CA2653928C - Molecular sieve ssz-75 composition of matter and synthesis thereof - Google Patents

Abstract

The present invention relates to new crystalline molecular sieve SSZ-75 having STI topology prepared using a tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication as a structure-directing agent, methods for synthesizing SSZ-75, and uses for SSZ-75.

Description

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4 BACKGROUND OF THE INVENTION
6 Field of the Invention 8 The present invention relates to new crystalline molecular sieve SSZ75, a 9 method for preparing SSZ-75 using a tetramethylene-1,4-bis-(N-methyipyrrolidinium) dication as a structure directing agent ("SDA") and uses 11 for SSZ-75.

Because of their unique sieving characteristics, as well as their catalytic 16 properties, crystalline molecular sieves and zeolites are especially useful in 17 applications such as hydrocarbon conversion, gas drying and separation.
18 Although many different crystalline molecular sieves have been disclosed, 19 there is a continuing need for new molecular sieves with desirable properties for gas separation and drying, hydrocarbon and chemical conversions, and 21 other applications. New molecular sieves may contain novel internal pore 22 architectures, providing enhanced selectivities in these processes.

26 The present invention is directed to a family of crystalline molecular sieves 27 with unique properties, referred to herein as "molecular sieve SSZ-75"
or 28 simply "SSZ-75". SSZ-75 has the framework topology designated "STI" by 29 the IZA. Materials having the STI topology include naturally occurring stilbite and the z.eolit.E.,. designated INU-10. Stilbite is disclosed in Breck, Zeolite 31 Molecular Sieves, 1984, Robert E. Krieger Publishing Company where it is 32 reported that stilbite has a typical silica/alumina mole ratio of 5.2.
TNU-10 is 33 reported in Hong et al., J. AM. CHEM. SOC. 2004, 126, 5817-5826 as having 34 a silica/alumina mole ratio of about 14. When attempts were made to 1 increase the silica/alumina mole ratio in the product, materials other than 2 TNU-10 were produced.

4 In accordance with the present invention there is provided .a crystalline .molecular sieve having STI topology and having a mole ratio of at least 15 of 6 (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element:
7 pentavalent element, second tetravalent element which is different from said 8 first tetravalent element or mixture thereof. The SSZ-75 molecular sieve has, 9 after calcinationõ the X-ray diffraction lines of Table II, It should be noted that the phrase "mole ratio of at least 15" includes the case where there is no 11 oxide (2), Le., the mole ratio of oxide (1) to oxide (2) is infinity. In that case 12 the molecular sieve is comprised of essentially all silicon oxide, 14 The present invention also provides a crystalline molecular sieve having STI
topology and having a mole ratio of at least 15 of (1) silicon oxide to (2) an 16 oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide:
17 titanium oxide, indium oxide and mixtures thereof. The $SZ-75 molecular 18 sieve has, after calcination, the X-ray diffraction lines of Table II.

The present invention further provides such a crystalline molecular sieve 21 having a composition comprising, as synthesized and in the anhydrous state, 22 in terms of mole ratios the following:

24 Si02/&0d at feast 15 (i.e., 15 - infinity) M2jn Si02 0 ¨ 0.03 26 Q Si02 0.02 ¨ 0.08 27 F ISi02 0..01 ¨0.04 29 wherein X is .aluminum, gallium, iron, boron, titanium, indium and mixtures thereof, c is 1 or 2; d is 2 when c is 1 (Le.., W is tetravalent) or d is 3 or

5 when 31 c is 2 d is 3 when W is 'trivalent or 5 when W is pentavalent), M is an 32 alkali metal cation, alkaline earth metal cation or mixtures thereof n is .the 1 valence of M (i.e., 1 or 2); Q is a letramethylene-1,4--bis-(N-methyl 2 pyrrolidinium) dication and F is .fluoride.

4 Also provided in accordance with the present invention is a method of preparing a crystalline .material, said method comprising contacting under

6 crystallization conditions a source(s) of (1) silicon oxide, (2) a source(s) of

7 aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium

8 oxide and mixtures thereof, (3) fluoride ions and (4) a structure directing agent :9 comprising a tetramethylene-1,4-bis--(N-methylpyrrolidinium) dication.
The present invention includes such a method wherein the crystalline material has 11 STI topology and wherein the molecular sieve has, after calcination, the X-ray 1.2. diffraction lines. of TableIL

14 The present invention includes such a method of preparing a crystalline 1.5 material which uses a. reaction mixture comprising (in terms of mole ratios), 16 the following:

18 S102 /X60b at least 15 (i.e., 15 - infinity) 19 OH- SiO2 0.20 ¨ 0,80 Q./ Si02 0.20.¨ 0.80 21 M21/ SiO2 0 - 0,04 22 H,20 / Si02 2.. 10 23 HF Si02 0.20 0.80 wherein X is aluminum, gallium; iron, boron, titanium, indium and mixtures 26 thereof, a is 1 or 2, b is 2 when a is 1 (Le., W is tetravalent); b is 3 when a is 2 27 W is trivalent), M is an .alkali metal cation, alkaline earth metal cation or 28 mixtures thereof; h is the valence of M (i:e.õ 1 or 2); and Q is a 29 tetramethylene-1,4-bis--(N-methylpyrrolidinium) dication, 30.
31 In accordance with the present invention there is provided a process for .32 converting hydrocarbons comprising contacting a hydrocarbonaceous feed at 3.3 hydrocarbon converting conditions with a catalyst comprising a crystalline 1 molecular sieve having ST1 topology and having a mole ratio of at least 15 of 2 (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, 3 pentavalent element, second tetravalent element which is different from said 4 first tetravalent element or mixture thereof. SSZ-75 has, after calcination, the X-ray diffraction lines of Table II. It should be noted that the phrase 'mole 6 ratio of at least 15" includes the case where there is no oxide (2). Le., the 7 mole ratio of oxide (1) to oxide (2) is infinity. In that case the molecular sieve 8 is comprised of essentially all silicon oxide. The molecular sieve may be

9 predominantly in the hydrogen form. It may also be substantially free of acidity.

12 Further provided by the present invention is a hydrocracking process 13 comprising contacting a hydrocarbon feedstock under hydrocracking 14 conditions with a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen form.

17 Also included in this invention is a process for increasing the octane of a 18 hydrocarbon feedstock to produce a product having an increased aromatics 19 content comprising contacting a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range 21 above about 40 C and less than about 200 C, under aromatic conversion 22 conditions with a catalyst comprising the molecular sieve of this invention 23 made substantially free of acidity by neutralizing said molecular sieve with a 24 basic metal. Also provided in this invention is such a process wherein the molecular sieve contains a Group VIII metal component.

27 Also provided by the present invention is a catalytic cracking process 28 comprising contacting a hydrocarbon feedstock in a reaction zone under 29 catalytic cracking conditions in the absence of added hydrogen with a catalyst comprising the molecular sieve of this invention, preferably predominantly in 31 the hydrogen form. Also included in this invention is such a catalytic cracking 32 process wherein the catalyst additionally comprises a large pore crystalline 33 cracking component.

2 This invention further provides an isomerization process for isomerizing C4 to 3 C7 hydrocarbons, comprising contacting a feed having normal and slightly 4 branched C4 to 07 hydrocarbons under isomerizing conditions with a catalyst comprising the molecular sieve of this invention, preferably predominantly in 6 the hydrogen form, The molecular sieve may be impregnated with at least 7 one Group VI1.1 metal, preferably platinum,. The catalyst may be calcined in a 8 steam/air mixture at .an elevated temperature after impregnation of the Group 9 VIII metal.
11 Also provided by the present invention is a process for alkylating an aromatic 12 hydrocarbon which comprises contacting under alkylation conditions at least a 13 molar excess of an aromatic hydrocarbon with a 02 tO 020 olefin under at least 14 partial liquid phase conditions and in the presence of a catalyst comprising the molecular sieve of this invention, preferably predominantly in the hydrogen 16 form. The olefin may be a C2 to 04 olefin, .and the aromatic hydrocarbon and 17 olefin may be present in a molar ratio of about 4:1 to about 20:1, respectively.
18 The aromatic hydrocarbon may be selected from the group consisting of .19 benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthatene or mixtures thereof.

22 Further provided in accordance with this invention is a process for 23 transalkylating an aromatic hydrocarbon which comprises contacting under 24 transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic .25 hydrocarbon under at least partial liquid phase conditions and in the presence:.
.26 of a catalyst comprising the molecular sieve of this invention, preferably :27 predominantly in the hydrogen form. The aromatic hydrocarbon and the 28: polyalkyl aromatic hydrocarbon may be present in a molar 'ratio of from about 29 1:1 to about 25:1, respectively.
31 The aromatic hydrocarbon may be selected from the group consisting of 32 benzene, toluene, ethylbenzeneõ xylene, or mixtures thereof, and the polyalkyl 33 aromatic hydrocarbon may be a dialkybenzene, 2 Further provided by this invention is a process to convert paraffins to 3 aromatics which comprises contacting paraffins under conditions which cause 4 paraffins to convert to aromatics with a catalyst comprising the molecular sieve of this invention, said catalyst comprising gallium, zinc, or a compound 6 of gallium or zinc.

8 In accordance with this invention there is also provided a process for 9 isomerizing olefins comprising contacting said olefin under conditions which cause isomerization of the olefin with a catalyst comprising the molecular 11 sieve of this invention.

13 Further provided in accordance with this invention is a process for isomerizing 14 an isomerization feed comprising an aromatic C8 stream of xylene isomers or mixtures of xylene isomers and ethylbenzene, wherein a more nearly 16 equilibrium ratio of ortho-, meta- and para-xyienes is obtained, said process 17 comprising contacting said feed under isomerization conditions with a catalyst 18 comprising the molecular sieve of this invention.

The present invention further provides a process for oligomerizing olefins 21 comprising contacting an olefin feed under oligomerization conditions with a 22 catalyst comprising the molecular sieve of this invention.

24 This invention also provides a process for converting oxygenated hydrocarbons comprising contacting said oxygenated hydrocarbon with a 26 catalyst comprising the molecular sieve of this invention under conditions to 27 produce liquid products. The oxygenated hydrocarbon may be a lower 28 alcohol.

Further provided in accordance with the present invention is a process tor the 31 production of higher molecular weight hydrocarbons from lower molecular 32 weight hydrocarbons comprising the steps of:

1 (a) introducing into a reaction zone a lower molecular weight 2 hydrocarbon-containing gas and contacting said gas in said zone under 'C,..hydrocarbon synthesis conditions with the 4 catalyst and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher mo/ecular 6 weight hydrocarbon; and 7 (b) withdrawing from said reaction zone a higher molecular weight 8 hydrocarbon-containing stream, The present invention further provides a process for hydrogenating a 11 hydrocarbon feed containing unsaturated hydrocarbons, the process 12 comprising contacting the feed and hydrogen under conditions which cause 13 hydrogenation with a catalyst comprising the molecular sieve of this invention.
14 The catalyst can also contain metals, salts or complexes wherein the metal is selected from the group consisting of platinum, palladium, rhodium, iridium or 16 combinations thereof, or the group consisting of nickel, molybdenum, cobalt, 17 tungsten, titanium, chromium, vanadium, rhenium, manganese and 18 combinations thereof.

The present invention also provides a catalyst composition for promoting 21 polymerization of 1-olefins, said composition comprising 22 (A) a crystalline molecular sieve having a mole ratio of at least 15 of 23 (1) an oxide of a first tetravalent element to (2) an oxide of a 24 trivalent element, penta.valent element, second tetravalent element which is different from said first tetravalent element or 26 mixture thereof and having, after calcination, the X-ray 27 diffraction lines of Table II; and 29 (B) an organotitanium or organochromiurn compound, 31 Also provided is a process for polymeriing 1-olefins, which process 32 comprises contacting 1-olefin monomer with a catalytically effective amount of 33 a catalyst composition comprising 2 (2k). a brystailine molecular sieve having a mole ratio of at least 15 of 3 (1) an oxide of a first tetravalent element to (2) an oxide of a 4 trivalent element, pentavalent element, second tetravalent.
element which is different from said first tetravalent element or 6 mixture thereof and having, after calcination, the X-ray 7 diffraction lines of Table II; and 9 (B) an organotitanium.or organochromium compound.
11 under polymerization conditions which include a temperature and pressure 12 suitable for initiating and promoting the polymerization reaction. The 1-olefin 13 may be ethylene.

The present invention further provides a dewaxing process comprising 16 contacting a hydrocarbon feedstock under dewaxing conditions with a catalyst 17 comprising a crystalline molecular sieve having STI topology and a mole ratio 18 of at least about 14 of (1) an oxide of a first tetravalent element to.
(2) an oxide 19 of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof. The 21 molecular sieve is preferably predominantly in the hydrogen form, 23. Also provided is a process for improving the viscosity index of a dewaxed 24 product of waxy hydrocarbon feeds comprising contacting a waxy hydrocarbon feed under isomerization dewaxing conditions with a catalyst 26 comprising a crystalline molecular sieve having STI topology and a mole ratio 27 of at least about 14 of (1) an oxide of a first tetravalent element to (2) an oxide 28 of a trivalent element, pentavalent element, second tetravalent element which 29 is different from said first tetravalent element or mixture thereof. The molecular sieve is preferably predominantly in the hydrogen .form.

32. Further provided by the present invention is a process for producing a C20+
33 iube oil from a C2o, olefin feed comprising isomerizing said olefin feed .under 1 isomerization conditions over a catalyst comprising a crystalline molecular 2 sieve having STI topology and a mole ratio of at least about 14 of (1) an oxide 3 of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent 4 element, second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve may be 6 predominantly in the hydrogen form. The catalyst may contain at least one 7 Group VlII metal.

