stocks tend 17 to be unstable to air and light and tend to form sludges spontaneously and 18 quickly.
19 Lube oil may be prepared using SSZ-56. For example, a C20+ lube oil may be made by isomerizing a C20+ olefin feed over a catalyst comprising SSZ-21 56 in the hydrogen form and at least one Group VIII metal. Alternatively, the 22 lubricating oil may be made by hydrocracking in a hydrocracking zone a 23 hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked 24 oil, and catalytically dewaxing the effluent at a temperature of at least about 400 F (204 C) and at a pressure of from about 15 psig to about 3000 psig 26 (0.103-20.7 Mpa gauge) in the presence of added hydrogen gas with a catalyst 27 comprising SSZ-56 in the hydrogen form and at least one Group VIII metal.

28 Aromatics Formation 29 SSZ-56 can be used to convert light straight run naphthas and similar mixtures to highly aromatic mixtures. Thus, normal and slightly branched 1 chained hydrocarbons, preferably having a boiling range above about 40 C
2 and less than about 200 C, can be converted to products having a substantial 3 higher octane aromatics content by contacting the hydrocarbon feed with a 4 catalyst comprising SSZ-56. It is also possible to convert heavier feeds into BTX or naphthalene derivatives of value using a catalyst comprising SSZ-56.
6 The conversion catalyst preferably contains a Group VIII metal 7 compound to have sufficient activity for commercial use. By Group VIII metal 8 compound as used herein is meant the metal itself or a compound thereof.
9 The Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium or tin or a mixture 11 thereof may also be used in conjunction with the Group VIII metal compound 12 and preferably a noble metal compound. The most preferred metal is 13 platinum. The amount of Group VIII metal present in the conversion catalyst 14 should be within the normal range of use in reforming catalysts, from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent.
16 It is critical to the selective production of aromatics in useful quantities 17 that the conversion catalyst be substantially free of acidity, for example, by 18 neutralizing the zeolite with a basic metal, e.g., alkali metal, compound.
19 Methods for rendering the catalyst free of acidity are known in the art.
See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 21 for a description of such methods.
22 The preferred alkali metals are sodium, potassium, rubidium and 23 cesium. The zeolite itself can be substantially free of acidity only at very high 24 silica:alumina mole ratios.
Catalytic Cracking 26 Hydrocarbon cracking stocks can be catalytically cracked in the 27 absence of hydrogen using SSZ-56, preferably predominantly in the hydrogen 28 form.
29 When SSZ-56 is used as a catalytic cracking catalyst in the absence of hydrogen, the catalyst may be employed in conjunction with traditional 31 cracking catalysts, e.g., any aluminosilicate heretofore employed as a 32 component in cracking catalysts. Typically, these are large pore, crystalline 33 aluminosilicates. Examples of these traditional cracking catalysts are 1 disclosed in the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent 2 No 5,316,753. When a traditional cracking catalyst (TC) component is 3 employed, the relative weight ratio of the TC to the SSZ-56 is generally 4 between about 1:10 and about 500:1, desirably between about 1:10 and about 200:1, preferably between about 1:2 and about 50:1, and most 6 preferably is between about 1:1 and about 20:1. The novel zeolite and/or the 7 traditional cracking component may be further ion exchanged with rare earth 8 ions to modify selectivity.
9 The cracking catalysts are typically employed with an inorganic oxide matrix component. See the aforementioned U.S. Patent No. 4,910,006 and 11 U.S. Patent No. 5,316,753 for examples of such matrix components.
12 Isomerization 13 The present catalyst is highly active and highly selective for isomerizing 14 C4 to C7 hydrocarbons. The activity means that the catalyst can operate at relatively low temperature which thermodynamically favors highly branched 16 paraffins. Consequently, the catalyst can produce a high octane product.
17 The high selectivity means that a relatively high liquid yield can be achieved 18 when the catalyst is run at a high octane.
19 The present process comprises contacting the isomerization catalyst, i.e., a catalyst comprising SSZ-56 in the hydrogen form, with a hydrocarbon 21 feed under isomerization conditions. The feed is preferably a light straight run 22 fraction, boiling within the range of 30 F to 250 F (-1 C to 121 C) and 23 preferably from 60 F to 200 F (16 C to 93 C). Preferably, the hydrocarbon 24 feed for the process comprises a substantial amount of C4 to C7 normal and slightly branched low octane hydrocarbons, more preferably C5 and C6 26 hydrocarbons.
27 It is preferable to carry out the isomerization reaction in the presence of 28 hydrogen. Preferably, hydrogen is added to give a hydrogen to hydrocarbon 29 ratio (H2/HC) of between 0.5 and 10 H2/HC, more preferably between 1 and 8 H2/HC. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent 31 No. 5,316,753 for a further discussion of isomerization process conditions.
32 A low sulfur feed is especially preferred in the present process. The 33 feed preferably contains less than 10 ppm, more preferably less than 1 ppm, 34 and most preferably less than 0.1 ppm sulfur. In the case of a feed which is 1 not already low in sulfur, acceptable levels can be reached by hydrogenating 2 the feed in a presaturation zone with a hydrogenating catalyst which is 3 resistant to sulfur poisoning. See the aforementioned U.S. Patent 4 No. 4,910,006 and U.S. Patent No. 5,316,753 for a further discussion of this hydrodesulfurization process.
6 It is preferable to limit the nitrogen level and the water content of the 7 feed. Catalysts and processes which are suitable for these purposes are 8 known to those skilled in the art.
9 After a period of operation, the catalyst can become deactivated by sulfur or coke. See the aforementioned U.S. Patent No. 4,910,006 and U.S.
11 Patent No. 5,316,753 for a further discussion of methods of removing this 12 sulfur and coke, and of regenerating the catalyst.
13 The conversion catalyst preferably contains a Group VIII metal 14 compound to have sufficient activity for commercial use. By Group VIII
metal compound as used herein is meant the metal itself or a compound thereof.
16 The Group VIII noble metals and their compounds, platinum, palladium, and 17 iridium, or combinations thereof can be used. Rhenium and tin may also be 18 used in conjunction with the noble metal. The most preferred metal is 19 platinum. The amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in isomerizing catalysts, from about 21 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent.
22 Alkylation and Transalkylation 23 SSZ-56 can be used in a process for the alkylation or transalkylation of 24 an aromatic hydrocarbon. The process comprises contacting the aromatic hydrocarbon with a C2 to C16 olefin alkylating agent or a polyalkyl aromatic 26 hydrocarbon transalkylating agent, under at least partial liquid phase 27 conditions, and in the presence of a catalyst comprising SSZ-56..
28 SSZ-56 can also be used for removing benzene from gasoline by 29 alkylating the benzene as described above and removing the alkylated product from the gasoline.
31 For high catalytic activity, the SSZ-56 zeolite should be predominantly 32 in its hydrogen ion form. It is preferred that, after calcination, at least 80% of 33 the cation sites are occupied by hydrogen ions and/or rare earth ions.

1 Examples of suitable aromatic hydrocarbon feedstocks which may be 2 alkylated or transalkylated by the process of the invention include aromatic 3 compounds such as benzene, toluene and xylene. The preferred aromatic 4 hydrocarbon is benzene. There may be occasions where naphthalene or naphthalene derivatives such as dimethylnaphthalene may be desirable.
6 Mixtures of aromatic hydrocarbons may also be employed.
7 Suitable olefins for the alkylation of the aromatic hydrocarbon are those 8 containing 2 to 20, preferably 2 to 4, carbon atoms, such as ethylene, 9 propylene, butene-1, trans-butene-2 and cis-butene-2, or mixtures thereof.
There may be instances where pentenes are desirable. The preferred olefins 11 are ethylene and propylene. Longer chain alpha olefins may be used as well.
12 When transalkylation is desired, the transalkylating agent is a polyalkyl 13 aromatic hydrocarbon containing two or more alkyl groups that each may 14 have from 2 to about 4 carbon atoms. For example, suitable polyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkyl aromatic hydrocarbons, 16 such as diethylbenzene, triethylbenzene, diethylmethylbenzene 17 (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene, dibutylbenzene, 18 and the like. Preferred polyalkyl aromatic hydrocarbons are the dialkyl 19 benzenes. A particularly preferred polyalkyl aromatic hydrocarbon is di-isopropylbenzene.
21 When alkylation is the process conducted, reaction conditions are as 22 follows. The aromatic hydrocarbon feed should be present in stoichiometric 23 excess. It is preferred that molar ratio of aromatics to olefins be greater than 24 four-to-one to prevent rapid catalyst fouling. The reaction temperature may range from 100 F to 600 F (38 C to 315 C), preferably 250 F to 450 F (121 C
26 to 232 C). The reaction pressure should be sufficient to maintain at least a 27 partial liquid phase in order to retard catalyst fouling. This is typically 50 psig 28 to 1000 psig (0.345 to 6.89 Mpa gauge) depending on the feedstock and 29 reaction temperature. Contact time may range from 10 seconds to 10 hours, but is usually from 5 minutes to an hour. The weight hourly space velocity 31 (WHSV), in terms of grams (pounds) of aromatic hydrocarbon and olefin per 32 gram (pound) of catalyst per hour, is generally within the range of about 0.5 to 33 50.