9 Also provided is a process for catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350T (177 C) and containing straight chain 11 and slightly branched chain hydrocarbons comprising contacting said 12 hydrocarbon oil feedstock in the presence of added hydrogen gas at a 13 hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) under dewaxing 14 conditions with a catalyst comprising a crystalline molecular sieve having STI
topology anci a mole ratio of at least about 14 of (1) an oxide of a first 16 tetravalent element to (2) an oxide of a trivalent element, pentavalent element, 17 second tetravalent element which is different from said first tetravalent 18 element or mixture thereof. The molecular sieve may be predominantly in the 19 hydrogen form. The catalyst may contain at least one Group VIII metal.
The catalyst may comprise a combination comprising a first catalyst comprising 21 the molecular sieve and at least one Group VIII metal, and a second catalyst 22 comprising an aluminosilicate zeolite which is more shape selective than the 23 molecular sieve of said first catalyst.

The present invention further provides a process for preparing a lubricating oil 26 which comprises.

28 hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to 29 obtain an effluent comprising a hydrocracked oil; and 31 catalytically dewaxing said effluent comprising hydrocracked oil at a 32 temperature of at least about 400 F (204 C) and at a pressure of from about 33 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge) in the presence of added hydrogen gas with a catalyst comprising a crystalline molecular sieve 2 having STI topology and a mole ratio of at least about 14 of (1) an oxide of a 3 first tetravalent element to (2) an oxide of a trivalent element, pentavalent 4 element. second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve may be 6 predominantly in the hydrogen form. The catalyst may contain at least one 7 Group VIII metal.

9 Also provided is a process for isomerization dewaxing a raffinate comprising contacting said raffinate in the presence of added hydrogen under 11 isomerization dewaxing conditions with a catalyst comprising a crystalline 12 molecular sieve having STI topology and a mole ratio of at least about 14 of 13 (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, 14 pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof, The raffinate may be bright 16 stock, and the molecular sieve may be predominantly in the hydrogen form, 17 The catalyst may contain at least one Group VIII metal.

19 In accordance with the present invention there is provided an improved process for separating gasses using a membrane containing a molecular 21 sieve, the improvement comprising using as the molecular sieve a crystalline 22 molecular sieve having STI topology and having a mole ratio of at least 15 of 23 (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, 24 pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve can have a 26 mole ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from 27 aluminum oxide, gallium oxide, iron oxide: boron oxide: titanium oxide, indium 28 oxide and mixtures thereof. The molecular sieve has, after calcination, the 29 kray diffraction lines of Table II.
31 In accordance with the present invention there is provided a process for 32 producing methylamine or dimethylamine comprising reacting methanol, 33 dimethyl ether or a mixture thereof and ammonia in the gaseous phase in the

-10-1 presence of a catalyst comprising a crystalline molecular sieve having 2 topology and having a mole ratio of 15 .and greater of (1) an oxide of a .first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, 4 second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve can have a mole ratio of 15 6 and greater of (1) silicon oxide to (2) an oxide selected from aluminum oxide, 7 gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and 8 mixtures thereof. The molecular sieve has, after calcination, the X-ray 9 diffraction lines of Table 11.

11 In accordance with this invention, there is provided a process for the reduction

12 of oxides of nitrogen contained in a gas stream wherein said process

13 comprises contacting the gas stream with a crystalline molecular sieve having

14 ST1 topology and having a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, 16 second tetravalent element which is different from said first tetravalent 17 element or mixture thereof. The molecular sieve can have a mole ratio of at 18 least 15 of (1) silicon oxide to (2) an oxide selected from aluminum oxide, 19 gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, The molecular sieve has, after calcination, the X-ray 21 diffraction lines of Table U. The molecular sieve may contain a metal or metal 22 ions (such as cobalt, copper, platinum, iron, chromium, manganese, 23 zinc, lanthanum, palladium, rhodium or mixtures thereof) Capable of catalyzing 24 the reduction of the oxides of nitrogen, and the process may be conducted in the presence of a stoichiornetric excess of oxygen. In a preferred 26 embodiment, the gas stream is the exhaust stream .of an internal combustion 27 engine, 29 This invention generally relates to a process for treating an engine exhaust stream and in particular to a process for minimizing emissions during the cold 31 start operation of an engine. Accordingly, the present invention provides a 32 process for treating a cold-start engine exhaust gas stream containing 33 hydrocarbons and other pollutants consisting of flowing .said engine exhaust 1 gas stream over a molecular sieve bed which preferentially adsorbs the 2 hydrocarbons over water to provide a first exhaust stream, and flowing the 3 first exhaust gas stream over a catalyst to convert any residual hydrocarbons 4 and other pollutants contained in the first exhaust gas stream to innocuous products and provide a treated exhaust stream and discharging the treated 6 exhaust stream into the atmosphere, the molecular sieve bed characterized in 7 that it comprises a crystalline molecular sieve having STI topology and having 8 a mole ratio of at least 15 of (1) an oxide of a first tetravalent element to (2) an 9 oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof. The 11 molecular sieve can have a mole ratio of at least 15 of (1) silicon oxide to (2) 12 an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron 13 oxide, titanium oxide, indium oxide and mixtures thereof. The molecular sieve 14 has the STI framework topology. It has, after calcination, the X-ray diffraction lines of Table II.

17 The present invention further provides such a process wherein the engine is 18 an internal combustion engine, including automobile engines, which can be 19 fueled by a hydrocarbonaceous fuel.
21 Also provided by the present invention is such a process wherein the 22 molecular sieve has deposited on it a metal selected from the group 23 consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof.

The present invention relates to a process for the production of light olefins 26 comprising olefins having from 2 to 4 carbon atoms per molecule from an 27 oxygenate feedstock. The process comprises passing the oxygenate 28 feedstock to an oxygenate conversion zone containing a molecular sieve 29 catalyst to produce a light olefin stream.
31 Thus, in accordance with the present invention there is provided a process for 32 the production of light olefins from a feedstock comprising an oxygenate or 33 mixture of oxygenates, the process comprising reacting the feedstock at , 1 effective conditions over a catalyst comprising a crystalline molecular sieve 2 having STI topology and having a mole ratio of at least 15 of (1) an oxide of a 3 first tetravalent element to (2) an oxide of a trivalent element, pentavalent 4 element, second tetravalent element which is different from said first tetravalent element or mixture thereof. The molecular sieve can have a mole 6 ratio of at least 15 of (1) silicon oxide to (2) an oxide selected from aluminum 7 oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and 8 mixtures thereof. The molecular sieve has, after calcination, the X-ray 9 diffraction lines of Table II.
11 In another aspect, there is provided a crystalline molecular sieve molecular 12 sieve having STI topology and having a mole ratio of at least 15 of (1) a 13 silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron 14 oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.
16 In another aspect, there is provided a crystalline molecular sieve having STI
17 topology and having a composition comprising, as synthesized and in the 18 anhydrous state, in terms of mole ratios, the following:

Si02 / XcOd at least 15 21 M21/SiO2 0 ¨ 0.03 22 Q / Si02 0.02 ¨ 0.08 23 F / S102 0.01 ¨ 0.04 wherein X is aluminum, gallium, iron, boron, titanium, indium and mixtures 26 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 27 metal cation, alkaline earth metal cation or mixtures thereof; n is the valence 28 of M, Q is a tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication and F is 29 fluoride.
31 In yet another aspect, there is provided a method of preparing a crystalline 32 molecular sieve having STI topology, said method comprising contacting 1 under crystallization conditions (1) a source of silicon oxide, (2) a source of 2 aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium 3 oxide and mixtures thereof, (3) fluoride ions and (4) a structure directing agent 4 comprising a tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication.
6 In another aspect, there is provided a process for converting hydrocarbons 7 comprising contacting a hydrocarbonaceous feed at hydrocarbon converting 8 conditions with a catalyst comprising a crystalline molecular sieve having STI
9 topology and a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium 11 oxide, indium oxide and mixtures thereof.

13 In another aspect, there is provided a process for converting oxygenated 14 hydrocarbons comprising contacting said oxygenated hydrocarbon under conditions to produce liquid products with a catalyst comprising a molecular 16 sieve having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide 17 selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium 18 oxide, indium oxide and mixtures thereof and having, after calcination, the 19 X-ray diffraction lines of Table II:
TABLE II
21 Calcined SSZ-75 2 Theta(a) d-spacing (Angstroms) Relative Integrated Intensity (%) 9.6 9.17 10.0 8.88 VS
10.1 8.79 13.1 6.73 19.4 4.58 21.0 4.22 22.4 3.97 M-S
24.2 V 3.68 28.4 3.14 30.2 2.96 23 (a) + 0.1 .

-13a-1 In another aspect, there is provided a catalyst composition for promoting 2 polymerization of 1-olefins, said composition comprising 4 (A) a crystalline molecular sieve having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron 6 oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof and 7 having, after calcination, the X-ray diffraction lines of Table II:

9 Calcined SSZ-75 2 Theta(a) d-sgacing (Angstroms) Relative Integrated Intensity (%) 9.6 9.17 10.0 8.88 VS
10.1 8.79 13.1 6.73 19.4 4.58 21.0 4.22 22.4 3.97 M-S
24.2 3.68 28.4 3.14 30.2 2.96 11 (a) + 0.1; and 12 (B) an organotitanium or organochromium compound.

14 In another aspect, there is provided a dewaxing process comprising contacting a hydrocarbon feedstock under dewaxing conditions with a catalyst 16 comprising a crystalline molecular sieve having STI topology and a mole ratio 17 of at least about 14 of (1) a silicon oxide to (2) an oxide selected from 18 aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium 19 oxide and mixtures thereof.
21 In another aspect, there is provided a process for improving the viscosity 22 index of a dewaxed product of waxy hydrocarbon feeds comprising contacting 23 a waxy hydrocarbon feed under isomerization dewaxing conditions with a 24 catalyst comprising a crystalline molecular sieve having STI topology and a -13b-1 mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected 2 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, 3 indium oxide and mixtures thereof.

In another aspect, there is provided a process for producing a C20+ lube oil 6 from a C20+ olefin feed comprising isomerizing said olefin feed under 7 isomerization conditions over a catalyst comprising a crystalline molecular 8 sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon 9 oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

12 In another aspect, there is provided a process for catalytically dewaxing a 13 hydrocarbon oil feedstock boiling above about 350 F (177 C) and containing 14 straight chain and branched chain hydrocarbons comprising contacting said hydrocarbon oil feedstock in the presence of added hydrogen gas at a 16 hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) under dewaxing 17 conditions with a catalyst comprising a crystalline molecular sieve having STI
18 topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an 19 oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

22 In another aspect, there is provided a process for preparing a lubricating oil 23 which comprises: hydrocracking in a hydrocracking zone a hydrocarbon-24 aceous feedstock to obtain an effluent comprising a hydrocracked oil;
and catalytically dewaxing said effluent comprising hydrocracked oil at a 26 temperature of at least about 400 F (204 C) and at a pressure of from about 27 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge) in the presence of 28 added hydrogen gas with a catalyst comprising a crystalline molecular sieve 29 having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron 31 oxide, titanium oxide, indium oxide and mixtures thereof.

-13c-, 1 In another aspect, there is provided a process for isomerization dewaxing a 2 raffinate comprising contacting said raffinate in the presence of added 3 hydrogen under isomerization dewaxing conditions with a catalyst comprising 4 a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, 6 gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and 7 mixtures thereof.

9 In another aspect, there is provided, in a process for separating gasses using a membrane containing a molecular sieve, the improvement comprising using 11 as the molecular sieve a crystalline molecular sieve having STI topology and 12 having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected 13 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, 14 indium oxide and mixtures thereof.
16 In another aspect, there is provided a process for producing methylamine or 17 dimethylamine comprising reacting methanol, dimethyl ether or a mixture 18 thereof and ammonia in the gaseous phase in the presence of a catalyst 19 comprising a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from 21 aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium 22 oxide and mixtures thereof.

24 In another aspect, there is provided a process for the reduction of oxides of nitrogen contained in a gas stream wherein said process comprises 26 contacting the gas stream with a crystalline molecular sieve having STI
27 topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an 28 oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, 29 titanium oxide, indium oxide and mixtures thereof.
31 In another aspect, there is provided a process for treating a cold-start engine 32 exhaust gas stream containing hydrocarbons and other pollutants consisting -13d-, 1 of flowing said engine exhaust gas stream over a molecular sieve bed which 2 preferentially adsorbs the hydrocarbons over water to provide a first exhaust 3 stream, and flowing the first exhaust gas stream over a catalyst to convert any 4 residual hydrocarbons and other pollutants contained in the first exhaust gas stream to innocuous products and provide a treated exhaust stream and 6 discharging the treated exhaust stream into the atmosphere, the molecular 7 sieve bed comprising a crystalline molecular sieve having STI topology and 8 having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected 9 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

12 In another aspect, there is provided a process for the production of light 13 olefins from a feedstock comprising an oxygenate or mixture of oxygenates, 14 the process comprising reacting the feedstock at effective conditions over a catalyst comprising a crystalline molecular sieve having STI topology and 16 having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected 17 from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, 18 indium oxide and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

22 The present invention comprises a molecular sieve designated herein 23 "molecular sieve SSZ-75" or simply "SSZ-75".

In preparing SSZ-75, a tetramethylene-1,4-bis-(N-methylpyrrolidinium) 26 dication is used as a structure directing agent ("SDA"), also known as a 27 crystallization template. The SDA useful for making SSZ-75 has the following 28 structure:

-13e-X- N¨(CH2)4¨N X-3 Tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication The SDA dication is associated with anions (k) which may be any anion that 6 is not detrimental to the formation of the SSZ-75. Representative anions 7 include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide, 8 acetate, sulfate, tetrafluoroborate, carboxylate, and the like. Hydroxide is the 9 most preferred anion. The structure directing agent (SDA) may be used to provide hydroxide ion. Thus, it is beneficial to ion exchange, for example, a 11 halide to hydroxide ion.

-13f-, , 1 The tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication SDA can be 2 prepared by a method similar to that described in U.S. Patent No.
5,166,111, 3 issued November 24, 1992 to Zones et al., which discloses a method for 4 preparing a bis(1,4-diazoniabicyclo[2.2.2]alpha, omega alkane compound, or U.S. Patent No. 5,268,161, issued December 7, 1993, which discloses a 6 method for preparing 1,3,3,8,8-pentamethy1-3-azoniabicyclo[3.2.1]octane 7 cation.

9 In general, SSZ-75 is prepared by contacting (1) an active source(s) of silicon oxide, and (2) an active source(s) of aluminum oxide, gallium oxide, iron 11 oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof with the 12 tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication SDA in the presence 13 of fluoride ion.

SSZ-75 is prepared from a reaction mixture comprising, in terms of mole 16 ratios, the following:

19 Reaction Mixture 21 S102 / Xa0b at least 15 (i.e., 15- infinity) 22 OH- / Si02 0.20 ¨ 0.80 23 Q / Si02 0.20 ¨ 0.80 24 M2/n / Si02 0 ¨ 0.04 H20 / Si02 2-10 26 HF / Si02 0.20 ¨ 0.80 28 where X is aluminum, gallium, iron, boron, titanium, indium and mixtures 29 thereof, a is 1 or 2, b is 2 when a is 1 (i.e., W is tetravalent); b is 3 when a is 2 (i.e., W is trivalent), M is an alkali metal cation, alkaline earth metal cation or 31 mixtures thereof; n is the valence of M (i.e., 1 or 2); Q is a tetramethylene-1,4-32 bis-(N-methylpyrrolidinium) dication and F is fluoride.

1 As noted above, the S102/ X,Ob mole ratio in the reaction mixture is 15.
2 This means that the Si02/ Xa0bmole ratio can be infinity, i,e.> there is no X,Ob 3 in the reaction mixture. This results in a version of SSZ-75 that is essentially 4 all silica. As used herein, "essentially all silicon oxide" or "essentially all-silica" means that the molecular sieve's crystal structure is comprised of only 6 silicon oxide or is comprised of silicon oxide and only trace amounts of other 7 oxides, such as aluminum oxide, which may be introduced as impurities in the 8 source of silicon oxide.

In practice, SSZ-75 is prepared by a process comprising:

12 (a) preparing an aqueous solution containing (1) a source(s) of 13 silicon oxide, (2) a source(s) of aluminum oxide, 14 gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, (3) a source of fluoride ion and (4) a 16 tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication 17 having an anionic counterion which is not detrimental to the 18 formation of SSZ-75;
19 (b) maintaining the aqueous solution under conditions sufficient to form crystals of SSZ-75; and 21 (c) recovering the crystals of SSZ-75, 23 The reaction mixture is maintained at an elevated temperature until the 24 crystals of the SSZ-75 are formed. The hydrothermal crystallization is usually conducted under autogenous pressure, at a temperature between 100 C and 26 200 C. preferably between 135')C and 180 C. The crystallization period is 27 typically greater than 1 day and preferably from about 3 days to about 28 20 days. The molecular sieve may be prepared using mild stirring or 29 agitation.
31 During the hydrothermal crystallization step, the SSZ-75 crystals can be 32 allowed to nucleate spontaneously from the reaction mixture. The use of 33 SSZ-75 crystals as seed material can be advantageous in decreasing the time

-15-1 necessary for complete crystallization to occur. In addition, seeding can lead 2 to an 'increased purity of the product obtained by promoting the nucleation.
3 and/or formation of SSZ---75 over any undesired phases. When used as 4 seeds, SSZ-75 crystals are added in an amount between 0,1 and 10% of the weight of the first tetravalent element oxide, e.g. silica, used in the reaction 6 mixture.

8 Once the molecular sieve crystals have formed, the solid product is separated 9 from the reaction mixture by standard mechanical separation techniques such as filtration, The crystals are water-washed and then dried, e.g., at 90 C to 11 150 C for from 8 to 24 hours, to obtain the as-synthesized SSZ-75 crystals.
12 The drying step can be performed at atmospheric pressure or under vacuum.
13.
14 SSZ-75 as prepared has the X-ray diffraction lines of Table I below..
$SZ-75 has a composition., as synthesized prior to removal of the SDA from the

16 SSZ-75) and in the anhydrous state, comprising the following (in terms of

17 mole ratios);

18

19 Si021Xõ.00 at least 15 (..e,, 15- infinity) M211 I Si02 0 - 0.03 21 Si02 0.02 ¨ 0,08 22 F Si02 0.01 ¨O04 24 wherein X is aluminum, gallium, iron, boron, titanium, indium and mixtures thereof, c is 1 or 2; d is 2 when g is 1 (i,e., \AI is tetravalent) or d is 3 or 5 when 26 c is 2 d is 3 when W is trivalent or 5 when W is pentavalent), M
is an .27 &kali metal cation, alkaline earth metal cation or mixtures thereof; n is the 28 valence of M (L.e., 1 or 2); 0 is a tetramethylene-1 29 pyrrolidinium) dication and F is fluoride,.
31 SSZ-75 (whether in the as synthesized or calcined version) has a Si021X...:00 32 mole ratio of at least 15 15 infinity), for example 20 - infinity or 40 33 infinity.

2 SSZ-75 has the 511 framework topology. It is characterized by its X-ray 3 diffraction pattern. SSZ-75, as-syntheSized, has a crystalline structure whose 4 X-ray powder diffraction pattern exhibits the characteristic lines shown in Table!.

As-Synthesized SSZ-75 2 Theta d-spacing (Angstroms) Reiattve. IntqgTated Intensity ( ,70 10.04 8.80 _____________________________________________ VS
1717 5.16 19.44 ____________________________ 4.56 t-........... 21.13 4.20 W-M
22.30 ----------------------------- 3.97 VS
22.49 ---------------------------- 3,95 24.19 ____________________________ 3.68 ........... 26.61 .335 28,49 ___________________________ 3.13 3020 _____________________________ 2,96 ii 12 + O. 1 13 The X-ray patterns provided are based on a relative intensity scale in 14 which the strongest iirsie in the X-ray pattern is assigned a value of 100:
W(weak) is less than 20; M(medium) is between 20 and 40; S(strong) 16 is between 40 and 60; VS(very strong) is greater than 60.

18 Table IA below shows the X-ray powder diffraction lines for as-synthesized 19 SSZ-75 including actual relative intensities, -17, 2 As-Synthesized SSZ-75 2 Theta d-spacing (Angstroms) Relative Integrated I ntensity_aa ...................................................
9.84 8.98 7 10.04 8.80 100 13,24 668 7 14.19 6.24 4 17.17 5.16 13 19.44 4.56 47

20,01 4.43 2 20.17 4.40 7

21,13 4.20 21 2.2.36 3.97 84

22.49 3.95 38 24.19 3.68 12 26.13 3,41 7 26.61 3.35 17 28.49 3.13 18 29.31 3.04 10 30,20 2.96 30 30.30 2.95 7 31.94 2.80 9 32.12 2.78 1 32.61 2.74 3 33.13 2.70 4 33,59 2,67 6 34.86 2.57 7 35.13 2.55 5 35.75 2.51 6 36,55 2.46 2 36.69 2,45 1 37.19 2.42 ..................................... 1 7 After calcination, the X-ray powder diffraction pattern for SSZ-75 exhibits the 8 characteristic lines shown in Table II below.

3 Calcined SSZ-75 2 Theta d-spacing (Anostromsi .Relative Integrated 9.64 9,17 9.95 ............... 8.88 --- 1 .......... vs ..
------------- 10,06 8.79 ___________________________________ 13.14 6,73 19.38 4.58 21,03 4.22 22.35 3.97 MS
L ----------- 24,19 3,68 28.37 3.14 _____________ 30,16 2.96 8 Table 11A below shows the X-ray powder diffraction lines for calcined SSZ-9 including actual relative intensities., 12 Calcined SSZ-75 13 ___ Ziheta d-wacing (Angstroms). Relative integrated =Intensity 9.64 9.17 8 9.95 8.88 100 10.06 8.79 24 13.14 6.73 7 14.17 6.25 2 17,13 5.17 2 17.25 5.14 =,) 19.38 I 4,58 15 20,23 4.39 1 21.03 4.22 10 22.35 3,97 39 22,54 3,94 24.19 3.68 25.24 3.53 6 26.08 3.41 2 26.48 3.36 ------------------- 6 28.37 3.14 7 29.25 3.05 3 30.16 2.96 13 30.32 2.95 2 32.18 2.78 1 33.02 2.71 33.54 2.67 =2 34.57 2.59 1 34.94 2.57 2 35.09 2.56 1 35.68 2.51 2 36.58 2.45 1 , 37.07 2.42 4 The X-ray powder diffraction patterns were determined by standard techniques. The radiation was CuKalpha radiation. The peak heights and the 6 positions, as a function of 20 where 0 is the Bragg angle, were read from the 7 relative intensities of the peaks, and d, the interplanar spacing in Angstroms 8 corresponding to the recorded lines, can be calculated.

The variation in the scattering angle (two theta) measurements, due to 11 instrument error and to differences between individual samples, is estimated 12 at 0.1 degrees.

14 Representative peaks from the X-ray diffraction pattern of as-synthesized 16 SSZ-75 are shown in Table I. Calcination can result in changes in the 16 intensities of the peaks as compared to patterns of the "as-synthesized' 17 material, as well as minor shifts in the diffraction pattern.

19 Crystalline SSZ-75 can be used as-synthesized, but preferably will be thermally treated (calcined). Usually, it is desirable to remove the alkali metal 21 cation (if any) by ion exchange and replace it with hydrogen, ammonium, or 22 any desired metal ion. Calcined SSZ-75 has an n-hexane adsorption capacity

23 of about 0.15 cc/g,

24 , , 1 SSZ-75 can be formed into a wide variety of physical shapes. Generally 2 speaking, the molecular sieve can be in the form of a powder, a granule, or a 3 molded product, such as extrudate having a particle size sufficient to pass 4 through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion with an 6 organic binder, the SSZ-75 can be extruded before drying, or, dried or 7 partially dried and then extruded.

9 SSZ-75 can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes. Such matrix 11 materials include active and inactive materials and synthetic or naturally 12 occurring zeolites as well as inorganic materials such as clays, silica and 13 metal oxides. Examples of such materials and the manner in which they can 14 be used are disclosed in U.S. Patent No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Patent No. 5,316,753, issued May 31, 1994 to 16 Nakagawa.

18 Hydrocarbon Conversion Processes SSZ-75 molecular sieves are useful in hydrocarbon conversion reactions.
21 Hydrocarbon conversion reactions are chemical and catalytic processes in 22 which carbon containing compounds are changed to different carbon 23 containing compounds. Examples of hydrocarbon conversion reactions in 24 which SSZ-75 is expected to be useful include hydrocracking, dewaxing, catalytic cracking and olefin and aromatics formation reactions. The catalysts 26 are also expected to be useful in other petroleum refining and hydrocarbon 27 conversion reactions such as isomerizing n-paraffins and naphthenes, 28 polymerizing and oligomerizing olefinic or acetylenic compounds such as 29 isobutylene and butene-1, polymerization of 1-olefins (e.g., ethylene), reforming, isomerizing polyalkyl substituted aromatics (e.g., m-xylene), and 31 disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, 32 xylenes and higher methylbenzenes and oxidation reactions. Also included are rearrangement reactions to make various naphthalene derivatives, and 2 -forming higher molecular weight hydrocarbons from 'lower :molecular weight 3 hydrocarbons (e,g., methane upgrading).
fi The SSZ-75 catalysts may have high selectivity, and under hydrocarbon 6 conversion conditions can provide a high percentage of desired products 7. relative to total products, = 9 For high catalytic activity, the SSZ-75 .molecular sieve should be predomina.ntly in its hydrogen ion form, Generally, the molecular sieve is 11 converted to its hydrogen form by =ammonium exchange followed by 12 calcination. If the molecular sieve is synthesized with a high enough ratio of 13 SDA cation to sodium ion, calcination alone may be sufficient. It is preferred 14 that, after calcination, at. least 80% of the cation sites are occupied by hydrogen ions and/or rare earth ions. As used herein,. "predominantly in the 16 hydrogen form" means that, after calcination, at least 80% of the cation siteF., 17 are occupied by hydrogen ions and/or rare earth ions.

SSZ-75 molecular sieves can be used in processing hydrocarbonaceous feedstocks. Hydrocarbonaceous feedstocks contain carbon compounds and 21 can be from many different sources, such as virgin petroleum fractions, 22 recycle petroleum fractions, shale oil, liquefied coal, tar sand oil, synthetic 23 paraffins from. NAO, recycled plastic feedstocks, Other feeds include.
24 synthetic feeds, such as those derived from a Fischer Tropsch process, including an oxygenate-contang Fischer Tropsch process boiling 'below 26 about 3710-(700F), In general, the feed can be any carbon containing 27 feedstock susceptible to zeolitic catalytic reactions. Depending on the type of 28 processing the hydrocarborlaceous feed is to undergo, the feed can contain 29 metal or be free of metals, it can also have high or low nitrogen or sulfur 80. i mp urities. It can be appreciated, however, that 41. general processing will be 31 more efficient (and the catalyst more active) the lower the metal, nitrogen, and 32 . sulfur content of the feedstock, 3.3 -22:-.