1 When transalkylation is the process conducted, the molar ratio of 2 aromatic hydrocarbon will generally range from about 1:1 to 25:1, and 3 preferably from about 2:1 to 20:1. The reaction temperature may range from 4 about 100 F to 600 F (38 C to 315 C), but it is preferably about 250 F to 450 F (121 C to 232 C). The reaction pressure should be sufficient to 6 maintain at least a partial liquid phase, typically in the range of about 50 psig 7 to 1000 psig (0.345 to 6.89 Mpa gauge), preferably 300 psig to 600 psig (2.07 8 to 4.14 Mpa gauge). The weight hourly space velocity will range from about 9 0.1 to 10. U.S. Patent No. 5,082,990 issued on January 21, 1992 to Hsieh, et al. describes such processes and is incorporated herein by reference.
11 Conversion of Paraffins to Aromatics 12 SSZ-56 can be used to convert light gas C2-C6 paraffins to higher 13 molecular weight hydrocarbons including aromatic compounds. Preferably, 14 the zeolite will contain a catalyst metal or metal oxide wherein said metal is selected from the group consisting of Groups IB, IIB, VIII and IIIA of the 16 Periodic Table. Preferably, the metal is gallium, niobium, indium or zinc in the 17 range of from about 0.05 to 5% by weight.
18 Isomerization of Olefins 19 SSZ-56 can be used to isomerize olefins. The feed stream is a hydrocarbon stream containing at least one C4_6 olefin, preferably a C4_6 21 normal olefin, more preferably normal butene. Normal butene as used in this 22 specification means all forms of normal butene, e.g., 1-butene, cis-2-butene, 23 and trans-2-butene. Typically, hydrocarbons other than normal butene or 24 other C4_6 normal olefins will be present in the feed stream. These other hydrocarbons may include, e.g., alkanes, other olefins, aromatics, hydrogen, 26 and inert gases.
27 The feed stream typically may be the effluent from a fluid catalytic 28 cracking unit or a methyl-tert-butyl ether unit. A fluid catalytic cracking unit 29 effluent typically contains about 40-60 weight percent normal butenes. A
methyl-tert-butyl ether unit effluent typically contains 40-100 weight percent 31 normal butene. The feed stream preferably contains at least about. 40 weight 32 percent normal butene, more preferably at least about 65 weight percent 33 normal butene. The terms iso-olefin and methyl branched iso-olefin may be 34 used interchangeably in this specification.

1 The process is carried out under isomerization conditions. The 2 hydrocarbon feed is contacted in a vapor phase with a catalyst comprising the 3 SSZ-56. The process may be carried out generally at a temperature from 4 about 625 F to about 950 F (329-510 C), for butenes, preferably from about 700 F to about 900 F (371-482 C), and about 350 F to about 650 F (177-6 343 C) for pentenes and hexenes. The pressure ranges from 7 subatmospheric to about 200 psig (1.38 Mpa gauge), preferably from about 8 15 psig to about 200 psig (0.103 to 1.38 Mpa gauge), and more preferably 9 from about 1 psig to about 150 psig (0.00689 to 1.03 Mpa gauge).
The liquid hourly space velocity during contacting is generally from 11 about 0.1 to about 50 hr 1, based on the hydrocarbon feed, preferably from 12 about 0.1 to about 20 hr 1, more preferably from about 0.2 to about 10 hr', 13 most preferably from about 1 to about 5 hrs. A hydrogen/hydrocarbon molar 14 ratio is maintained from about 0 to about 30 or higher. The hydrogen can be added directly to the feed stream or directly to the isomerization zone. The 16 reaction is preferably substantially free of water, typically less than about two 17 weight percent based on the feed. The process can be carried out in a 18 packed bed reactor, a fixed bed, fluidized bed reactor, or a moving bed 19 reactor. The bed of the catalyst can move upward or downward. The mole percent conversion of, e.g., normal butene to iso-butene is at least 10, 21 preferably at least 25, and more preferably at least 35.
22 Xylene Isomerization 23 SSZ-56 may also be useful in a process for isomerizing one or more 24 xylene isomers in a C8 aromatic feed to obtain ortho-, meta-, and para-xylene in a ratio approaching the equilibrium value. In particular, xylene 26 isomerization is used in conjunction with a separate process to manufacture 27 para-xylene. For example, a portion of the para-xylene in a mixed C8 28 aromatics stream may be recovered by crystallization and centrifugation.
The 29 mother liquor from the crystallizer is then reacted under xylene isomerization conditions to restore ortho-, meta- and para-xylenes to a near equilibrium 31 ratio. At the same time, part of the ethylbenzene in the mother liquor is 32 converted to xylenes or to products which are easily separated by filtration.
33 The isomerate is blended with fresh feed and the combined stream is distilled 1 to remove heavy and light by-products. The resultant C8 aromatics stream is 2 then sent to the crystallizer to repeat the cycle.
3 Optionally, isomerization in the vapor phase is conducted in the 4 presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (e.g., ethylbenzene). If hydrogen is used, the catalyst should comprise about 0.1 to 6 2.0 wt.% of a hydrogenation/dehydrogenation component selected from 7 Group VIII (of the Periodic Table) metal component, especially platinum or 8 nickel. By Group VIII metal component is meant the metals and their 9 compounds such as oxides and sulfides.
Optionally, the isomerization feed may contain 10 to 90 wt. of a diluent 11 such as toluene, trimethylbenzene, naphthenes or paraffins.
12 Oligomerization 13 It is expected that SSZ-56 can also be used to oligomerize straight and 14 branched chain olefins having from about 2 to 21 and preferably 2-5 carbon atoms. The oligomers which are the products of the process are medium to 16 heavy olefins which are useful for both fuels, i.e., gasoline or a gasoline 17 blending stock and chemicals.
18 The oligomerization process comprises contacting the olefin feedstock 19 in the gaseous or liquid phase with a catalyst comprising SSZ-56.
The zeolite can have the original cations associated therewith replaced 21 by a wide variety of other cations according to techniques well known in the 22 art. Typical cations would include hydrogen, ammonium and metal cations 23 including mixtures of the same. Of the replacing metallic cations, particular 24 preference is given to cations of metals such as rare earth metals, manganese, calcium, as well as metals of Group II of the Periodic Table, e.g., 26 zinc, and Group VIII of the Periodic Table, e.g., nickel. One of the prime 27 requisites is that the zeolite have a fairly low aromatization activity, i.e., in 28 which the amount of aromatics produced is not more than about 20% by 29 weight. This is accomplished by using a zeolite with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably from about 0.1 to 31 about 100, as measured by its ability to crack n-hexane.
32 Alpha values are defined by a standard test known in the art, e.g., as 33 shown in U.S. Patent No. 3,960,978 issued on,June 1, 1976 to Givens et al.
34 If required, such zeolites 1 may be obtained by steaming, by use in a conversion process or by any other 2 method which may occur to one skilled in this art.
3 Condensation of Alcohols 4 SSZ-56 can be used to condense lower aliphatic alcohols having 1 to 10 carbon atoms to a gasoline boiling point hydrocarbon product comprising 6 mixed aliphatic and aromatic hydrocarbon. The process disclosed in U.S.
7 Patent No. 3,894,107, issued July 8, 1975 to Butter et al., describes the 8 process conditions used in this process, The catalyst may be in the hydrogen form or may be base exchanged 11 or impregnated to contain ammonium or a metal cation complement, 12 preferably in the range of from about 0.05 to 5% by weight. The metal cations 13 that may be present include any of the metals of the Groups I through VIII
of 14 the Periodic Table. However, in the case of Group IA metals, the cation content should in no case be so large as to effectively inactivate the catalyst, 16 nor should the exchange be such as to eliminate all acidity. There may be 17 other processes involving treatment of oxygenated substrates where a basic 18 catalyst is desired.
19 Methane Upgrading Higher molecular weight hydrocarbons can be formed from lower 21 molecular weight hydrocarbons by contacting the lower molecular weight 22 hydrocarbon with a catalyst comprising SSZ-56 and a metal or metal 23 compound capable of converting the lower molecular weight hydrocarbon to a 24 higher molecular weight hydrocarbon. Examples of such reactions include the conversion of methane to C2+ hydrocarbons such as ethylene or benzene or 26 both. Examples of useful metals and metal compounds include lanthanide 27 and or actinide metals or metal compounds.
28 These reactions, the metals or metal compounds employed and the 29 conditions under which they can be run are disclosed in U.S. Patents No.
4,734,537, issued March 29, 1988 to Devries et al.; 4,939,311, issued July 3, 31 1990 to Washecheck et al.; 4,962,261, issued October 9, 1990 to Abrevaya et 32 al.; 5,095,161, issued March 10, 1992 to Abrevaya et al.; 5,105,044, issued 33 April 14, 1992 to Han et al.; 5,105,046, issued April 14, 1992 to Washecheck;
34 5,238,898, issued August 24, 1993 to Han et al.; 5,321,185, issued June 14, 1 1994 to van der Vaart; and 5,336,825, issued August 9, 1994 to Choudhary et 2 al.
3 Polymerization of 1-Olefins 4 The molecular sieve of the present invention may be used in a catalyst for the polymerization of 1-olefins, e.g., the polymerization of ethylene. To 6 form the olefin polymerization catalyst, the molecular sieve as hereinbefore 7 described is reacted with a particular type of organometallic compound.
8 Organometallic compounds useful in forming the polymerization catalyst 9 include trivalent and tetravalent organotitanium and organochromium compounds having alkyl moieties and, optionally, halo moieties. In the 11 context of the present invention the term "alkyl" includes both straight and 12 branched chain alkyl, cycloalkyl and alkaryl groups such as benzyl.
13 Examples of trivalent and tetravalent organochromium and 14 organotitanium compounds are disclosed in U. S. Patent No. 4,376,722, issued March 15, 1983 to Chester et al., U. S. Patent No. 4,377,497, issued 16 March 22, 1983 to Chester et al., U. S. Patent No. 4,446,243, issued May 1, 17 1984 to Chester et al., and U. S. Patent No. 4,526,942, issued July 2, 1985 to 18 Chester et al.