1 The conversion of hydrocarbonaceous feeds can take place in any convenient 2 mode, for example, in fluidized bed, moving bed, or fixed bed reactors 3 depending on the types of process desired. The formulation of the catalyst 4 particles will vary depending on the conversion process and method of operation.

7 Other reactions which can be performed using the catalyst of this invention 8 containing a metal, e.g., . a Group VIII metal such platinum, include 9 hydrogenation-dehydrogenation reactions, denitrogenation and desulfurization reactions.

12 The .following table indicates typical reaction conditions which may be 13 employed when using catalysts comprising SS.Z-75 in the hydrocarbon 14 conversion reactions of this invention. Preferred conditions are indicated in parentheses, Process Temp.,cC Pressure LIASV
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.-- 0.5-50 (atm.-5 atm.) Oligornerization 232-649 0.1-50 atniT2'' 0.2-50' 10-2324 0.05-205 (27-204)4 (0.1-10) Paraffins to 100-700 0-1000 psig 005 aromatics Condensation of 260-538 0.5-1000 psig, 0.5-505-alcohols 0.00345-6.89 Mpa gauge lsomerization 93-538 50-1000 psig, 1-10 (204-315) 0.345-6.89 Mpa (1-4) gauge Xylene 260-593 0.5-50 atm-.7¨ 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 Liquid phase reaction 7 Other reaction conditions and parameters are provided below.

2. Hydrocrackinq 4 Using a catalyst which comprises SSZ-75, preferably predominantly in the hydrogen form, and a hydrogenation promoter, heavy petroleum residual 6 feedstocks, cyclic stocks and other hydrocrackate charge stocks can be 7 hydrocracked using the process conditions and catalyst components 8 disclosed in the aforementioned U.S. Patent No. 4,910,006 and U.S, Patent 9 No. 5,316,753.
11 The hydrocracking catalysts contain an effective amount of at least one 12 hydrogenation component of the type commonly employed in hydrocracking 13 catalysts. The hydrogenation component is generally selected from the group 14 of hydrogenation catalysts consisting of one or more metals of Group VIB
and Group VIII. including the salts, complexes and solutions containing such. The 16 hydrogenation catalyst is preferably selected from the group of metals, salts 17 and complexes thereof of the group consisting of at least one of platinum, 18 palladium, rhodium, iridium, ruthenium and mixtures thereof or the group 19 consisting of at least one of nickel, molybdenum. cobalt, tungsten, titanium, chromium and mixtures thereof. Reference to the catalytically active metal or 21 metals is intended to encompass such metal or metals in the elemental state 22 or in some form such as an oxide, sulfide, halide, carboxylate and the like.
23 The hydrogenation catalyst is present in an effective amount to provide the 24 hydrogenation function of the hydrocracking catalyst, and preferably in the range of from 0.05 to 25% by weight.

27 Dewaxinq 29 For dewaxing processes, the catalyst comprises a molecular sieve having STI
tpology and having a mole ratio of at least 15 of (1) an oxide of a first 31 tetravalent element to (2) an oxide of a trivalent element, pentavalent element.
32 second tetravalent element which is different from said first tetravalent 33 element or mixture thereof. Thus, the molecular sieve may be SSZ-75 or 1 TNU-10, preferably predominantly in the hydrogen form. The catalyst can be 2 used to dewax hydrocarbonaceous feeds by selectively removing straight 3 chain paraffins. Typically, the viscosity index of the dewaxed product is 4 improved (compared to the waxy feed) when the waxy feed is contacted with SSZ-75 or TNU-10 under isomerization dewaxing conditions.

7 The catalytic dewaxing conditions are dependent in large measure on the 8 feed used and upon the desired pour point. Hydrogen is preferably present in 9 the reaction zone during the catalytic dewaxing process. The hydrogen to feed ratio is typically between about 500 and about 30,000 SCF/bbl (standard 11 cubic feet per barrel) (0.089 to 5.34 SCM/liter (standard cubic meters/liter)), 12 preferably about 1000 to about 20,000 SCF/bbl (0.178 to 3.56 SCM/liter).
13 Generally, hydrogen will be separated from the product and recycled to the 14 reaction zone. Typical feedstocks include light gas oil, heavy gas oils and reduced crudes boiling above about 350T (177CC).

17 A typical dewaxing process is the catalytic dewaxing of a hydrocarbon oil 18 feedstock boiling above about 350 F (177T) and containing straight chain 19 and slightly branched chain hydrocarbons by contacting the hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pressure of 21 about 15-3000 psi (0.103-20.7 lvlpa) with a catalyst comprising SSZ-75 and at 22 least one Group VIII metal, 24 The SSZ-75 or TNU-10 hydrociewaxing catalyst may optionally contain a hydrogenation component of the type commonly employed in dewaxing 26 catalysts. See the aforementioned U.S. Patent No, 4,910,006 and U.S.
27 Patent No, 5,316,753 for examples of these hydrogenation components.

29 The hydrogenation component is present in an effective amount to provide an effective hydrodewaxing and hydroisomerization catalyst preferably in the 31 range of from about 0.05 to 5% by weight. The catalyst may be run in such a 32 mode to increase isomerization dewaxing at the expense of cracking 33 reactions.

1 The feed may be hydrocracked, followed by dewaxing. This type of two stage 2 process and typical hydrocracking conditions are described in U.S. Patent 3 No. 4,921,594, issued May 1, 1990 to Miller.

SSZ-75 or TNU-10 may also be utilized as a combination of catalysts. That 6 is, the catalyst comprises a combination comprising molecular sieve SSZ-7 or TNU-10 and at least one Group VIII metal, and a second catalyst 8 comprising an aluminosilicate zeolite which is more shape selective than 9 molecular sieve SSZ-75 or TNU-10. The combination may be comprised of layers. The use of layered catalysts is disclosed in U.S. Patent 11 No. 5,149,421, issued September 22, 1992 to Miller. The layering may also 12 include a bed of SSZ-75 or TNU=10 layered with a non-zeolitic component 13 designed for either hydrocracking or hydrofinishing.

SSZ-75 or TNU-10 may also be used to dewax raffinates, including bright 16 stock, under conditions such as those disclosed in U. S. Patent 17 No. 4,181,598, issued January 1, 1980 to Gillespie et al.

19 It is often desirable to use mild hydrogenation (sometimes referred to as hydrofinishing) to produce more stable dewaxed products. The hydrofinishing 21 step can be performed either before or after the dewaxing step, and 22 preferably after. Hydrofinishing is typically conducted at temperatures ranging 23 from about 190 C to about 340 C at pressures from about 400 psig to about 24 3000 psig (2.76 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 26 (0.071 to 0.27 SCM/liter). The hydrogenation catalyst employed must be 27 active enough not only to hydrogenate the olefins, diolefins and color bodies 28 which may be present, but also to reduce the aromatic content. Suitable 29 hydrogenation catalyst are disclosed in U. S. Patent No. 4,921,594, issued May 1, 1990 to Miller. The hydrofinishing step is beneficial in preparing an 31 acceptably stable product (e.g., a lubricating oil) since dewaxed products 1 prepared from hydrocracked stocks tend to be unstable to air and light and 2 tend to form sludges spontaneously and quickly.

4 Lube oil may be prepared using SSZ-75 or TNU-10. For example, a C20+ lube oil may be made by isomerizing a C20+ olefin feed over a catalyst comprising 6 SSZ-75 or TNU-10 in the hydrogen form and at least one Group VIII metal.
7 Alternatively, the lubricating oil may be made by hydrocracking in a 8 hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent 9 comprising a hydrocracked oil, and catalytically dewaxing the effluent at a temperature of at least about 400 F (204 C) and at a pressure of from about 11 15 psig to about 3000 psig (0.103-20.7 Mpa gauge) in the presence of added 12 hydrogen gas with a catalyst comprising SSZ-75 or TNU-10F in the hydrogen 13 form and at least one Group VIII metal.

Aromatics Formation 17 SSZ-75 can be used to convert light straight run naphthas and similar 18 mixtures to highly aromatic mixtures. Thus, normal and slightly branched 19 chained hydrocarbons, preferably having a boiling range above about 40 C
and less than about 200 C, can be converted to products having a substantial 21 higher octane aromatics content by contacting the hydrocarbon feed with a 22 catalyst comprising SSZ-75. It is also possible to convert heavier feeds into 23 BTX or naphthalene derivatives of value using a catalyst comprising SSZ-75.

The conversion catalyst preferably contains a Group VIII metal compound to 26 have sufficient activity for commercial use. By Group VIII metal compound as 27 used herein is meant the metal itself or a compound thereof. The Group VIII
28 noble metals and their compounds, platinum, palladium, and iridium, or 29 combinations thereof can be used. Rhenium or tin or a mixture thereof may also be used in conjunction with the Group VIII metal compound and 1 preferably a noble metal compound. The most preferred metal is platinum.
2 The amount of Group VIII metal present in the conversion catalyst should be 3 within the normal range of use in reforming catalysts, from about 0.05 to 4 . 2,0 weight percent, preferably 0.2 to 0,8 weight percent, 6 It is critical to the selective production of aromatics in useful quantities that the 7 Conversion catalyst be substantially free of acidity, for example, by 8 neutralizing the molecular sieve with a basic metal, e.g.., alkali metal, 9 compound, 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 11 No, 5,316,753 for a description of such methods.

13 The preferred alkali metals are sodium, potassium, rubidium and cesium.
The 14 molecular sieve itself can be substantially free of acidity only at very high silica:alumina mole ratios.

17 Catajytic Cracking 19 Hydrocarbon cracking stocks can be catalytically cracked in the absence of hydrogen using SSZ-75, preferably predominantly in the hydrogen form.

22 When SSZ-75 is used as a Catalytic cracking catalyst in the absence of 23 hydrogen, the catalyst may be employed in conjunction with traditional 24 cracking catalysts, e.g.., any aluminosilicate heretofore employed, as a component in cracking catalysts. Typically, these are large pore, crystalline .26 aiuminosiiica:tes. Examples Of these traditional cracking catalysts are 27 disclosed in the aforementioned 'U.S. Patent No. 4,910,006 and U.S.
Patent 28 No 5,316õ753. When a traditional cracking catalyst (IC) component is 29 employed, the relative weight ratio of the TC to the SSZ-75 is generally between about 1:10 and about 500:1, desirably between about 1.10 and 31 about 200:1, preferably between about 1:2 and about 50:1, and most 32 preferably is between about 1:1 and about 20:1. The novel molecular sieve "29-1 and/or the traditional cracking component may be further ion exchanged with 2 rare earth ions to modify selectivity, 4 The cracking catalysts are typically employed with an inorganic oxide matrix component. See the aforementioned U.S. Patent No, 4910,006 and U.S.
6 Patent No. 1.6,753 for examples of such matrix components.

8 lsomerization The present catalyst is highly active and highly selective for isomerizing C
to 11 C7 hydrocarbons, The activity means that the catalyst can operate at 12 relatively low temperature which thermodynamically favors highly branched 13 paraffins, Consequently, the catalyst can produce a high octane product.
14 The high selectivity means that a relatively high liquid yield can be achieved when the catalyst is run at a high octane, 16.
17 The present process comprises contacting the isomerization catalyst, i.e., a 18 catalyst comprising SSZ-75 in the hydrogen form, with a hydrocarbon feed 19 under isomerization conditions.. The feed is preferably a light straight run fraction, boiling within the range of 30'F to 250'f: (-1 C to 121 C) and 21 preferably from 60'F to 200T (16 C to 93 C). Preferably, the hydrocarbon 22 feed for the process comprises a substantial amount of C4 to C7 normal and 23 slightly branched low octane hydrocarbons, more preferably C5 and C6 24 hydrocarbons,.
26 it is preferable to carry out the isomerization reaction in the presence of 27 hydrogen. Preferably, hydrogen is added to give a hydrogen to hydrocarbon 28 ratio (H2/1-1C) of between 0.5 and 10 H2/1-1C, more preferably between 1 and 29 8 H2/HC. See the aforementioned U.S. Patent No. 4,910,006 and U.S.
Patent 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 feed 33 preferably contains less than 10 pprn, more preferably less than 1 ppm, and 1 most preferably less than 0.1 ppm sulfur. in the case of a feed which is not=
2 already low in sulfur, acceptable levels can be reached by hydrogenating the a feed in a presaturation zone with a hydrogenating catalyst which is resistant .to 4 sulfur poisoning. See the aforementioned U.S. Patent No, 4,910,006 and U.S, Patent No. 5,316,753 for a further discussion of this hydrodesulfurization 6 process.

8 It is preferable to limit the nitrogen level and the water content of the feed:
9. Catalysts and processes which are suitable for these purposes are known to those skilled in the art.

12 After a period of operation, the catalyst can become deactivated by sulfur or 13 coke. See the aforementioned :U.S. Patent No. 4,910,006 and U.S. Patent.
14 No. 5,316,753 for a further discussion of methods of removing this sulfur and coke, and of regenerating the catalyst.

17 The conversion catalyst preferably contains a Group VIII metal compound to 18 have sufficient activity for commercial use, By Group VIII metal compound as 19 used herein is meant the metal itself or a compound thereof. The Group VIII
noble metals and their compounds, platinum, palladium, and iridium, or 21 combinations thereof can be used. Rhenium and tin may also be used in 22 conjunction with the noble metal. The most preferred metal is platinum.
The 23 amount of Group VIII metal present in the conversion catalyst should be within 24 the normal range of use in i=somerizin=d catalysts, from about 0.05 to 2,0 weight percent, preferably 0.2 to 0.8 weight percent.

27 All:sylation and Transalkylation 29 .SSZ-75 can be used in a process for the alkylation or transalkylation of an aromatic hydrocarbbn. The process comprises contacting the aromatic 31 hydrocarbon with a C2 to Cis olefin alkylating agent or a polyalkyl aromatic.
32 hydrocarbon transalkylating agent, under at least partial liquid phase 33 conditions, and in the presence of a catalyst comprising SSZ-75.
-31.=

2 SSZ-75 can also be used for removing benzene from gasoline by alkylating 3 the benzene as described above and removing the alkylated product from the 4 gasoline, 6 For high catalytic activity,. the SSZ-75 molecular sieve should be 7 predominantly in its hydrogen ion form. It is preferred that, after calcination, at.
8 least 80% of the cation sites are occupied by hydrogen ions andiorrare earth 9 ions.
11 Examples of suitable aromatic hydrocarbon feedstocks which may be 12 alkylated or trensalkylated by the process of the invention include aromatic 13 compounds such as benzene, toluene and xylene. The preferred aromatic 14 hydrocarbon is benzene. There may be occasions where naphthalene or naphthalene derivatives such as dimethylnaphthalene may be desirable, 16 Mixtures of aromatic hydrocarbons may also be employed, 18 Suitable olefins for the alkylation of the aromatic hydrocarbon are those 19 containing 2 to 20, preferably 2 to 4, carbon atoms, such as ethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, or mixtures thereof.
21 There may be instances where pentenes are desirable, The preferred olefins 22 are ethylene and propylene. Longer chain alpha olefins may be used as well.

24 When transalkylation is desired, the transalkylating agent is a polyalkyl aromatic: hydrocarbon containing two or more alkyl groups that each may 26 have from 2 to about 4 carbon atoms. For example, suitable polyalkyl 27 aromatic hydrocarbons include di-, tri-.and tetra-alkyl aromatic hydrocarbons, 28 such as diethylbenzene, triethylbenzene, diethylmethylbenzene 29 (diethyltoluene), di-isopropylbenzene, di-lsopropyltoluene, dibutylben,zene, and the like. Preferred polyalkyl aromatic hydrocarbons are the dialkyl 31 benzenes, A particularly preferred polyalkyl aromatic hydrocarbon is 32 di-isopropylbenzene.
33:
-.3..2.-, , 1 When alkylation is the process conducted, reaction conditions are as follows.
2 The aromatic hydrocarbon feed should be present in stoichiometric excess.
It 3 is preferred that molar ratio of aromatics to olefins be greater than four-to-one 4 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 to 232 C).
6 The reaction pressure should be sufficient to maintain at least a partial liquid 7 phase in order to retard catalyst fouling. This is typically 50 psig to 1000 psig 8 (0.345 to 6.89 Mpa gauge) depending on the feedstock and reaction 9 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 (WHSV), 11 in terms of grams (pounds) of aromatic hydrocarbon and olefin per gram 12 (pound) of catalyst per hour, is generally within the range of about 0.5 to 50.

14 When transalkylation is the process conducted, the molar ratio of aromatic hydrocarbon will generally range from about 1:1 to 25:1, and preferably from 16 about 2:1 to 20:1. The reaction temperature may range from about 100 F
to 17 600 F (38 C to 315 C), but it is preferably about 250 F to 450 F (121 C
to 18 232 C). The reaction pressure should be sufficient to maintain at least a 19 partial liquid phase, typically in the range of about 50 psig to 1000 psig (0.345 to 6.89 Mpa gauge), preferably 300 psig to 600 psig (2.07 to 4.14 Mpa 21 gauge). The weight hourly space velocity will range from about 0.1 to 10.
22 U.S. Patent No. 5,082,990 issued on January 21, 1992 to Hsieh, et al.
23 describes such processes.

Conversion of Paraffins to Aromatics 27 SSZ-75 can be used to convert light gas C2-C6 paraffins to higher molecular 28 weight hydrocarbons including aromatic compounds. Preferably, the 29 molecular sieve 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 31 Periodic Table. Preferably, the metal is gallium, niobium, indium or zinc in the 32 range of from about 0.05 to 5% by weight.

1 Isomerization of Olefins 3 SSZ-75 can be used to isomerize olefins. The feed stream is a hydrocarbon 4 stream containing at least one C4.6 olefin, preferably a CA-6 normal olefin, more preferably normal butane. Normal butene as used in this specification means 6 all forms of normal butene, e.g., 1-butene, cis-2-butene, and trans-2-butene.
7 Typically, hydrocarbons other than normal butane or other C4.6 normal olefins 8 will be present in the feed stream. These other hydrocarbons may include, 9 e.g., alkanes, other olefins, aromatics, hydrogen, and inert gases.
11 The feed stream typically may be the effluent from a fluid catalytic cracking 12 unit or a methyl-tert-butyl ether unit. A fluid catalytic cracking unit effluent 13 typically contains about 40-60 weight percent normal butenes. A
14 methyl-tert-butyl ether unit effluent typically contains 40-100 weight percent normal butane The feed stream preferably contains at least about 40 weight 16 percent normal butane, more preferably at least about 65 weight percent 17 normal butane. The terms iso-olefin and methyl branched iso-olefin may be 18 used interchangeably in this specification.

The process is carried out under isomerization conditions. The hydrocarbon 21 feed is contacted in a vapor phase with a catalyst comprising the SSZ-75.
22 The process may be carried out generally at a temperature from about 625 F
23 to about 950 F (329-510 C), for butenes, preferably from about 700 F to 24 about 900 F (371-482 C), and about 350 F to about 650 F (177-343 C) for pentenes and hexenes. The pressure ranges from subatmospheric to about 26 200 psig (1.38 Mpa gauge), preferably from about 15 psig to about 200 psig 27 (0.103 to 1.38 Mpa gauge), and more preferably from about 1 psig to about 28 150 psig (0.00689 to 1.03 Mpa gauge).

The liquid hourly space velocity during contacting is generally from about 0.1 31 to about 50 II( based on the hydrocarbon feed, preferably from about 0.1 to 32 about 20 hr", more preferably from about 0.2 to about 10 hr-', most preferably 33 from about 1 to about 5 WI. A hydrogen/hydrocarbon molar ratio is 1 maintained from about 0 to about 30 or higher. The hydrogen can be added 2 directly to the feed stream or directly to the isOmerization zone. The reaction 3 is preferably -substantially free of water, typically less than about two weight 4 percent based on the feed. The process can be carried out in a packed bed reactor, a fixed bed, fluidized bed reactor, or a moving bed reactor, The 'bed.
of the catalyst can move upward or downward. The mole percent conversion 7 of, e.g., normal butane to iso-butane is at least 10, preferably at least

25, and 8 more preferably at least 35.

XvIene Isomer zation 12 -SSZ-75 may also be useful in a process for isomerizino one or more xylerie=
13 isomers in a C aromatic feed to obtain orthom meta-, and para-xylene in a 14 ratio approaching the equilibrium value: In particular, xylene isomerization is used in conjunction with a separate process to manufacture para-xyleneõ For 16 example, a portion of the para-xylene in a mixed Ca aromatics stream may be 17 recovered by crystallization and centrifugation. The mother liquor from the 18 crystallizer is then reacted under .xylene isomeriz.ation conditions to restore 19 ortho-, meta- and para-xylenes to a near equilibrium ratio. At the same time part of the ethylbenzene in the mother liquor is converted to xylenes or to 21 products which are easily separated by filtration. The isomerate is blended 22 with fresh feed and the combined stream is distilled to remove heavy and light 23 by-products. The resultant Ca-aromatics stream is then sent to the crystallizer 24 to repeat the cycle.
25 Optionally, isomerization in the vapor phase is: conducted in the presence of 27 3.0 to 30,0 moles of hydrogen per mole of alkylbenzene ethylbenzene)., 28 If hydrogen is used, the catalyst should comprise about 0.1 to 2.0 wt.%
of a 29 hydrogenation/dehydrogenation component selected from Group VIII (of the Periodic Table) metal component; especially platinum or nickel. By Group VIII
31 metal component is meant the metals and their compounds such as. oxides 32 and sulfides, -35,.

, 1 Optionally, the isomerization feed may contain 10 to 90 wt. of a diluent such 2 as toluene, trimethylbenzene, naphthenes or paraffins.

4 Oliqomerization 6 It is expected that SSZ-75 can also be used to oligomerize straight and 7 branched chain olefins having from about 2 to 21 and preferably 2-5 carbon 8 atoms. The oligomers which are the products of the process are medium to 9 heavy olefins which are useful for both fuels, i.e., gasoline or a gasoline blending stock and chemicals.

12 The oligomerization process comprises contacting the olefin feedstock in the 13 gaseous or liquid phase with a catalyst comprising SSZ-75.

The molecular sieve can have the original cations associated therewith 16 replaced by a wide variety of other cations according to techniques well 17 known in the art. Typical cations would include hydrogen, ammonium and 18 metal cations including mixtures of the same. Of the replacing metallic 19 cations, particular preference is given to cations of metals such as rare earth metals, manganese, calcium, as well as metals of Group II of the Periodic 21 Table, e.g., zinc, and Group VIII of the Periodic Table, e.g., nickel.
One of the 22 prime requisites is that the molecular sieve have a fairly low aromatization 23 activity, i.e., in which the amount of aromatics produced is not more than 24 about 20% by weight. This is accomplished by using a molecular sieve with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably

26 from about 0.1 to about 100, as measured by its ability to crack n-hexane.

27

28 Alpha values are defined by a standard test known in the art, e.g., as shown

29 in U.S. Patent No. 3,960,978 issued on June 1, 1976 to Givens et al. If required, such molecular sieves may be obtained by steaming, by use in a 31 conversion process or by any other method which may occur to one skilled in 32 this art.

2 Condensation of Alcohols 4 SSZ-75 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 or 11 impregnated to contain ammonium or a metal cation complement, preferably 12 in the range of from about 0.05 to 5% by weight. The metal cations that may 13 be present include any of the metals of the Groups I through VIII of the 14 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, nor 16 should the exchange be such as to eliminate all acidity. There may be other 17 processes involving treatment of oxygenated substrates where a basic 18 catalyst is desired.

Methane Upgrading 22 Higher molecular weight hydrocarbons can be formed from lower molecular 23 weight hydrocarbons by contacting the lower molecular weight hydrocarbon 24 with a catalyst comprising SSZ-75 and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular 26 weight hydrocarbon. Examples of such reactions include the conversion of 27 methane to 02+ hydrocarbons such as ethylene or benzene or both.
28 Examples of useful metals and metal compounds include lanthanide and or 29 actinide metals or metal compounds.
31 These reactions, the metals or metal compounds employed and the 32 conditions under which they can be run are disclosed in U.S. Patents No.

, 1 4,734,537, issued March 29, 1988 to Devries et al.; 4,939,311, issued July 3, 2 1990 to Washecheck et al.; 4,962,261, issued October 9, 1990 to Abrevaya et 3 al.; 5,095,161, issued March 10,1992 to Abrevaya et al.; 5,105,044, issued 4 April 14, 1992 to Han et al.; 5,105,046, issued April 14, 1992 to Washecheck;
5,238,898, issued August 24, 1993 to Han et at.; 5,321,185, issued June 14, 6 1994 to van der Vaart; and 5,336,825, issued August 9, 1994 to Choudhary et 7 at.

9 Polymerization of 1-Olefins 11 The molecular sieve of the present invention may be used in a catalyst for the 12 polymerization of 1-olefins, e.g., the polymerization of ethylene. To form the 13 olefin polymerization catalyst, the molecular sieve as hereinbefore described 14 is reacted with a particular type of organometallic compound.
Organometallic compounds useful in forming the polymerization catalyst include trivalent and 16 tetravalent organotitanium and organochromium compounds having alkyl 17 moieties and, optionally, halo moieties. In the context of the present invention 18 the term "alkyl" includes both straight and branched chain alkyl, cycloalkyl and 19 alkaryl groups such as benzyl.
21 Examples of trivalent and tetravalent organochromium and organotitanium 22 compounds are disclosed in U. S. Patent No. 4,376,722, issued March 15, 23 1983 to Chester et at., U. S. Patent No. 4,377,497, issued March 22, 1983 to 24 Chester et at., U. S. Patent No. 4,446,243, issued May 1, 1984 to Chester et al., and U. S. Patent No. 4,526,942, issued July 2, 1985 to Chester et at.

27 Examples of the organometallic compounds used to form the polymerization 28 catalyst include, but are not limited to, compounds corresponding to the 29 general formula:
31 MYnXm-n 1 wherein M is a metal selected from titanium and chromium; Y is alkyl.; X
is 2 halogen (e,g,. Ci or Br); n is 1-4: and M is greater than or equal to n and is 3 3. 01 4.

Examples of organotitanium and organochromium compounds encompassed 6 by such a formula include compounds of the formula CrY4, 7 CrY2X, CrY2k.; CrYX2õ CrYX3, TiY4, TiY3, T1Y3X, TiY2X, TiY2X2, TIYX2, TiY.X3.4 wherein X can be CI or Br and V can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, text-butyl, peaty!, isopentyi, neopentyl, hexyl, isohexyl, neohe.xyl, 2-ethybutyl, octyl, 2-ethylhexyl, 2,2-diethylbutyl, 2-isopropyI-3-11 methylbutyl, etc., cyclohexylalkyls such as, for example, .cyclohexylmethyl, 2-12 cyclohexylethyl, 3-cyclyhexylpropyi, 4-cyclohexylbutyl, and the corresponding 13 alkyl-substituted cyclohexyl radicals as, for example, .(4, 14 methylcyclohexyl)methyl, neophyl, ie, beta, beta-dimethyl-phenethyl, benzyl, ethylbenzyl, and p-isopropylbenzyl.. Preferred examples of Y include 16 especially butyl, 18 The arganotitanium and organochromium materials employed in the catalyst 19 can be prepared by techniques well known in the art. See, for example the aforementioned Chester et al, patents.