Examples of the organometallic compounds used to form the 21 polymerization catalyst include, but are not limited to, compounds 22 corresponding to the general formula:

24 MYnXm_n 26 wherein M is a metal selected from titanium and chromium; Y is alkyl; X is 27 halogen (e.g., Cl or Br); n is 1-4; and m is greater than or equal to n and is 3 28 or 4.
29 Examples of organotitanium and organochromium compounds encompassed by such a formula include compounds of the formula CrY4, 31 CrY3, CrY3X, CrY2X, CrY2X2, CrYX2, CrYX3, TiY4, TiY3, TiY3X, TiY2X, TiY2X2, 32 TiYX2, TiYX3, wherein X can be CI or Br and Y can be methyl, ethyl, propyl, 33 isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 34 hexyl, isohexyl, neohexyl, 2-ethybutyl, octyl, 2-ethyihexyl, 2,2-diethylbutyl, 2-1 isopropyl-3-methylbutyl, etc., cyclohexylalkyls such as, for example, 2 cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclyhexjrlpropyl, 4-cyclohexylbutyl, 3 and the corresponding alkyl-substituted cyclohexyl radicals as, for example, 4 (4-m ethylcyclohexyl)methyl, neophyl, i.e., beta, beta-dimethyl-phenethyl, benzyl, ethylbenzyl, and p-isopropylbenzyl. Preferred examples of Y include 6 C1_5 alkyl, especially butyl.
7 The organotitanium and organochromium materials employed in the 8 catalyst can be prepared by techniques well known in the art. See, for 9 example the aforementioned Chester et al. patents.
The organotitanium or organochromium compounds can be with the 11 molecular sieve of the present invention, such as by reacting the 12 organometallic compound and the molecular sieve, in order to form the olefin 13 polymerization catalyst. Generally, such a reaction takes place in the same 14 reaction medium used to prepare the organometallic compound under conditions which promote formation of such a reaction product. The 16 molecular sieve can simply be added to the reaction mixture after formation of 17 the organometallic compound has been completed. Molecular sieve is added 18 in an amount sufficient to provide from about 0.1 to 10 parts by weight, 19 preferably from about 0.5 to 5 parts by weight, of organometallic compound in the reaction medium per 100 parts by weight of molecular sieve.
21 Temperature of the reaction medium during reaction of organometallic 22 compound with molecular sieve is also maintained at a level which is low 23 enough to ensure the stability of the organometallic reactant. Thus, 24 temperatures in the range of from-about -150 C. to 50 C., preferably from about -80 C. to 0 C. can be usefully employed. Reaction times of from 26 about 0.01 to 10 hours, more preferably from about 0.1 to 1 hour, can be 27 employed in reacting the organotitanium or organochromium compound with 28 the molecular sieve.
29 Upon completion of the reaction, the catalyst material so formed may be recovered and dried by evaporating the reaction medium solvent under a 31 nitrogen atmosphere. Alternatively, olefin polymerization reactions can be 32 conducted in this same solvent based reaction medium used to form the 33 catalyst.
34 The polymerization catalyst can be used to catalyze polymerization of 1 1-olefins. The polymers produced using the catalysts of this invention are 2 normally solid polymers of at least one mono-1-olefin containing from 2 to 8 3 carbon atoms per molecule. These polymers are normally solid 4 homopolymers of ethylene or copolymers of ethylene with another mono-1-olefin containing 3 to 8 carbon atoms per molecule. Exemplary copolymers 6 include those of ethylene/propylene, ethylene/1-butene, ethylene/1-hexane, 7 and ethylene/1-octene and the like. The major portion of such copolymers is 8 derived from ethylene and generally consists of about 80-99, preferably 95-9 mole percent of ethylene. These polymers are well suited for extrusion, blow molding, injection molding and the like.
11 The polymerization reaction can be conducted by contacting monomer 12 or monomers, e.g., ethylene, alone or with one or more other olefins, and in 13 the substantial absence of catalyst poisons such as moisture and air, with a 14 catalytic amount of the supported organometallic catalyst at a temperature and at a pressure sufficient to initiate the polymerization reaction. If desired, 16 an inert organic solvent may be used as a diluent and to facilitate materials 17 handling if the polymerization reaction is conducted with the reactants in the 18 liquid phase, e.g. in a particle form (slurry) or solution process. The reaction 19 may also be conducted with reactants in the vapor phase, e.g., in a fluidized bed arrangement in the absence of a solvent but, if desired, in the presence of 21 an inert gas such as nitrogen.
22 The polymerization reaction is carried out at temperatures of from 23 about 30 C. or less, up to about 200 C. or more, depending to a great extent 24 on the operating pressure, the pressure of the olefin monomers, and the particular catalyst being used and its concentration. Naturally, the selected 26 operating temperature is also dependent upon the desired polymer melt index 27 since temperature is definitely a factor in adjusting the molecular weight of the 28 polymer. Preferably, the temperature used is from about 30 C. to about 100 29 C. in a conventional slurry or "particle forming" process or from 100 C.
to 150 C. in a "solution forming" process. A temperature of from about 70 C to 31 110 C. can be employed for fluidized bed processes.
32 The pressure to be used in the polymerization reactions can be any 33 pressure sufficient to initiate the polymerization of the monomer(s) to high 34 molecular weight polymer. The pressure, therefore, can range from 1 subatmospheric pressures, using an inert gas as diluent, to superatmospheric 2 pressures of up to about 30,000 psig or more. The preferred pressure is from 3 atmospheric (0 psig) up to about 1000 psig. As a general rule, a pressure of 4 20 to 800 psig is most preferred.
The selection of an inert organic solvent medium to be employed in the 6 solution or slurry process embodiments of this invention is not too critical, but 7 the solvent should be inert to the supported organometallic catalyst and olefin 8 polymer produced, and be stable at the reaction temperature used. It is not 9 necessary, however, that the inert organic solvent medium also serve as a solvent for the polymer to be produced. Among the inert organic solvents 11 applicable for such purposes may be mentioned saturated aliphatic 12 hydrocarbons having from about 3 to 12 carbon atoms per molecule such as 13 hexane, heptane, pentane, isooctane, purified kerosene and the like, 14 saturated cycloaliphatic hydrocarbons having from about 5 to 12 carbon atoms per molecule such as cyclohexane, cyclopentane, 16 dimethylcyclopentane and methylcyclohexane and the like and aromatic 17 hydrocarbons having from about 6 to 12 carbon atoms per molecule such as 18 benzene, toluene, xylene, and the like. Particularly preferred solvent media 19 are cyclohexane, pentane, hexane and heptane.
Hydrogen can be introduced into the polymerization reaction zone in 21 order to decrease the molecular weight of the polymers produced (i.e., give a 22 much higher Melt Index, MI). Partial pressure of hydrogen when hydrogen is 23 used can be within the range of 5 to 100 psig, preferably-25 to 75 psig.
The 24 melt indices of the polymers produced in accordance with the instant invention can range from about 0.1 to about 70 or even higher.
26 More detailed description of suitable polymerization conditions 27 including examples of particle form, solution and fluidized bed polymerization 28 arrangements are found in Karapinka; U.S. Pat. No. 3,709,853; Issued Jan.
9, 29 1973 and Karol et al; U.S. Pat. No. 4,086,408; Issued Apr. 25, 1978.
31 Hydrotreating 32 SSZ-56 is useful in a hydrotreating catalyst. During hydrotreatment, 33 oxygen, sulfur and nitrogen present in the hydrocarbonaceous feed is reduced 34 to low levels. Aromatics and olefins, if present in the feed, may also have 1 their double bonds saturated. In some cases, the hydrotreating catalyst and 2 hydrotreating conditions are selected to minimize cracking reactions, which can 3 reduce the yield of the most desulfided product (typically useful as a fuel).
4 Hydrotreating conditions typically include a reaction temperature between 900 F (204-482CC), preferably 650-850 F (343-454CC); a pressure between 500 6 and 5000 psig (3.5-34.6 Mpa), preferably 1000 to 3000 psig (7.0-20.8 MPa); a 7 feed rate (LHSV) of 0.5 hr' to 20 hr' (v/v); and overall hydrogen consumption 8 300 to 2000 scf per barrel of liquid hydrocarbon feed (53.4-356 m3 H2/m3 feed).
9 The hydrotreating catalyst will typically be a composite of a Group VI metal or compound thereof, and a Group VIII metal or compound thereof supported on 11 the molecular sieve of this invention. Typically, such hydrotreating catalyst are 12 presulfided.
13 Catalysts useful for hydrotreating hydrocarbon feeds are disclosed in 14 U.S. Patent Nos. 4,347,121, issued August 31, 1982 to Mayer et al, and 4,810,357, issued March 7, 1989 to Chester et al. Suitable catalysts include 16 noble metals from Group VIII, such as Fe, Co, Ni, Pt or Pd, and/or Group VI
17 metals, such as Cr, Mo, Sn or W. Examples of combinations of Group VIII and 18 Group VI metals include Ni-Mo or Ni-Sn. Other suitable catalysts are described 19 in U.S. Patent Nos. 4,157,294, issued June 5, 1979 to Iwao et al, and 3,904,513, issued September 9, 1975 to Fischer et al. U. S. Patent No. 3,852,207, issued 21 December 3, 1974 to Strangeland et al, describes suitable noble metal catalysts 22 and mild hydrotreating conditions.
23 The amount of hydrogenation component(s) in the catalyst suitably range 24 from about 0.5% to about 10% by weight of Group VIII component(s) and from 5% to about 25% by weight of Group VI metal component(s), calculated as metal 26 oxide(s) per 100 parts by weight of total catalyst., where the percentages by 27 weight are based on the weight of the catalyst before sulfiding. The 28 hydrogenation component(s) in the catalyst may be in the oxidic and/or sulfidic 29 form.
Hydrogenation 31 SSZ-56 can be used in a catalyst to catalyze hydrogenation of a 32 hydrocarbon feed containing unsaturated hydrocarbons. The unsaturated 1 hydrocarbons can comprise olefins, dienes, polyenes, aromatic compounds 2 and the like.
3 Hydrogenation is accomplished by contacting the hydrocarbon feed 4 containing unsaturated hydrocarbons with hydrogen in the presence of a catalyst comprising SSZ-56. The catalyst can also contain one or more 6 metals of Group VIB and Group VIII, including salts, complexes and solutions 7 thereof. Reference to these catalytically active metals is intended to 8 encompass such metals or metals in the elemental state or in some form such 9 as an oxide, sulfide, halide, carboxylate and the like. Examples of such metals include metals, salts or complexes wherein the metal is selected from 11 the group consisting of platinum, palladium, rhodium, iridium or combinations 12 thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, 13 titanium, chromium, vanadium, rhenium, manganese and combinations 14 thereof.
The hydrogenation component of the catalyst (i.e., the aforementioned 16 metal) is present in an amount effective to provide the hydrogenation function 17 of the catalyst, preferably in the range of from 0.05 to 25% by weight.
18 Hydrogenation conditions, such as temperature, pressure, space 19 velocities, contact time and the like are well known in the art.
21 Reduction of Oxides of Nitrogen ~n a Gas Stream 23 SSZ-56 may be used for the catalytic reduction of the oxides of 24 nitrogen in a gas stream. Typically, the gas stream also contains oxygen, often a stoichiometric excess thereof. Also, the SSZ-56 may contain a metal 26 or metal ions within or on it which are capable of catalyzing the reduction of 27 the nitrogen oxides. Examples of such metals or metal ions include cobalt, 28 copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, 29 palladium, rhodium and mixtures thereof.
One example of such a process for the catalytic reduction of oxides of 31 nitrogen in the presence of a zeolite is disclosed in U.S. Patent No..4,297,328, 32 issued October 27, 1981 to Ritscher et al. There, the catalytic process 33 is the combustion of carbon monoxide and hydrocarbons and the catalytic 34 reduction of the oxides of nitrogen 1 contained in a gas stream, such as the exhaust gas from an internal 2 combustion engine. The zeolite used is metal ion-exchanged, doped or 3 loaded sufficiently so as to provide an effective amount of catalytic copper 4 metal or copper ions within or on the zeolite. In addition, the process is conducted in an excess of oxidant, e.g., oxygen.