22 The organotitanium or organochromium compounds can be with the 23 molecular sieve of the present invention, such as by reacting the 24 organometallic compound and the molecular sieve, in order to form the olefin polymerization catalyst. Generally, such a reaction takes place in the same 26 reaction medium used to prepare the organometallic compound under 27 conditions which promote formation of such a reaction product. The 28 molecular sieve can simply be added to the reaction mixture after formation of 29 the organometallic compound has been completed. Molecular sieve is added in an amount sufficient to provide from about 0.1 to 10 parts by weight, 31 preferably from about 0,5 to 5 parts by weight, of organometallic compound in 32 the reaction medium per 100 parts by weight of molecular sieve, 2 Temperature of the reaction medium during reaction of organometallic 3 compound with molecular sieve is also maintained at a level which is low 4 enough to ensure the stability of the organometallic reactant. Thus, temperatures in the range of from about -1504 C. to 504 C., preferably from 6 about -804 C. to 0* C. can be usefully employed. Reaction times of from 7 about 0.01 to 10 hours, more preferably from about 0.1 to 1 hour; can be 8 employed in reacting the organotitanium or organochromium compound with 9 the molecular sieve.
11 Upon completion of the reaction, the catalyst material so formed may be 12 recovered and dried by evaporating the reaction medium solvent under a 13 nitrogen atmosphere. Alternatively, olefin polymerization reactions can be 14 conducted in this same solvent based reaction medium used to form the catalyst.

17 The polymerization catalyst can be used to catalyze polymerization of 1-18 olefins. The polymers produced using the catalysts of this invention are 19 normally solid polymers of at least one mono-l-olefin containing from 2 to 8 carbon atoms per molecule. These polymers are normally solid 21 homopolymers of ethylene or copolymers of ethylene with another mono-1-22 olefin containing 3 to 8 carbon atoms per molecule. Exemplary copolymers 23 include those of ethylene/propylene, ethylene/1-butene, ethylene/1-hexane, 24 and ethylene/I-octane and the like. The major portion of such copolymers is derived from ethylene and generally consists of about 80-99, preferably 95-99 26 mole percent of ethylene. These polymers are well suited for extrusion, blow 27 molding, injection molding and the like.

29 The polymerization reaction can be conducted by contacting monomer or monomers. e.g., ethylene, alone or with one or more other olefins, and in the 31 substantial absence of catalyst poisons such as moisture and air, with a 32 catalytic amount of the supported organometallic catalyst at a temperature 33 and at a pressure sufficient to initiate the polymerization reaction. If desired, 1 an inert organic solvent may be used as a diluent and to facilitate materials 2 handling if the polymerization reaction is conducted with the reactants in the 3 liquid phase, e,g, in a particle form (slurry) or solution process. The reaction 4 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 6 an inert gas such as 'nitrogen.

8 The polymerization reaction is carried out at temperatures of from about

30 9 C. or less, up to about 200' C. or more, depending to a great extent on the.
operating pressure, the pressure.. of the olefin monomers., and the particular 11 catalyst being used and its concentration. Naturally, the selected operating 12 temperature is also dependent upon the desired polymer melt index since 13 temperature is definitely a factor in adjusting the molecular weight of the 14 polymer. Preferably, the temperature used is from about 30' C. to about 100' C. in a conventional slurry or "particle forming" process or from 100' C. to 16 150 C. in a "solution forming" process. A temperature of from about 70 C
to 17 110" C. can be employed for fluidized bed processes.

19 The pressure to be used in the polymerization reactions can be any pressure sufficient to initiate the polymerization of the monomer(s) to high molecular 21 weight polymer. The pressure, therefore, can range from subatmospheric 22 pressures, using an inert gas as diluent, to superatrnospheric pressures of up 23 to about 30,000 psig or more, The preferred pressure is from atmospheric (0 24 psig) up to about 1000 psig. As a general rule, a pressure of 20 to 800 psig is most preferred.

27 The selection of an inert organic solvent medium to be employed in the.
28 solution or slurry process embodiments of this invention is not too critical, but 29 the solvent should be inert to the supported organometallic catalyst and olefin polymer produced, and be stable at the reaction temperature used. It is not

31 necessary, however, that the inert organic solvent medium also serve as a

32 solvent for the polymer to be produced. Among the inert organic solvents

33 applicable for such purposes May be mentioned saturated aliphatic 1 hydrocarbons having from about 3 to 12 carbon atoms per molecule such as 2 hexane, heptane, pentane, isooctane, purified kerosene and the like, 3 saturated cycloaliphatic hydrocarbons having from about 5 to 12 carbon 4 atoms per molecule such as cyclohexane, cyclopentane, dimethylcyclopentane and methylcyclohexane and the like and aromatic 6 hydrocarbons having from about 6 to 12 carbon atoms per molecule such as 7 benzene, toluene, xylene, and the like. Particularly preferred solvent media 8 are cyclohexane, pentane, hexane and heptane.

Hydrogen can be introduced into the polymerization reaction zone in order to 11 decrease the molecular weight of the polymers produced (i.e., give a much 12 higher Melt Index, MI). Partial pressure of hydrogen when hydrogen is used 13 can be within the range of 5 to 100 psig, preferably 25 to 75 psig. The melt 14 indices of the polymers produced in accordance with the instant invention can range from about 0.1 to about 70 or even higher.

17 More detailed description of suitable polymerization conditions including 18 examples of particle form, solution and fluidized bed polymerization 19 arrangements are found in Karapinka; U.S. Pat. No. 3,709,853; Issued Jan. 9, 1973 and Karol et al; U.S. Pat. No. 4,086,408; Issued Apr. 25, 1978.

22 Hydrocienation 24 SSZ-75 can be used in a catalyst to catalyze hydrogenation of a hydrocarbon feed containing unsaturated hydrocarbons. The unsaturated hydrocarbons 26 can comprise olefins, dienes, polyenes, aromatic compounds and the like.

28 Hydrogenation is accomplished by contacting the hydrocarbon feed 29 containing unsaturated hydrocarbons with hydrogen in the presence of a catalyst comprising SSZ-75. The catalyst can also contain one or more 31 metals of Group VIB and Group VIII, including salts, complexes and solutions 32 thereof. Reference to these catalytically active metals is intended to 33 encompass such metals or metals in the elemental state or in some form such

34 as an oxide, sulfide, halide, carboxylate and the like. Examples of such , 1 metals include metals, salts or complexes wherein the metal is selected from 2 the group consisting of platinum, palladium, rhodium, iridium or combinations 3 thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, 4 titanium, chromium, vanadium, rhenium, manganese and combinations thereof.

7 The hydrogenation component of the catalyst (i.e., the aforementioned metal) 8 is present in an amount effective to provide the hydrogenation function of the 9 catalyst, preferably in the range of from 0.05 to 25% by weight.
11 Hydrogenation conditions, such as temperature, pressure, space velocities, 12 contact time and the like are well known in the art.

14 SSZ-75 is useful as an adsorbent for gas separations (owing to its high pore volume while maintaining diffusion control and hydrophobicity). SSZ-75 can 16 also be used in a catalyst for converting oxygenates (such as methanol) to 17 olefins, and for making small amines. SSZ-75 can be used to reduce oxides 18 of nitrogen in gas streams (such as automotive exhaust). SSZ-75 can also be 19 used as a cold start hydrocarbon trap in combustion engine pollution control systems. SSZ-75 is particularly useful for trapping C3 fragments.

22 The molecular sieve of the present invention can be used to separate gasses.
23 For example, it can be used to separate carbon dioxide from natural gas.
24 Typically, the molecular sieve is used as a component in a membrane that is used to separate the gasses. Examples of such membranes are disclosed in 26 U. S. Patent No. 6,508,860, issued January 21, 2003 to Kulkarni et al.

28 The molecular sieve of the present invention can be used in a catalyst to 29 prepare methylamine or dimethylamine. Dimethylamine is generally prepared in industrial quantities by continuous reaction of methanol (and/or 31 dimethylether) and ammonia in the presence of a silica-alumina catalyst.
The 32 reactants are typically combined in the vapor phase, at temperatures in the 33 range of 300 C to 500 C, and at elevated pressures. Such a process is 34 disclosed in U. S. Patent No. 4,737,592, issued April 12, 1988 to Abrams et , 1 al.

3 The catalyst is used in its acid form. Acid forms of molecular sieves can be 4 prepared by a variety of techniques. Preferably, the molecular sieve used to prepare dimethylamine will be in the hydrogen form, or have an alkali or 6 alkaline earth metal, such as Na, K, Rb, or Cs, ion-exchanged into it.

8 The process of the present invention involves reacting methanol, 9 dimethylether or a mixture thereof and ammonia in amounts sufficient to provide a carbon/nitrogen (C/N) ratio from about 0.2 to about 1.5, preferably 11 about 0.5 to about 1.2. The reaction is conducted at a temperature from 12 about 250 C to about 450 C, preferably about 300 C to about 400 C.
13 Reaction pressures can vary from about 7-7000 kPa (1-1000 psi), preferably 14 about 70-3000 kPa (10-500 psi). A methanol and/or dimethylether space time of about 0.01-80 hours, preferably 0.10-1.5 hours, is typically used. This 16 space time is calculated as the mass of catalyst divided by the mass flow rate 17 of methanol/dimethylether introduced into the reactor.

19 SSZ-75 may be used for the catalytic reduction of the oxides of nitrogen in a gas stream. Typically, the gas stream also contains oxygen, often a 21 stoichiometric excess thereof. Also, the molecular sieve may contain a metal 22 or metal ions within or on it which are capable of catalyzing the reduction of 23 the nitrogen oxides. Examples of such metals or metal ions include cobalt, 24 copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium and mixtures thereof.

27 One example of such a process for the catalytic reduction of oxides of 28 nitrogen in the presence of a zeolite is disclosed in U.S. Patent No.
4,297,328, 29 issued October 27, 1981 to Ritscher et al.

, 1 There, the catalytic process is the combustion of carbon monoxide and 2 hydrocarbons and the catalytic reduction of the oxides of nitrogen contained in 3 a gas stream, such as the exhaust gas from an internal combustion engine.
4 The zeolite used is metal ion-exchanged, doped or loaded sufficiently so as to provide an effective amount of catalytic copper metal or copper ions within or 6 on the zeolite. In addition, the process is conducted in an excess of oxidant, 7 e.g., oxygen.

9 Gaseous waste products resulting from the combustion of hydrocarbonaceous fuels, such as gasoline and fuel oils, comprise carbon monoxide, 11 hydrocarbons and nitrogen oxides as products of combustion or incomplete 12 combustion, and pose a serious health problem with respect to pollution of the 13 atmosphere. While exhaust gases from other carbonaceous fuel-burning 14 sources, such as stationary engines, industrial furnaces, etc., contribute substantially to air pollution, the exhaust gases from automotive engines are a 16 principal source of pollution. Because of these health problem concerns, the 17 Environmental Protection Agency (EPA) has promulgated strict controls on 18 the amounts of carbon monoxide, hydrocarbons and nitrogen oxides which 19 automobiles can emit. The implementation of these controls has resulted in the use of catalytic converters to reduce the amount of pollutants emitted from 21 automobiles.

23 In order to achieve the simultaneous conversion of carbon monoxide, 24 hydrocarbon and nitrogen oxide pollutants, it has become the practice to employ catalysts in conjunction with air-to-fuel ratio control means which 26 functions in response to a feedback signal from an oxygen sensor in the 27 engine exhaust system. Although these three component control catalysts 28 work quite well after they have reached operating temperature of about 29 C., at lower temperatures they are not able to convert substantial amounts of the pollutants. What this means is that when an engine and in particular an 31 automobile engine is started up, the three component control catalyst is not 32 able to convert the hydrocarbons and other pollutants to innocuous 33 compounds.

2 Adsorbent beds have been used to adsorb the hydrocarbons during the cold 3 start portion of the engine. Although the process typically will be used with 4 hydrocarbon fuels, the instant invention can also be used to treat exhaust streams from alcohol fueled engines. The adsorbent bed is typically placed 6 immediately before the catalyst. Thus, the exhaust stream is first flowed 7 through the adsorbent bed and then through the catalyst. The adsorbent bed 8 preferentially adsorbs hydrocarbons over water under the conditions present 9 in the exhaust stream. After a certain amount of time, the adsorbent bed has reached a temperature (typically about 150.-' C.) at which the bed is no longer 11 able to remove hydrocarbons from the exhaust stream. That is, hydrocarbons 12 are actually desorbed from the adsorbent bed instead of being adsorbed.
This 13 regenerates the adsorbent bed so that it can adsorb hydrocarbons during a 14 subsequent cold start.
16 The prior art reveals several references dealing with the use of adsorbent 17 beds to minimize hydrocarbon emissions during a cold start engine operation.
18 One such reference is U.S. Pat. No. 3,699,683 in which an adsorbent bed is 19 placed after both a reducing catalyst and an oxidizing catalyst. The patentees disclose that when the exhaust gas stream is below 200 C. the gas stream is 21 flowed through the reducing catalyst then through the oxidizing catalyst and 22 finally through the adsorbent bed, thereby adsorbing hydrocarbons on the 23 adsorbent bed. When the temperature goes above 200* C. the gas stream 24 which is discharged from the oxidation catalyst is divided into a major and 26 minor portion, the major portion being discharged directly into the atmosphere 26 and the minor portion passing through the adsorbent bed whereby unburned 27 hydrocarbon is desorbed and then flowing the resulting minor portion of this 28 exhaust stream containing the desorbed unburned hydrocarbons into the 29 engine where they are burned.
31 Another reference is U.S. Pat. No. 2,942,932 which teaches a process for 32 oxidizing carbon monoxide and hydrocarbons which are contained in exhaust 33 gas streams. The process disclosed in this patent consists of flowing an exhaust stream which is below 800 F. into an adsorption zone which adsorbs 2 the carbon monoxide and hydrocarbons and then passing the resultant 3 stream from this adsorption zone into an oxidation zone. When the 4 temperature of the exhaust gas stream reaches about 800 F. the exhaust stream is no longer passed through the adsorption zone but is passed directly 6 to the oxidation zone with the addition of excess air.