7 Cold-Start Emmissions 9 Gaseous waste products resulting from the combustion of hydrocarbonaceous fuels, such as gasoline and fuel oils, comprise carbon 11 monoxide, hydrocarbons and nitrogen oxides as products of combustion or 12 incomplete combustion, and pose a serious health problem with respect to 13 pollution of the atmosphere. While exhaust gases from other carbonaceous 14 fuel-burning sources, such as stationary engines, industrial furnaces, etc., contribute substantially to air pollution, the exhaust gases from automotive 16 engines are a principal source of pollution. Because of these health problem 17 concerns, the Environmental Protection Agency (EPA) has promulgated strict 18 controls on the amounts of carbon monoxide, hydrocarbons and nitrogen 19 oxides which automobiles can emit. The implementation of these controls has resulted in the use of catalytic converters to reduce the amount of pollutants 21 emitted from automobiles.
22 In order to achieve the simultaneous conversion of carbon monoxide, 23 hydrocarbon and nitrogen oxide pollutants, it has become the practice to 24 employ catalysts in conjunction with air-to-fuel ratio control means which functions in response to a feedback signal from an oxygen sensor in the 26 engine exhaust system. Although these three component control catalysts 27 work quite well after they have reached operating temperature of about 300 28 C., at lower temperatures they are not able to convert substantial amounts of 29 the pollutants. What this means is that when an engine and in particular an automobile engine is started up, the three component control catalyst is not 31 able to convert the hydrocarbons and other pollutants to innocuous 32 compounds.
33 Adsorbent beds have been used to adsorb the hydrocarbons during the 34 cold start portion of the engine. Although the process typically will be used 1 with hydrocarbon fuels, the instant invention can also be used to treat exhaust 2 streams from alcohol fueled engines. The adsorbent bed is typically placed 3 immediately before the catalyst. Thus, the exhaust stream is first flowed 4 through the adsorbent bed and then through the catalyst. The adsorbent bed preferentially adsorbs hydrocarbons over water under the conditions present 6 in the exhaust stream. After a certain amount of time, the adsorbent bed has 7 reached a temperature (typically about 150 C.) at which the bed is no longer 8 able to remove hydrocarbons from the exhaust stream. That is, hydrocarbons 9 are actually desorbed from the adsorbent bed instead of being adsorbed. This regenerates the adsorbent bed so that it can adsorb hydrocarbons during a 11 subsequent cold start.
12 The prior art reveals several references dealing with the use of 13 adsorbent beds to minimize hydrocarbon emissions during a cold start engine 14 operation. One such reference is U.S. Pat. No. 3,699,683 in which an adsorbent bed is placed after both a reducing catalyst and an oxidizing 16 catalyst. The patentees disclose that when the exhaust gas stream is below 17 200 C. the gas stream is flowed through the reducing catalyst then through 18 the oxidizing catalyst and finally through the adsorbent bed, thereby adsorbing 19 hydrocarbons on the adsorbent bed. When the temperature goes above 200 C. the gas stream which is discharged from the oxidation catalyst is divided 21 into a major and minor portion, the major portion being discharged directly into 22 the atmosphere and the minor portion passing through the adsorbent bed 23 whereby unburned hydrocarbon is desorbed and then flowing the resulting 24 minor portion of this exhaust stream containing the desorbed unburned hydrocarbons into the engine where they are burned.
26 Another reference is U.S. Pat. No. 2,942,932 which teaches a process 27 for oxidizing carbon monoxide and hydrocarbons which are contained in 28 exhaust gas streams. The process disclosed in this patent consists of flowing 29 an exhaust stream which is below 800 F. into an adsorption zone which adsorbs the carbon monoxide and hydrocarbons and then passing the 31 resultant stream from this adsorption zone into an oxidation zone. When the 32 temperature of the exhaust gas stream reaches about 800 F. the exhaust 33 stream is no longer passed through the adsorption zone but is passed directly 34 to the oxidation zone with the addition of excess air.

1- U. S. Patent No. 5,078,979, issued January 7, 1992 to Dunne, discloses 2 treating an exhaust gas stream from an engine to prevent cold start emissions 3 using a molecular sieve adsorbent bed. Examples of the molecular sieve include 4 faujasites, clinoptilolites, mordenites, chabazite, silicalite, zeolite Y, ultrastable zeolite Y, and ZSM-5.
6 Canadian Patent No. 1,205,980 discloses a method of reducing exhaust 7 emissions from an alcohol fueled automotive vehicle. This method consists of 8 directing the cool engine startup exhaust gas through a bed of zeolite particles 9 and then over an oxidation catalyst and then the gas is discharged to the atmosphere. As the exhaust gas stream warms up it is continuously passed over 11 the adsorption bed and then over the oxidation bed.
12 As stated this invention generally relates to a process for treating an 13 engine exhaust stream and in particular to a process for minimizing emissions 14 during the cold start operation of an engine. The engine consists of any internal or external combustion engine which generates an exhaust gas stream 16 containing noxious components or pollutants including unburned or thermally 17 degraded hydrocarbons or similar organics. Other noxious components usually 18 present in the exhaust gas include nitrogen oxides and carbon monoxide. The 19 engine may be fueled by a hydrocarbonaceous fuel. As used in this specification and in the appended claims, the term "hydrocarbonaceous fuel" includes 21 hydrocarbons, alcohols and mixtures thereof. Examples of hydrocarbons which 22 can be used to fuel the engine are the mixtures of hydrocarbons which make up 23 gasoline or diesel fuel. The alcohols which may be used to fuel engines include 24 ethanol and methanol. Mixtures of alcohols and mixtures of alcohols and hydrocarbons can also be used. The engine may be a jet engine, gas turbine, 26 internal combustion engine, such as an automobile, truck or bus engine, a diesel 27 engine or the like. The process of this invention is particularly suited for 28 hydrocarbon, alcohol, or hydrocarbon-alcohol mixture, internal combustion 29 engine mounted in an automobile. For convenience the description will use hydrocarbon as the fuel to exemplify the invention. The use of hydrocarbon in 31 the subsequent description is not to be construed as limiting the invention to 32 hydrocarbon fueled engines.

1 When the engine is started up, it produces a relatively high 2 concentration of hydrocarbons in the engine exhaust gas stream as well as 3 other pollutants. Pollutants will be used herein to collectively refer to any 4 unburned fuel components and combustion byproducts found in the exhaust stream. For example, when the fuel is a hydrocarbon fuel, hydrocarbons, 6 nitrogen oxides, carbon monoxide and other combustion byproducts will be 7 found in the engine exhaust gas stream. The temperature of this engine 8 exhaust stream is relatively cool, generally below 5000 C. and typically in the 9 range of 200 to 400 C. This engine exhaust stream has the above characteristics during the initial period of engine operation, typically for the 11 first 30 to 120 seconds after startup of a cold engine. The engine exhaust 12 stream will typically contain, by volume, about 500 to 1000 ppm 13 hydrocarbons.
14 The engine exhaust gas stream which is to be treated is flowed over a molecular sieve bed comprising molecular sieve SSZ-56 a first exhaust 16 stream. Molecular sieve SSZ-56 is described below. The first exhaust stream 17 which is discharged from the molecular sieve bed is now flowed over a 18 catalyst to convert the pollutants contained in the first exhaust stream to 19 innocuous components and provide a treated exhaust stream which is discharged into the atmosphere. It is understood that prior to discharge into 21 the atmosphere, the treated exhaust stream may be flowed through a muffler 22 or other sound reduction apparatus well known in the art.
23 The catalyst which is used to convert the pollutants to innocuous 24 components is usually referred to in the art as a three-component control catalyst because it can simultaneously oxidize any residual hydrocarbons 26 present in the first exhaust stream to carbon dioxide and water, oxidize any 27 residual carbon monoxide to carbon dioxide and reduce any residual nitric 28 oxide to nitrogen and oxygen. In some cases the catalyst may not be required 29 to convert nitric oxide to nitrogen and oxygen, e.g., when an alcohol is used as the fuel. In this case the catalyst is called an oxidation catalyst.
Because of 31 the relatively low temperature of the engine exhaust stream and the first 32 exhaust stream, this catalyst does not function at a very high efficiency, 33 thereby necessitating the molecular sieve bed.

1 When the molecular sieve bed reaches a sufficient temperature, 2 typically about 150-200 C., the pollutants which are adsorbed in the bed 3 begin to desorb and are carried by the first exhaust stream over the catalyst.
4 At this point the catalyst has reached its operating temperature and is therefore capable of fully converting the pollutants to innocuous components.
6 The adsorbent bed used in the instant invention can be conveniently 7 employed in particulate form or the adsorbent can be deposited onto a solid 8 monolithic carrier. When particulate form is desired, the adsorbent can be 9 formed into shapes such as pills, pellets, granules, rings, spheres, etc. In the employment of a monolithic form, it is usually most convenient to employ the 11 adsorbent as a thin film or coating deposited on an inert carrier material which 12 provides the structural support for the adsorbent. The inert carrier material 13 can be any refractory material such as ceramic or metallic materials. It is 14 desirable that the carrier material be unreactive with the adsorbent and not be degraded by the gas to which it is exposed. Examples of suitable ceramic 16 materials include sillimanite, petalite, cordierite, mullite, zircon, zircon mullite, 17 spondumene, alumina-titanate, etc. Additionally, metallic materials which are 18 within the scope of this invention include metals and alloys as disclosed in 19 U.S. Pat. No. 3,920,583 which are oxidation resistant and are otherwise capable of withstanding high temperatures.
21 The carrier material can best be utilized in any rigid unitary 22 configuration which provides a plurality of pores or channels extending in the 23 direction of gas flow. It is preferred that the configuration be a honeycomb 24 configuration. The honeycomb structure can be used advantageously in either unitary form, or as an arrangement of multiple modules. The honeycomb 26 structure is usually oriented such that gas flow is generally in the same 27 direction as the cells or channels of the honeycomb structure. For a more 28 detailed discussion of monolithic structures, refer to U.S. Pat. Nos.
3,785,998 29 and 3,767,453.
The molecular sieve is deposited onto the carrier by any convenient.
31 way well known in the art. A preferred method involves preparing a slurry 32 using the molecular sieve and coating the monolithic honeycomb carrier with 33 the slurry. The slurry can be prepared by means known in the art such as 34 combining the appropriate amount of the molecular sieve and a binder with 1 water. This mixture is then blended by using means such as sonification, milling, 2 etc. This slurry is used to coat a monolithic honeycomb by dipping the 3 honeycomb into the slurry, removing the excess slurry by draining or blowing out 4 the channels, and heating to about 100 C. If the desired loading of molecular sieve is not achieved, the above process may be repeated as many times as 6 required to achieve the desired loading.
7 Instead of depositing the molecular sieve onto a monolithic honeycomb 8 structure, one can take the molecular sieve and form it into a monolithic 9 honeycomb structure by means known in the art.
The adsorbent may optionally contain one or more catalytic metals 11 dispersed thereon. The metals which can be dispersed on the adsorbent are the 12 noble metals which consist of platinum, palladium, rhodium, ruthenium, and 13 mixtures thereof. The desired noble metal may be deposited onto the adsorbent, 14 which acts as a support, in any suitable manner well known in the art. One example of a method of dispersing the noble metal onto the adsorbent support 16 involves impregnating the adsorbent support with an aqueous solution of a 17 decomposable compound of the desired noble metal or metals, drying the 18 adsorbent which has the noble metal compound dispersed on it and then 19 calcining in air at a temperature of about 400 to about 500 C for a time of about 1 to about 4 hours. By decomposable compound is meant a compound which 21 upon heating in air gives the metal or metal oxide. Examples of the 22 decomposable compounds which can be used are set forth in U.S. Pat. No.
23 4,791,091. Preferred decomposable compounds are chloroplatinic acid, rhodium 24 trichloride, chloropalladic acid, hexachloroiridate (IV) acid and hexachlororuthenate. It is preferable that the noble metal be present in an 26 amount ranging from about 0.01 to about 4 weight percent of the adsorbent 27 support. Specifically, in the case of platinum and palladium the range is 0.1 to 4 28 weight percent, while in the case of rhodium and ruthenium the range is from 29 about 0.01 to 2 weight percent.
These catalytic metals are capable of oxidizing the hydrocarbon and 31 carbon monoxide and reducing the nitric oxide components to innocuous 32 products. Accordingly, the adsorbent bed can act both as an adsorbent and as a 33 catalyst.
34 The catalyst which is used in this invention is selected from any three component control or oxidation catalyst well known in the art. Examples of 36 catalysts are those described in U.S. Pat. Nos. 4,528,279; 4,791,091;
4,760,044;

1 4,868,148; and 4,868,149. Preferred catalysts well known in the art are those 2 that contain platinum and rhodium and optionally palladium, while oxidation 3 catalysts usually do not contain rhodium. Oxidation catalysts usually contain 4 platinum and/or palladium metal. These catalysts may also contain promoters and stabilizers such as barium, cerium, lanthanum, nickel, and iron. The noble 6 metals promoters and stabilizers are usually deposited on a support such as 7 alumina, silica, titania, zirconia, alumino silicates, and mixtures thereof with 8 alumina being preferred. The catalyst can be conveniently employed in 9 particulate form or the catalytic composite can be deposited on a solid monolithic carrier with a monolithic carrier being preferred. The particulate form and 11 monolithic form of the catalyst are prepared as described for the adsorbent 12 above.

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

16 Example 1 17 Synthesis of the directing agent N,N-Diethyl-2-Methyldecahydroguinolinium 18 Hydroxide 19 The parent amine 2-Methyldecahydroquinoline was obtained by hydrogenation of 2-methylquinoline (quinaldine) as described below. A 1000-ml 21 stainless steel hydrogenation vessel was charged with 200 gm (1.4 mol) of 2-22 methylquinoline (quinaldine), purchased from Aldrich Chemical Company, and 23 300 ml glacial acetic acid, 10 gm of PtO2 and 15 ml concentrated H2SO4. The 24 mixture was purged twice with nitrogen (the vessel was pressurized with nitrogen to 1000 psi and evacuated). Then, the reaction vessel was pressurized to 1500-26 psi of hydrogen gas and allowed to stir at 50 C overnight. The pressure dropped 27 overnight and the vessel was pressurized back to 1500 psi (with H2 gas) and let 28 to stir until no further drop in the pressure was observed. Once the reaction was 29 complete, the mixture was filtered and the 1 filtrate was treated with 50wt% aqueous sodium hydroxide solution until a pH
2 of -9 was achieved. The treated filtrate was diluted with 1000 ml diethyl 3 ether. The organic layer was separated, washed with water and brine, and 4 dried over anhydrous MgSO4. Concentration under vacuum (using rotary evaporator) gave the amine as a pair of isomers (cis-fused and trans-fused 6 ring system with the methyl group in the equatorial position in both isomers) in 7 97% yield (208 gm) in a ratio of 1.1:0.9 trans-fused:cis-fused. The 8 authenticity of the product was established by spectral data analysis including 9 NMR, IR and GCMS spectroscopy. In principle, there are four likely isomers, but only two isomers were produced.

11 N-Ethyl-2-methyldecahydroquinolinium hydroiodide was prepared 12 according to the method described below. To a solution 100 gm (0.65 mol) of 13 2-methyldecahydroquinoline (trans and cis) in 350 ml acetonitrile, 111 gm 14 (0.72 mole) of ethyl iodide was added. The mixture was stirred (using an overhead stirrer) at room temperature for 96 hours. Then, an additional 1/2 16 mole equivalent of ethyl iodide was added and the mixture was heated at 17 reflux for 6 hours. The reaction mixture was concentrated on a rotary 18 evaporator at reduced pressure and the obtained solids were rinsed with 500 19 ml ethyl ether to remove any unreactive amines and excess iodide. The reaction afforded a mixture of two N-ethyl-2-methyl-decahydroquinolinium 21 hydroiodide salts (mono-ethyl derivatives) and a small mixture of the 22 quaternized derivatives. The products were isolated by recrystallization from 23 isopropyl alcohol several times to give the pure trans-fused ring N-ethyl-2-24 methyl-decahydroquinolinium hydroiodide and the pure cis-fused ring N-ethyl-2-methyl-decahydroquinolinium hydroiodide (see the scheme below).