8 U. S. Patent No. 5,078,979, issued January 7, 1992 to Dunne discloses 9 treating an exhaust gas stream from an engine to prevent cold start emissions using a molecular sieve adsorbent bed. Examples of the molecular sieve 11 include faujasites, clinoptilolites, mordenites, chabazite, silicalite, zeolite Y, 12 ultrastable zeolite Y, and ZSM-5.

14 Canadian Patent No. 1,205,980 discloses a method of reducing exhaust emissions from an alcohol fueled automotive vehicle. This method consists of 16 directing the cool engine startup exhaust gas through a bed of zeolite particles 17 and then over an oxidation catalyst and then the gas is discharged to the 18 atmosphere. As the exhaust gas stream warms up it is continuously passed 19 over the adsorption bed and then over the oxidation bed.
21 As stated this invention generally relates to a process for treating an engine 22 exhaust stream and in particular to a process for minimizing emissions during 23 the cold start operation of an engine. The engine consists of any internal or 24 external combustion engine which generates an exhaust gas stream containing noxious components or pollutants including unburned or thermally 26 degraded hydrocarbons or similar organics. Other noxious components 27 usually present in the exhaust gas include nitrogen oxides and carbon 28 monoxide. The engine may be fueled by a hydrocarbonaceous fuel. As used 29 in this specification and in the appended claims, the term "hydrocarbonaceous fuel" includes hydrocarbons, alcohols and mixtures thereof. Examples of 31 hydrocarbons which can be used to fuel the engine are the mixtures of 32 hydrocarbons which make up gasoline or diesel fuel. The alcohols which may 1 be used to fuel engines include ethanol and methanol. Mixtures of alcohols 2 and mixtures of alcohols and hydrocarbons can also be used. The engine 3 may be a jet engine, gas turbine, internal combustion engine, such as an 4 automobile, truck or bus engine, a diesel engine or the like. The process of this invention is particularly suited for hydrocarbon, alcohol, or hydrocarbon-6 alcohol mixture, internal combustion engine mounted in an automobile. For 7 convenience the description will use hydrocarbon as the fuel to exemplify the 8 invention. The use of hydrocarbon in the subsequent description is not to be 9 construed as limiting the invention to hydrocarbon fueled engines.
11 When the engine is started up, it produces a relatively high concentration of 12 hydrocarbons in the engine exhaust gas stream as well as other pollutants.
13 Pollutants will be used herein to collectively refer to any unburned fuel 14 components and combustion byproducts found in the exhaust stream. For example, when the fuel is a hydrocarbon fuel, hydrocarbons. nitrogen oxides, 16 carbon monoxide and other combustion byproducts will be found in the engine 17 exhaust gas stream. The temperature of this engine exhaust stream is 18 relatively cool, generally below 500* C. and typically in the range of 200 to 19 4004 C. This engine exhaust stream has the above characteristics during the initial period of engine operation, typically for the first 30 to 120 seconds after 21 startup of a cold engine. The engine exhaust stream will typically contain, by 22 volume, about 500 to 1000 ppm hydrocarbons.

24 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 26 stream. Molecular sieve SSZ-56 is described below. The first exhaust stream 27 which is discharged from the molecular sieve bed is now flowed over a 28 catalyst to convert the pollutants contained in the first exhaust stream to 29 innocuous components and provide a treated exhaust stream which is discharged into the atmosphere. It is understood that prior to discharge into 31 the atmosphere, the treated exhaust stream may be flowed through a muffler 32 or other sound reduction apparatus well known in the art.

2 The catalyst which is used to convert the pollutants to innocuous components 3 is usually referred to in the art as a three-component control catalyst because 4 it can simultaneously oxidize any residual hydrocarbons present in the first exhaust stream to carbon dioxide and water, oxidize any residual carbon 6 monoxide to carbon dioxide and reduce any residual nitric oxide to nitrogen 7 and oxygen. In some cases the catalyst may not be required to convert nitric 8 oxide to nitrogen and oxygen, e.g., when an alcohol is used as the fuel.
In this 9 case the catalyst is called an oxidation catalyst. Because of the relatively low temperature of the engine exhaust stream and the first exhaust stream. this 11 catalyst does not function at a very high efficiency, thereby necessitating the 12 molecular sieve bed.

14 When the molecular sieve bed reaches a sufficient temperature, typically about 150-200* C., the pollutants which are adsorbed in the bed begin to 16 desorb and are carried by the first exhaust stream over the catalyst. At this 17 point the catalyst has reached its operating temperature and is therefore 18 capable of fully converting the pollutants to innocuous components.

The adsorbent bed used in the instant invention can be conveniently 21 employed in particulate form or the adsorbent can be deposited onto a solid 22 monolithic carrier. When particulate form is desired, the adsorbent can be 23 formed into shapes such as pills, pellets, granules, rings, spheres, etc. In the 24 employment of a monolithic form, it is usually most convenient to employ the 2$ adsorbent as a thin film or coating deposited on an inert carrier material which 26 provides the structural support for the adsorbent. The inert carrier material 27 can be any refractory material such as ceramic or metallic materials. It is 28 desirable that the carrier material be unreactive with the adsorbent and not be 29 degraded by the gas to which it is exposed. Examples of suitable ceramic materials include sillimanite, petalite, cordierite, mullite, zircon, zircon mullite, 31 spondumene, alumina-titanate, etc. Additionally, metallic materials which are 32 within the scope of this invention include metals and alloys as disclosed in -4q-U.S. Pat, No, 3,.92.0,583 which are oxidation resistant and are otherwise 2 capable of withstanding high temperatures.

4 The carrier material can best be utilized in any rigid unitary configuration which provides a plurality of pores or channels extending in the direction of 6 gas flow. It is preferred that the configuration be a honeycomb configuration.
7 The honeycomb structure can be used advantageously in either unitary form, 8 or as an arrangement of multiple modules. The honeycomb structure is 9 usually oriented such that gas flow is generally in the same direction as the cells or channels of the honeycomb structure. For a more detailed discussion ii of monolithic structures, refer to U.S. Pat, Nos. 3õ785,998. and 3,767,453.

13 The molecular sieve is deposited onto the carrier by any convenient way well 14 known in the art. A preferred method involves preparing a slurry using the Molecular sieve and coating the monolithic honeycomb carrier with the slurry.
16 The slurry can be prepared by means known in the art such as combining the 17 appropriate amount of the molecular sieve and a binder with water. This 18 mixture is then blended .by using means such as sonification, milling, etc. This 19 slurry is used to coat a monolithic honeycomb by dipping the honeycomb into the slurry, removing the excess .slurry by draining or blowing out the channels, 21 and heating to about 100 C. It the desired loading of molecular sieve is not 22 achieved, the above process may be repeated as many times as required to 23 achieve the desired loading.

Instead of depositing the molecular sieve onto a 'monolithic honeycomb 26 structure, one can take the molecular sieve and form it into a monolithic 27 honeycomb structure by means known in the art.

29 The adsorbent may optionally contain one or more catalytic metals dispersed .30 thereon. The metals which can be dispersed on the adsorbent are the noble 31 metals which consist of platinum, palladium, rhodium, ruthenium, and 32 mixtures thereof. The desired noble metal may be deposited onto the 33 adsorbent, which acts as a support, in any suitable manner well kno\,vn in the , , 1 art. One example of a method of dispersing the noble metal onto the 2 adsorbent support involves impregnating the adsorbent support with an 3 aqueous solution of a decomposable compound of the desired noble metal or 4 metals, drying the adsorbent which has the noble metal compound dispersed on it and then calcining in air at a temperature of about 400 to about 500 C.
6 for a time of about 1 to about 4 hours. By decomposable compound is meant 7 a compound which upon heating in air gives the metal or metal oxide.
8 Examples of the decomposable compounds which can be used are set forth 9 in U.S. Pat. No. 4,791,091. Preferred decomposable compounds are chloroplatinic acid, rhodium trichloride, chloropalladic acid, hexachloroiridate 11 (IV) acid and hexachlororuthenate. It is preferable that the noble metal be 12 present in an amount ranging from about 0.01 to about 4 weight percent of the 13 adsorbent support. Specifically, in the case of platinum and palladium the 14 range is 0.1 to 4 weight percent, while in the case of rhodium and ruthenium the range is from about 0.01 to 2 weight percent.

17 These catalytic metals are capable of oxidizing the hydrocarbon and carbon 18 monoxide and reducing the nitric oxide components to innocuous products.
19 Accordingly, the adsorbent bed can act both as an adsorbent and as a catalyst.

22 The catalyst which is used in this invention is selected from any three 23 component control or oxidation catalyst well known in the art. Examples of 24 catalysts are those described in U.S. Pat. Nos. 4,528,279; 4,791,091;
4,760,044; 4,868,148; and 4,868,149. Preferred catalysts well known in the 26 art are those that contain platinum and rhodium and optionally palladium, 27 while oxidation catalysts usually do not contain rhodium. Oxidation catalysts 28 usually contain platinum and/or palladium metal. These catalysts may also 29 contain promoters and stabilizers such as barium, cerium, lanthanum, nickel, and iron. The noble metals promoters and stabilizers are usually deposited on 31 a support such as alumina, silica, titania, zirconia, alumino silicates, and 32 mixtures thereof with alumina 1 being preferred. The catalyst can be conveniently employed in particulate 2 form or the catalytic composite can be deposited on a solid monolithic carrier 3 with a monolithic carrier being preferred. The particulate form and monolithic 4 form of the catalyst are prepared as described for the adsorbent above.
6 The molecular sieve used in the adsorbent bed, SSZ-75, comprises a 7 crystalline molecular sieve having STI topology and having a mole ratio of at 8 least 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a 9 trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element or mixture thereof.

12 The present invention comprises a process for catalytic conversion of a 13 feedstock comprising one or more oxygenates comprising alcohols and ethers 14 to a hydrocarbon product containing fight olefins, i.e., C2, C3 and/or C4 olefins.
The feedstock is contacted with the molecular sieve of the present invention 16 at effective process conditions to produce light olefins.

18 The term "oxygenate" as used herein designates compounds such as 19 alcohols, ethers and mixtures thereof. Examples of oxygenates include, but are not limited to, methanol and dimethyl ether.

22 The process of the present invention may be conducted in the presence of 23 one or more diluents which may be present in the oxygenate feed in an 24 amount between about 1 and about 99 molar percent, based on the total number of moles of all feed and diluent components. Diluents include, but are 26 not limited to, helium, argon, nitrogen, carbon monoxide, carbon dioxide, 27 hydrogen, water, paraffins, hydrocarbons (such as methane and the like), 28 aromatic compounds, or mixtures thereof. U. S. Patents No. 4,861,938 and 29 4,677,242 emphasize the use of a diluent to maintain catalyst selectivity toward the production of light olefins, particularly ethylene.

1 The oxygenate conversion is preferably conducted in the vapor phase such 2 that the oxygenate feedstock is contacted in a vapor phase in a reaction zone 3 with the molecular sieve of this invention at effective process conditions to 4 produce hydrocarbons, i.e.. an effective temperature, pressure, weight hourly space velocity om-isv) and, optionally, an effective amount of diluent. The 6 process is conducted for a period of time sufficient to produce the desired light 7 olefins. In general, the residence time employed to produce the desired 8 product can vary from seconds to a number of hours. It will be readily 9 appreciated that the residence time will be determined to a significant extent by the reaction temperature , the molecular sieve catalyst, the WHSV, the 11 phase (liquid or vapor) and process design characteristics. The oxygenate 12 feedstock flow rate affects olefin production. Increasing the feedstock flow 13 rate increases WHSV and enhances the formation of olefin production relative 14 to paraffin production. However, the enhanced olefin production relative to paraffin production is offset by a diminished conversion of oxygenate to 16 hydrocarbons.

18 The oxygenate conversion process is effectively carried out over a wide range 19 of pressures, including autogenous pressures. At pressures between about 0.01 atmospheres (0.1 kPa) and about 1000 atmospheres (101.3 kPa), the 21 formation of light olefins will be affected although the optimum amount of 22 product will not necessarily be formed at all pressures. The preferred 23 pressure is between about 0.01 atmospheres (0.1 kPa) and about 100 24 atmospheres (10.13 kPa). More preferably, the pressure will range from about 1 to about 10 atmospheres (101.3 kPa to 1.013 Mpa), The pressures 26 referred to herein are exclusive of the diluent, if any, that is present and refer 27 to the partial pressure of the feedstock as it relates to oxygenate compounds.

29 The temperature which may be employed in the oxygenate conversion process may vary over a wide range depending, at least in part, on the 31 molecular sieve catalyst. In general, the process can be conducted at an 32 effective temperature between about 200 C and about 700 C, At the lower 33 end of the temperature range, and thus generally at a lower rate of reaction, 1 the formation of the desired light olefins may become low. At the upper end of 2 the range õ the process may not form an optimum amount of light olefins and 3 catalyst deactivation may be rapid.