26 N,N-Diethyl-2-methyldecahydroquinolinium iodide was prepared 27 according to the procedure shown below. The procedure below is typical for 28 making the N,N-diethyl-2-methyl-decahydro-quinolinium iodide. The obtained 29 transfused ring N-ethyl-2-methyl-decahydroquinolinium hydroiodide (28 gm, 0.09 mol) was added to an acetonitrile (150 ml) and KHCO3 (14 gm, 0.14 mol) 31 solution. To this solution, 30 gm (0.19 mol) of ethyl iodide was added and the 32 resulting mixture was stirred (with an overhead stirrer) at room temperature 33 for 72 hours. Then, one more mole equivalent of ethyl iodide was added and 1 the reaction was heated to reflux and allowed to stir at the reflux temperature 2 for 6 hours. Heating was stopped and the reaction was allowed to further stir 3 at room temperature overnight. The reaction was worked up by removing the 4 excess ethyl iodide and the solvent at reduced pressure on a rotary evaporator. The resulting solids were suspended in 500 ml chloroform, which 6 dissolves the desired product and leaves behind the unwanted KHCO3 and its 7 salt by-products. The solution was filtered, and the filtrate was dried over 8 anhydrous MgSO4. Filtration followed by concentration at reduced pressure 9 on a rotary evaporator, gave the desired N,N-diethyl-2-methyl-decahydroquinolinium iodide as a pale tan-colored solid. The solid was 11 further purified by recrystallization in isopropyl alcohol. The reaction afforded 12 26.8 gm (87% yield). The N,N-diethyl-2-methyl-decahydro-quinolinium iodide 13 of the cis-fused ring isomer was made according to the procedure described 14 above. The trans-fused ring derivative A (see the scheme 1 below) is the templating agent (SDA) useful for making SSZ-56.
16 N,N-Diethyl-2-methyldecahydroquinolinium hydroxide 17 The hydroxide version of N,N-diethyl-2-methyldecahydro-quinolinium 18 cation was prepared by ion exchange as described in the procedure below.
19 To a solution of 20 gm (0.06 mol) of N,N-diethyl-2-methyldecahydro-quinolinium iodide in 80 ml water, 80 gm of OH-ion exchange resin (BIO
21 RAD AGI-X8) was added, and the resulting mixture was allowed to gently 22 stir at room temperature for few hours. The mixture was filtered and the ion 23 exchange resin was rinsed with additional 30 ml water (to ensure removing all 24 the cations from the resin). The rinse and the original filtrate were combined and titration analysis on a small sample of the filtrate with 0.1 N HCI
indicated 26 a 0.5M OH ions concentration (0.055 mol cations). Scheme 1 below depicts 27 the synthesis of the templating agent.

Me Me Me Pt02/1-12 N 1500 Psi NH EtI (@DNH-Et CH3CO2H/ CH3CN Ie H
"Re crystallization"

M-,9, isopropyl alcohol Me a NH Me I Et I Et 1) EtI
2) Ion Exchange-OH

Et Et YNO
I~Me 9 Me H OH Et Et Trans-Fused-Ring [SSZ-56 SDA] Cis-Fused-Ring 2 Scheme 1 3 There are 4 possible isomers (depicted below) from the synthesis, but only 4 two isomers were produced: trans-fused-equatorial methyl A and cis-fused-equatorial methyl B.

Me Me + Me +
A C Me Me Trans-Fused-Equatorial-Methyl Trans-Fused-Axial-Methyl 1,1-Diethyl-2-methyl-decahydro-quinolinium 1, 1 -Diethyl-2-methyl-decahydro-quinolinium H H H H
/'--Me + '---Me Me Me Me Me B D
Cis-Fused-Equatorial-Methyl Cis-Fused-Axial-Methyl 6 1,1-Diethyl-2-methyl-decahydro-quinolinium 1, 1 -Diethyl-2-methyl-decahydro-quinolinium 8 Example 2 9 Synthesis of Borosilicate SSZ-56 from Calcined Boron-BETA Zeolite In a 23 cc Teflon liner, 3 gm of 0.5M solution (1.5 mmol) of N,N-diethyl-1 2-methyldecahydroquinolinium hydroxide (the trans-fused ring isomer), 0.5 2 gm of 1.0N solution of aqueous NaOH (0.5 mmol), 4.5 gm of de-ionized water, 3 and 0.65 gm of calcined boron-BETA zeolite were all mixed. The Teflon liner 4 was capped and placed in a Parr reactor and heated in an oven at 150 C
while tumbling at about 43 rpm. The reaction progress was checked by 6 monitoring the gel's pH and by looking for crystal formation using Scanning 7 Electron Microscopy (SEM) at 3-6 days intervals. The reaction was usually 8 completed after heating for 18-24 days (shorter crystallization periods were 9 achieved at 160 C). The final pH at the end of the reaction ranged from 10.8-11.6. Once the crystallization was completed (by SEM analysis), the reaction 11 mixture (usually a white fine powdery precipitate with clear liquid) was filtered.
12 The collected solids were rinsed a few times with de-ionized water (-1000 ml), 13 and then let to air-dry overnight followed by drying in an oven at 120 C
for 15-14 20 minutes. The reaction yielded about 0.55 -0.6 gm of pure boron-SSZ-56 as determined by XRD analysis.

16 Example 3 17 Seeded Preparation of Borosilicate SSZ-56 18 In a 23 cc Teflon liner, 3 gm of 0.5M solution (1.5 mmol) of N,N-diethyl-19 2-methyldecahydroquinolinium hydroxide (the trans-fused ring isomer), 0.5 gm of 1.ON solution of aqueous NaOH (0.5 mmol), 4.5 gm of de-ionized water, 21 0.65 gm of calcined boron-BETA zeolite and 0.03 gm of SSZ-56 (made as 22 described above) were mixed. The Teflon liner was capped and placed in a 23 Parr reactor and heated in an oven at 150 C while tumbling at about 43 rpm.
24 The reaction progress was checked by monitoring the gel's pH and by looking for crystal formation using Scanning Electron Microscopy (SEM) at 3 day 26 intervals. The crystallization was complete (SEM analysis) after heating for 6 .27 days. The final pH at the end of the reaction was usually 11.2. Once 28 completed, the reaction mixture was filtered, and the collected solids were 29 rinsed with de-ionized water (-1000 ml), and then let to air-dry overnight followed by drying in an oven at 120 C for 15-20 minutes. The reaction 31 yielded 0.6 gm of pure boron-SSZ-56. Identity and characterization of the 32 material was determined by XRD analysis.

1 Example 4 2 Direct Synthesis of Borosilicate SSZ-56 from Sodium Borate Decahydrate as 3 the Boron Sources and CAB-O-SIL M-5 as the Silicon Source 4 In a 23 cc Teflon liner, 6 gm of 0.5M solution (3 mmol) of N,N-diethyl-2-methyldecahydroquinolinium hydroxide (the trans-fused ring isomer), 1.2 gm 6 of 1.ON solution of aqueous NaOH (1.2 mmol), 4.8 gm of de-ionized water, 7 and 0.065 gm of sodium borate decahydrate were mixed and stirred until the 8 sodium borate was completely dissolved. Then, 0.9 gm of Cab-O-Sil M-5 9 (-98% SiO2) was added and thoroughly mixed. The resulting gel was capped and placed in a Parr reactor and heated in an oven at 160 C while tumbling at 11 about 43 rpm. The reaction progress was checked by monitoring the gel's pH
12 and by looking for crystal formation using Scanning Electron Microscopy 13 (SEM) at 6 days intervals. The reaction was usually completed after heating 14 for 18-24 days. The final pH at the end of the reaction ranged from 11.5-12.3.
Once the crystallization was completed (by SEM analysis), the reaction 16 mixture, a white fine powdery precipitate with clear liquid, was filtered.
The 17 collected solids were rinsed few times with de-ionized water (-1000 ml), and 18 then air-dried overnight followed by drying in an oven at 120 C for 15 minutes.
19 The reaction usually yields about 0.75-0.9 gm of pure boron-SSZ-56.

Example 5 21 Seeded Synthesis of Borosilicate SSZ-56 from Sodium Borate Decahydrate 22 as the Boron Source and CAB-O-SIL M-5 as the Silicon Source 23 In a 23 cc Teflon liner, 6 gm of 0.5M solution (3 mmol) of N,N-diethyl-2-24 methyldecahydroquinolinium hydroxide (the trans-fused ring isomer), 1.2 gm of 1.ON solution of aqueous NaOH (1.2 mmol), 4.8 gm of de-ionized water, 26 and 0.062 gm of sodium borate decahydrate were mixed and stirred until the 27 sodium borate was completely dissolved. Then, 0.9 gm of Cab-O-Sil M-5 28 (-98% SiO2) and 0.04 gm of B-SSZ-56 made as in Example 4 were added 29 and thoroughly mixed. The resulting gel was capped and placed in a Parr reactor and heated in an oven at 160 C while tumbling at about 43 rpm. The 31 reaction progress was checked by monitoring the gel's pH and by looking for 1 crystal formation using Scanning Electron Microscopy (SEM) at 3-5 days 2 intervals. The reaction was completed after heating for 7 days. The final pH
3 at the end of the reaction was about 12.2. Once the crystallization was 4 completed (by SEM analysis), the reaction mixture, a white fine powdery precipitate with clear liquid, was filtered. The collected solids were rinsed few 6 times with de-ionized water (1000 ml), and then air-dried overnight followed 7 by drying in an oven at 120 C for 15 minutes. The reaction yielded 0.88 gm of 8 pure boron-SSZ-56.

9 Example 6 Calcination of SSZ-56 11 Removing the templating agent molecules (structure-directing agents:
12 SDAs) from zeolite SSZ-56 to free its channels and cavities was 13 accomplished by the calcination method described below. A sample of the 14 as-made SSZ-56 synthesized according to the procedures of Examples 2, 3, 4 or 5 discussed above is calcined by preparing a thin bed of SSZ-56 in a 16 calcination dish which was heated in a muffle furnace from room temperature 17 to 595 C in three stages. The sample was heated to120 C at a rate of 18 1 C/minute and held for 2 hours. Then, the temperature was ramped up to 19 540 C at a rate of VC/minute and held for 5 hours. The temperature was then ramped up again at 1 C/minute to 595 C and held there for 5 hours. A
21 nitrogen stream with a slight bleed of air was passed over the zeolite at a rate 22 of 20 standard cubic feet (0.57 standard cubic meters) per minute during 23 heating the calcination process.

Example 7 27 Ammonium- Ion Exchange of SSZ-56 29 The Na+ form of SSZ-56 prepared as in Examples 2, 3, 4 or 5 and calcined as in Example 6 was converted to NH4+-SSZ-56 form by heating the 31 material in an aqueous solution of NH4NO3 (typically 1gm NH4NO3/1 gm SSZ-32 56 in 20 ml H20) at 90 C for 2-3 hours. The mixture was then filtered and the 33 step was repeated as many times as desired (usually done 2-3 times). After 1 filtration, the obtained NH4-exchanged-product was washed with de-ionized 2 water and air dried. The NH4+ form of SSZ-56 can be converted to the H+
3 form by calcination to 540 C (as described in Example 6 above stopping at 4 the end of the second stage).
6 Example 8 7 Preparation of Aluminosilicate SSZ-56 by Aluminum Exchange of Boron-SSZ-9 The aluminosilicate version of SSZ-56 was prepared by way of exchanging borosilicate SSZ-56 with aluminum nitrate according to the 11 procedure described below. The H+ version of calcined borosilicate SSZ-56 12 (prepared as in Examples 2, 3, 4 or 5 and treated with ammonium nitrate and 13 calcined as Example 6) was easily converted to the aluminosilicate SSZ-56 by 14 suspending the zeolite (H+/borosilicate SSZ-56) in 1 M solution of aluminum nitrate nonahydrate (10 ml of 1 M AI(N03)3.9H20 soln./1 gm SSZ-56). The 16 suspension was heated at reflux overnight. The resulting mixture was then 17 filtered and the collected solids were thoroughly rinsed with de-ionized water 18 and air-dried overnight. The solids were further dried in an oven at 120 C
for 19 2 hours. The exchange can also be done on the Na+ version of SSZ-56 (as prepared in Examples 2, 3, 4 or 5 and calcined as in Example 6).

22 Example 9 23 Nitrogen Adsorption (MicroPore Volume Analysis) The Na+ and H+ forms of SSZ-56 as synthesized in Examples 2 and 4 26 above and treated as in Examples 6 and 7 was subjected to a surface area 27 and micropore volume analysis using N2 as adsorbate and via the BET
28 method. The zeolite exhibited a considerable void volume with a micropore 29 volume of 0.18 cc/g for Na+ form, and 0.19 cc/gm for the H+ form.

1 Example 10 2 Argon Adsorption (MicroPore Volume Analysis) 4 A calcined sample of Na+ version of borosilicate SSZ-56 (synthesized as in Example 2 and calcined as in Example 6) had a micropore volume of 6 0.16 cc/gm based on argon adsorption isotherm at 87.5 K (-186 C) recorded 7 on ASAP 2010 equipment from Micromerities. The sample was first 8 degassed at 400 C for 16 hours prior to argon adsorption. The low-pressure 9 dose was 2.00 cm3/g (STP). A maximum of one hour equilibration time per dose was used and the total run time was 37 hours. The argon adsorption 11 isotherm was analyzed using the density function theory (DFT) formalism and 12 parameters developed for activated carbon slits by Olivier (Porous Mater.
13 1995, 2, 9) using the Saito Foley adaptation of the Horvarth-Kawazoe 14 formalism (Microporous Materials, 1995, 3, 531) and the conventional t-plot method (J. Catalysis, 1965, 4, 319).

17 Example 11 18 Constraint Index Test The hydrogen form of SSZ-56 synthesized as in Example 2 was 21 calcined and ammonium exchanged as in Examples 6 and 7 was aluminum 22 exchanged as in Example 8. The obtained aluminum-exchanged sample of 23 SSZ-56 was then ammonium exchanged as in Example 7 followed by 24 calcination to 540 C as in Example 6. The H-Al-SSZ-56 was pelletized at 4 KPSI, crushed and granulated to 20-40 mesh. A 0.6 gram sample of the 26 granulated material was calcined in air at 540 C for 4 hours and cooled in a 27 desiccator to ensure dryness. Then, 0.5 gram was packed into a 3/8 inch 28 stainless steel tube with alundum on both sides of the molecular sieve bed.
A
29 Lindburg furnace was used to heat the reactor tube. Helium was introduced into the reactor tube at 10 cc/min. and at atmospheric pressure. The reactor 31 was heated to about 315 C, and a 50/50 feed of n-hexane and 3-32 methylpentane is introduced into the reactor at a rate of 8 dal/min. The feed 33 was delivered by a Brownlee pump. Direct sampling into a GC began after 10 34 minutes of feed introduction. The Constraint Index (CI) value was calculated 1 from the GC data using methods known in the art. SSZ-56 had a Cl of 0.76 2 and a conversion of 79% after 15 minutes on stream. The material fouled 3 rapidly and at 105 minutes the Cl was 0.35 and the conversion was 25.2%.
4 The Cl test showed the material was very active catalytic material.
6 Example 12 7 n-Hexadecane Hydrocracking Test 9 A 1 gm sample of SSZ-56 (prepared as described for the Constraint Index test in Example 11) was suspended in 10 gm de-ionized water. To this 11 suspension, a solution of Pd(NH3)4(NO3)2 at a concentration which would 12 provide 0.5 wt. % Pd with respect to the dry weight of the molecular sieve 13 sample was added. The pH of the solution was adjusted to pH of 9.2 by a 14 drop-wise addition of 0.15N solution of ammonium hydroxide. The mixture was then heated in an oven at 75 C for 48 hours. The mixture was then 16 filtered through a glass frit, washed with de-ionized water, and air-dried.
The 17 collected Pd-SSZ-56 sample was slowly calcined up to 482 C in air and held 18 there for three hours.
19 The calcined Pd/SSZ-56 catalyst was pelletized in a Carver Press and granulated to yield particles with a 20/40 mesh size. Sized catalyst (0.5 g) 21 was packed into a % inch OD tubing reactor in a micro unit for n-hexadecane 22 hydroconversion. The table below gives the run conditions and the products 23 data for the hydrocracking test on n-hexadecane.
24 As the results show in the table below, SSZ-56 is a very active and isomerisation selective catalyst at 96.5% n-C16 conversion at 256 C.

Temperature 256 C (496 F) Time-on-Stream (hrs.) 71.4-72.9 WHSV 1.55 Titrated? NO
n-16, % Conversion 96.5 Hydrocracking Conv. 35.2 Isomerization Selectivity, 63.5 Cracking Selectivity, % 36.5 C4_ % 2.3 C5/C4 15.2 C5+C6/C5, % 19.3 DMB/MP 0.05 C4-C13 i/n 3.7 C7-C13 yield 27.7

Claims (85)

WHAT IS CLAIMED IS:

1. A molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.

2. A molecular sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table 2.

3. A molecular sieve according to Claim 2 wherein the oxide of (2) is aluminum oxide.

4. A molecular sieve according to Claim 2 wherein the oxide of (2) is boron oxide.

5. A molecular sieve according to Claim 1 or 2 wherein said molecular sieve is predominantly in the hydrogen form.

6. A molecular sieve according to Claim 1 or 2 wherein said molecular sieve is substantially free of acidity.

7. A molecular sieve having a composition, as synthesized and in the anhydrous state, in terms of mole ratios as follows:

YO2/ W c O d 15 - infinity M2/n/YO2 0.01 - 0.03 Q/YO2 0.02-0.05 wherein Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; c is 1 or 2; d is 2 when c is 1 or d is 3 or 5 when c is 2; M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M; and Q is a trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium cation.

8. A method of preparing a crystalline material comprising (1) a first oxide comprising silicon oxide and (2) a second oxide comprising boron oxide and having a mole ratio of the first oxide to the second oxide greater than about and having, after calcination, the X-ray diffraction lines of Table 2, said method comprising contacting under crystallization conditions sources of said oxides and a structure directing agent comprising a trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium cation.

9. The method according to Claim 8 wherein the molecular sieve is prepared from a reaction mixture comprising, in term of mole ratios:

YO2/W a O b >=15 OH-/YO2 0.10-0.50 Q/YO2 0.05-0.50 M2/n/YO2 0.02-0.40 where Y is silicon; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; a is 1 or 2, b is 2 when a is 1; b is 3 when a is 2;
M is an alkali metal cation, alkaline earth metal cation or mixtures thereof;
n is the valence of M; and Q is a trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium cation.

10. A process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with a catalyst comprising a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.

11. The process of Claim 10 wherein the molecular sieve is substantially free of acidity.

12. The process of Claim 10 wherein the process is a hydrocracking process comprising contacting the catalyst with a hydrocarbon feedstock under hydrocracking conditions.

13. The process of Claim 10 wherein the process is a dewaxing process comprising contacting the catalyst with a hydrocarbon feedstock under dewaxing conditions.

14. The process of Claim 10 wherein the process is a process for improving the viscosity index of a dewaxed product of waxy hydrocarbon feeds comprising contacting the catalyst with a waxy hydrocarbon feed under isomerization dewaxing conditions.

15. The process of Claim 10 wherein the process is a process for producing a C20+
lube oil from a C20+ olefin feed comprising isomerizing said olefin feed under isomerization conditions over the catalyst.

16. The process of Claim 15 wherein the catalyst further comprises at least one Group VIII metal.

17. The process of Claim 10 wherein the process is a process for catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350°
F(177°C) and containing straight chain and slightly branched chain hydrocarbons comprising contacting said hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) under dewaxing conditions with the catalyst.