The molecular sieve catalyst preferably is incorporated into solid particles in 6 which the catalyst is present in an amount effective to promote the desired, 7 conversion of oxygenates to light olefins. In one aspect, the solid particles 8 comprise a catalytically effective amount of the catalyst and at least one 9 matrix material selected from the group consisting of binder materials, filler materials and mixtures thereof to provide a desired property or properties, 11 e.g,, desired catalyst dilution, mechanical strength and the like to the solid 12 particles. Such matrix materials are often, to some extent, porous in nature 13 and may or may not be effective to promote the desired reaction. Filler and 14 binder materials include, for example, synthetic and naturally occurring substances such as metal oxides, clays, silicas, alumines, 16 silica-magnesias, silica-zirconias, silica-thorias and the like. If matrix 17 materials are included in the catalyst composition, the molecular sieve 18 preferably comprises about 1 to 99%., more preferably about 5 to 90%, and 19 still more preferably about 10 to 80% by weight of the total composition.

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

Example 1 26 Synthesis of Ai-Containing SSZ-75 28: 1..5 mM of tetramethylene-1õ4-bis-(N-methylpyrrolidinium) dication SIM
29 (3 mM OK) was mixed in a Teflon cup (for a Parr 23 ml reactor) with 1,26 grams of tetraethylorthosilicate and the cup was placed in a hood to 31 evaporate (as ethanol is formed from hydrolysis) over several days. When all 32 of the visible liquid was done, the Teflon cup was reweighed and water was 33 added to bring the H20/Si%. mole ratio to about four. Then, 12 mg of Reheiss 34 F2000 (50% Ak0,-) was added and dissolved into the reaction mixture.
This represents a starting synthesis mole ratio of Si02I Al-203 of 100. Lastly, 0.135 gram of 50% HF was added using a plastic pipette. The gel was mixed with a Z plastic .spatula and then the resulting reaction mixture was heated in a closed 3 vessel rotating at 43 RPM at 150 C for 16 days, A crystalline product formed 4 which was recovered and found by X-ray diffraction analysis to be molecular sieve SSZ-75 7 Example 2 8 Synthesis of Al-Containinq SSZ-75 The procedure described in Example 1 was repeated, except that the source 11 of aluminum was 1,2-210 zeolite (a form of clealuminated FAU) and the Siaq 12 Al.Q.3 mole ratio was 70. The reaction formed SSZ75 in 10 days,.

14 Example 3 S.ynthesis of Al-Containing SSZ-75 17 The procedure described in Example 1 was repeated, except that the source 18 of aluminum was Catapai B (a form of pseudoboehmite alumina). The 19 reaction formed SSZ-75 in 10 daysõ
21 Examples 4-7 22 Synthesis of All-Silica S.SZ-75 .23 24 A procedure similar to that of Example 1 was repeated using the reaction mixture (expressed as mole ratios) and conditions shown in the table below..
26 The reactions were run until a Crystalline product was observed by .SEM, and 27 then the product was recovered. The products are also shown in the table.

Ex. SDA/ Si02 Ni-f4F/=Sich SO2 11201 SiCh 'CiFIPIVI Prod. -4 0.50 0.0 0,50 5.0 150/43 SSZ-75 0.40 0.1 0.40 5,0 150/43. SSZ-75 6 030 0.2 0,30 5.0 150/43 Nirr,N
7 0.20 0.3 020 5.0 150/43 Amor.
ZSM-3 Example 8 4 Calcination of SSZ-75 6 The product from Example 1 was calcined in the following manner. A thin bed 7 of material was heated in a flowing bed of air in a muffle furnace from room 8 temperature to 120'C at a rate of 1 C. per minute and held at 120 C for two 9 hours. The temperature is then ramped up to 540'C at the same rate and held at this temperature for three hours, after which it was increased to 594`C
11 and held there for another three hours.

13 Example 9 14 Conversion of Methanol 16 The calcined material of Example 8 (0,10) gram) was pe.ileted and meshed 17 (with recycling) to 20-40 mesh and packed into a 3/8 inch stainless steel 18 reactor. After sufficient purge with nitrogen carrier gas (20 ccimin), the 19 catalyst was heated to 7501: (399'C). A feed of 22.6% methanol in water was introduced into the reactor via syringe pump at a rate of 1,59 cc/hr. A
21 sample of the effluent stream was diverted to an on-line gas chromatograph at 22 ten Minute point of feed introduction. SSZ-75 showed the following behavior:

24, Methanol conversion 100%
No dimethylether detected 26 C2-C4 is about Ark of the product 05+ showed a mixture of olefins and saturates 2 Aromatics were made with ethylbenzene the most abundant single product 3 Trimethylbenzene isomers were observed as the heaviest products At 100 minutes on stream the SSZ-75 was fouling, but still produced the same 6 products (although very few aromatics were observed).

-57.

Claims (83)

WHAT IS CLAIMED IS:

1. A crystalline molecular sieve molecular sieve having STI topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

2. The molecular sieve of claim 1 having, after calcination, the X-ray diffraction lines of Table II:

3. A crystalline molecular sieve having STI topology and having a composition comprising, as synthesized and in the anhydrous state, in terms of mole ratios, the following:
SiO2 / X c O d at least 15 M2/n / SiO2 0 ¨ 0.03 Q / SiO2 0.02 ¨ 0.08 F / SiO2 0.01 ¨ 0.04 wherein X is aluminum, gallium, iron, boron, titanium, indium and 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; Q is a tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication and F is fluoride.

4. A method of preparing a crystalline molecular sieve having STI topology, said method comprising contacting under crystallization conditions (1) a source of silicon oxide, (2) a source of aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof, (3) fluoride ions and (4) a structure directing agent comprising a tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication.

5. The method of claim 4 wherein the crystalline material is prepared from a reaction mixture comprising silicon oxide and, in terms of mole ratios, the following:
SiO2/ X a O b at least 15 OH- / SiO2 0.20 ¨ 0.80 Q / SiO2 0.20 ¨ 0.80 M2/n / SiO2 0 ¨ 0.04 H2O / SiO2 2 - 10 HF / SiO2 0.20 ¨ 0.80 wherein X is aluminum, gallium, iron, boron, titanium, indium and 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 tetramethylene-1,4-bis-(N-methylpyrrolidinium) dication.

6. A process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

7. The process of Claim 6 wherein the molecular sieve is predominantly in the hydrogen form.

8. The process of Claim 6 wherein the molecular sieve is substantially free of acidity.

9. The process of Claim 6 wherein the process is a hydrocracking process comprising contacting the catalyst with a hydrocarbon feedstock under hydrocracking conditions.

10. The process of Claim 6 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.

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

12. The process of Claim 10 wherein the molecular sieve contains a Group VIII metal component.

13. The process of Claim 6 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.

14. The process of Claim 13 wherein the catalyst additionally comprises a large pore crystalline cracking component.

15. The process of Claim 6 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.

16. The process of Claim 15 wherein the molecular sieve is impregnated with at least one Group VIII metal.

17. The process of Claim 15 wherein the catalyst is calcined in a steam/air mixture at an elevated temperature after impregnation of the Group VIII
metal.

18. The process of Claim 16 wherein the Group VIII metal is platinum.

19. The process of Claim 6 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.

20. The process of Claim 19 wherein the olefin is a C2 to C4 olefin.

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

22. The process of Claim 20 wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene and mixtures thereof.

23. The process of Claim 6 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.

24. The process of Claim 23 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.

25. The process of Claim 23 wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, and mixtures thereof.

26. The process of Claim 23 wherein the polyalkyl aromatic hydrocarbon is a dialkylbenzene.

27. The process of Claim 6 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.

28. The process of Claim 6 wherein the process is a process for isomerizing olefins comprising contacting said olefin under conditions which cause isomerization of the olefin with the catalyst.

29. The process of Claim 6 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.

30. The process of Claim 6 wherein the process is a process for oligomerizing olefins comprising contacting an olefin feed under oligomerization conditions with the catalyst.

31. 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 of at least 15 of (1) a 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 II:

32. The process of Claim 31 wherein the oxygenated hydrocarbon is a lower alcohol.

33. The process of Claim 32 wherein the lower alcohol is methanol.

34. The process of Claim 6 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 02+ hydrocarbon synthesis conditions with the catalyst and a metal or metal compound for 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.

35. The process of Claim 34 wherein the metal or metal compound comprises a lanthanide or actinide metal or metal compound.

36. The process of Claim 34 wherein the lower molecular weight hydrocarbon is methane.

37. A catalyst composition for promoting polymerization of 1-olefins, said composition comprising (A) a crystalline molecular sieve having a mole ratio of at least 15 of (1) a 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 II:

(B) an organotitanium or organochromium compound.

38. The process of Claim 6 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 crystalline molecular sieve having STI topology and having a mole ratio of at least 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 (B) an organotitanium or organochromium compound.
under polymerization conditions which include a temperature and pressure suitable for initiating and promoting the polymerization reaction.

39. The process of Claim 38 wherein the 1-olefin monomer is ethylene.

40. The process of Claim 6 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.

41. The process of Claim 40 wherein the catalyst contains metals, salts or complexes wherein the metal is selected from the group consisting of platinum, palladium, rhodium, iridium and combinations thereof, or the group consisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium, rhenium, manganese and combinations thereof.

42. A dewaxing process comprising contacting a hydrocarbon feedstock under dewaxing conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

43. A process for improving the viscosity index of a dewaxed product of waxy hydrocarbon feeds comprising contacting a waxy hydrocarbon feed under isomerization dewaxing conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

44. A process for producing a C20+ lube oil from a C20+ olefin feed comprising isomerizing said olefin feed under isomerization conditions over a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

45. The process of Claim 44 wherein the catalyst further comprises at least one Group VIII metal.

46. A process for catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350°F (177°C) and containing straight chain and 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 a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

47. The process of Claim 46 wherein the catalyst further comprises at least one Group VIII metal.

48. The process of Claim 46 wherein said catalyst comprises a combination comprising a first catalyst comprising the molecular sieve and at least one Group VIII metal, and a second catalyst comprising an aluminosilicate zeolite which is more shape selective than the molecular sieve of said first catalyst.

49. 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 a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

50. The process of Claim 49 wherein the catalyst further comprises at least one Group VIII metal.

51. A process for isomerization dewaxing a raffinate comprising contacting said raffinate in the presence of added hydrogen under isomerization dewaxing conditions with a catalyst comprising a crystalline molecular sieve having STI topology and a mole ratio of at least about 14 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

52. The process of Claim 51 wherein the catalyst further comprises at least one Group VIII metal.

53. The process of Claim 51 wherein the raffinate is bright stock.

54. The process of any one of Claims 43 to 53 wherein the molecular sieve has a mole ratio of at least about 14 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.

55. The process of Claim 9, 13, 15, 19, 23, 42, 43, 44, 46, 49 or 51 wherein the molecular sieve has at least 80% of the cation sites occupied by hydrogen ions and/or rare earth ions.

56. In a process for separating gasses using a membrane containing a molecular sieve, the improvement comprising using as the molecular sieve a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

57. The process of Claim 56 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II:

58. A process for producing methylamine or dimethylamine comprising reacting methanol, dimethyl ether or a mixture thereof and ammonia in the gaseous phase in the presence of a catalyst comprising a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

59. The process of Claim 58 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II:

60. The process of Claim 58 wherein the methanol, dimethylether or mixture thereof and ammonia are present in amounts sufficient to provide a carbon/nitrogen ratio from about 0.2 to about 1.5.

61. The process of Claim 58 conducted at a temperature of from about 250°C to about 450°C.

62. A process for the reduction of oxides of nitrogen contained in a gas stream wherein said process comprises contacting the gas stream with a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

63. The process of Claim 62 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II:

64. The process of Claim 62 conducted in the presence of oxygen.

65. The process of Claim 62 wherein said molecular sieve contains a metal or metal ions for catalyzing the reduction of the oxides of nitrogen.

66. The process of Claim 65 wherein the metal is cobalt, copper, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof.

67. The process of Claim 62 wherein the gas stream is the exhaust stream of an internal combustion engine.

68. The process of Claim 66 wherein the gas stream is the exhaust stream of an internal combustion engine.

69. 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 comprising a crystalline molecular sieve having STI
topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

70. The process of Claim 69 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II:

71. The process of Claim 69 wherein the engine is an internal combustion engine.

72. The process of Claim 71 wherein the internal combustion engine is an automobile engine.

73. The process of Claim 69 wherein the engine is fueled by a hydrocarbonaceous fuel.

74. The process of Claim 69 wherein a metal is deposited on the molecular sieve, the metal is selected from the group consisting of platinum, palladium, rhodium, ruthenium, and mixtures thereof.

75. The process of Claim 74 wherein the metal is platinum.

76. The process of Claim 74 wherein the metal is palladium.

77. The process of Claim 74 wherein the metal is a mixture of platinum and palladium.

78. A process for the production of light olefins from a feedstock comprising an oxygenate or mixture of oxygenates, the process comprising reacting the feedstock at effective conditions over a catalyst comprising a crystalline molecular sieve having STI topology and having a mole ratio of at least 15 of (1) a silicon oxide to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide and mixtures thereof.

79. The process of Claim 78 wherein the molecular sieve has, after calcination, the X-ray diffraction lines of Table II:

80. The process of Claim 78 wherein the light olefins are ethylene, propylene, butylene or mixtures thereof.

81. The process of Claim 80 wherein the light olefin is ethylene.

82. The process of Claim 78 wherein the oxygenate is methanol, dimethyl ether or a mixture thereof.

83. The process of Claim 82 wherein the oxygenate is methanol.