18. The process of Claim 17 wherein the catalyst further comprises at least one Group VIII metal.

19. The process of Claim 17 wherein said catalyst comprises a layered catalyst comprising a first layer comprising the molecular sieve and at least one Group VIII metal, and a second layer comprising an aluminosilicate zeolite which is more shape selective than the molecular sieve of said first layer.

20. The process of Claim 10 wherein the process is a process for preparing a lubricating oil which comprises:

hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil; and catalytically dewaxing said effluent comprising hydrocracked oil at a temperature of at least about 400°F (204° C) and at a pressure of from about 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge) in the presence of added hydrogen gas with the catalyst.

21. The process of Claim 20 wherein the catalyst further comprises at least one Group VIII metal.

22. The process of Claim 10 wherein the process is a process for isomerization dewaxing a raffinate comprising contacting said raffinate in the presence of added hydrogen under isomerization dewaxing conditions with the catalyst.

23. The process of Claim 22 wherein the catalyst further comprises at least one Group VIII metal.

24. The process of Claim 22 wherein the raffinate is bright stock.

25. The process of Claim 10 wherein the process is a process for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatics content comprising contacting a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range above about 40° C and less than about 200°C under aromatic conversion conditions with the catalyst.

26. The process of Claim 25 wherein the molecular sieve is substantially free of acid.

27. The process of Claim 25 wherein the molecular sieve contains a Group VIII
metal component.

28. The process of Claim 10 wherein the process is a catalytic cracking process comprising contacting a hydrocarbon feedstock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with the catalyst.

29. The process of Claim 28 wherein the catalyst additionally comprises a large pore crystalline cracking component.

30. The process of Claim 10 wherein the process is an isomerization process for isomerizing C4 to C7 hydrocarbons, comprising contacting a feed having normal and slightly branched C4 to C7 hydrocarbons under isomerizing conditions with the catalyst.

31. The process of Claim 30 wherein the molecular sieve has been impregnated with at least one Group VIII metal.

32. The process of Claim 30 wherein the catalyst has been calcined in a steam/air mixture at an elevated temperature after impregnation of the Group VIII metal.

33. The process of Claim 31 wherein the Group VIII metal is platinum.

34. The process of Claim 10 wherein the process is a process for alkylating an aromatic hydrocarbon which comprises contacting under alkylation conditions at least a molar excess of an aromatic hydrocarbon with a C2 to C20 olefin under at least partial liquid phase conditions and in the presence of the catalyst.

35. The process of Claim 34 wherein the olefin is a C2 to C4 olefin.

36. The process of Claim 35 wherein the aromatic hydrocarbon and olefin are present in a molar ratio of about 4:1 to about 20:1, respectively.

37. The process of Claim 35 wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene or mixtures thereof.

38. The process of Claim 10 wherein the process is a process for transalkylating an aromatic hydrocarbon which comprises contacting under transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of the catalyst.

39. The process of any one of Claims 10, 12 to 15, 17, 20, 22, 28, 30, 34 and 38, wherein the molecular sieve is predominantly in the hydrogen form.

40. The process of Claim 38 wherein the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon are present in a molar ratio of from about 1:1 to about 25:1, respectively.

41. The process of Claim 38 wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof.

42. The process of Claim 38 wherein the polyalkyl aromatic hydrocarbon is a dialkylbenzene.

43. The process of Claim 10 wherein the process is a process to convert paraffins to aromatics which comprises contacting paraffins under conditions which cause paraffins to convert to aromatics with a catalyst comprising the molecular sieve and gallium, zinc, or a compound of gallium or zinc.

44. The process of Claim 10 wherein the process is a process for isomerizing olefins comprising contacting said olefin under conditions which cause isomerization of the olefin with the catalyst.

45. The process of Claim 10 wherein the process is a process for isomerizing an isomerization feed comprising an aromatic C8 stream of xylene isomers or mixtures of xylene isomers and ethylbenzene, wherein a more nearly equilibrium ratio of ortho-, meta and para-xylenes is obtained, said process comprising contacting said feed under isomerization conditions with the catalyst.

46. The process of Claim 10 wherein the process is a process for oligomerizing olefins comprising contacting an olefin feed under oligomerization conditions with the catalyst.

47. A process for converting oxygenated hydrocarbons comprising contacting said oxygenated hydrocarbon under conditions to produce liquid products with a catalyst comprising a molecular sieve having a mole ratio greater than about of an oxide of a first tetravalent element to an oxide of a second tetravalent element which is different from said first tetravalent element, trivalent element, pentavalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.

48. The process of Claim 47 wherein the oxygenated hydrocarbon is a lower alcohol.

49. The process of Claim 48 wherein the lower alcohol is methanol.

50. The process of Claim 10 wherein the process is a process for the production of higher molecular weight hydrocarbons from lower molecular weight hydrocarbons comprising the steps of:

(a) introducing into a reaction zone a lower molecular weight hydrocarbon-containing gas and contacting said gas in said zone under C2+ hydrocarbon synthesis conditions with the catalyst and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon; and (b) withdrawing from said reaction zone a higher molecular weight hydrocarbon-containing stream.

51. The process of Claim 50 wherein the metal or metal compound comprises a lanthanide or actinide metal or metal compound.

52. The process of Claim 50 wherein the lower molecular weight hydrocarbon is methane.

53. A catalyst composition for promoting polymerization of 1-olefins, said composition comprising:

(A) a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2; and (B) an organotitanium or organochromium compound.

54. The catalyst composition of Claim 53 wherein oxide (1) is silicon oxide, and oxide (2) is an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide.

55. The process of Claim 10 wherein the process is a process for polymerizing 1-olefins, which process comprises contacting 1-olefin monomer with a catalytically effective amount of a catalyst composition comprising:

(A) a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2; and (B) an organotitanium or organochromium compound under polymerization conditions which include a temperature and pressure suitable for initiating and promoting the polymerization reaction.

56. The process of Claim 55 wherein oxide (1) is silicon oxide, and oxide (2) is an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide.

57. The process of Claim 55 wherein the 1-olefin monomer is ethylene.

58. The process of Claim 56 wherein the 1-olefin monomer is ethylene.

59. The process of Claim 10 wherein the process is a process for hydrogenating a hydrocarbon feed containing unsaturated hydrocarbons, the process comprising contacting the feed with hydrogen under conditions which cause hydrogenation with the catalyst.

60. The process of Claim 59 wherein the catalyst contains metals, salts or complexes wherein the metal is selected from the group consisting of platinum, palladium, rhodium, iridium or combinations thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, rhenium, manganese and combinations thereof.

61. A process for hydrotreating a hydrocarbon feedstock comprising contacting the feedstock with a hydrotreating catalyst and hydrogen under hydrotreating conditions, wherein the catalyst comprises a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.

62. The process of Claim 61 wherein the catalyst contains a Group VIII metal or compound, a Group VI metal or compound or combinations thereof.

63. A process for hydrotreating a hydrocarbon feedstock comprising contacting the feedstock with a hydrotreating catalyst and hydrogen under hydrotreating conditions, wherein the catalyst comprises a molecular sieve having a mole ratio greater than about 15 of (1) an silicon oxide (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table 2.

64. The process of Claim 63 wherein the oxide of (2) is aluminum oxide.

65. The process of Claim 63 wherein the oxide of (2) is boron oxide.

66. The process of Claim 63 wherein the catalyst contains a Group VIII metal or compound, a Group VI metal or compound or combinations thereof.

67. A process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with a catalyst comprising a molecular sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table 2.

68. A process for the reduction of oxides of nitrogen contained in a gas stream wherein said process comprises contacting the gas stream with a molecular sieve, the molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.

69. A process for the reduction of oxides of nitrogen contained in a gas stream wherein said process comprises contacting the gas stream with a molecular sieve, the molecular sieve having a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table 2.

70. The process of Claim 68 or 69 conducted in the presence of oxygen.

71. The process of Claim 68 or 69 wherein said molecular sieve contains a metal or metal ions capable of catalyzing the reduction of the oxides of nitrogen.

72. The process of Claim 71 wherein the metal is cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof.

73. The process of Claim 68 or 69 wherein the gas stream is the exhaust stream of an internal combustion engine.

74. The process of Claim 71 wherein the gas stream is the exhaust stream of an internal combustion engine.

75. A process for treating a cold-start engine exhaust gas stream containing hydrocarbons and other pollutants consisting of flowing said engine exhaust gas stream over a molecular sieve bed which preferentially adsorbs the hydrocarbons over water to provide a first exhaust stream, and flowing the first exhaust gas stream over a catalyst to convert any residual hydrocarbons and other pollutants contained in the first exhaust gas stream to innocuous products and provide a treated exhaust stream and discharging the treated exhaust stream into the atmosphere, the molecular sieve bed characterized in that it comprises a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table 2.

76. The process of Claim 75 wherein the molecular sieve has a mole ratio greater than about 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, and having, after calcination, the X-ray diffraction lines of Table 2.

77. The process of Claim 76 wherein the oxide of (2) is aluminum oxide.

78. The process of Claim 76 wherein the oxide of (2) is boron oxide.

79. The process of Claim 75 wherein the engine is an internal combustion engine.

80. The process of Claim 79 wherein the internal combustion engine is an automobile engine.

81. The process of Claim 75 wherein the engine is fueled by a hydrocarbonaceous fuel.

82. The process of Claim 75 wherein the molecular sieve has deposited on it a metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof.

83. The process of Claim 82 wherein the metal is platinum.

84. The process of Claim 82 wherein the metal is palladium.

85. The process of Claim 82 wherein the metal is a mixture of platinum and palladium.