Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
  • C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
  • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
  • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
  • C07D211/12—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with only hydrogen atoms attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
  • C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms

Definitions

• This invention relates to the synthesis of crystalline molecular sieves of the MSE framework-type, such as MCM-68, and to their use in organic conversion processes.
• MCM-68 is a single crystalline phase molecular sieve material which has a unique 3 -dimensional channel structure comprising one 12-membered ring channel system and two 10-membered ring channel systems, in which the channels of each system extend perpendicul ar to the ch annels of the other systems and in which the 12-ring channels are generally straight and the 10-ring channels are tortuous (sinusoidal).
• the framework structure of MCM-68 has been assigned code MSE by the Structure Commission of the International Zeolite Association.
• U.S. Patent No. 6,049,018 exemplifies the use of MCM-68 as a catalyst in aromatic alkylation and transalkylation reactions
• U.S. Patent No. 7,198,711 discloses that MCM-68 shows activity in the catalytic cracking of hydrocarbon feedstocks to produce an enhanced yield of butylenes and isobutene, with the MCM-68 either being the primary cracking catalyst or an additive component in conjunction with a conventional large pore cracking catalyst, such as zeolite Y.
• cations described herein are effecti ve as structure directing agents in the synthesis of MCM-68. Furthermore, it has been found that these cations may be produced conveniently and inexpensively from commercially available raw materials. Moreover, it has been found that MCM-68 can be prepared with these cations without the need to be seeded with MCM-68 seeds.
• the present invention resides in a method of synthesizing a crystalline molecular sieve having a structure of the MS E framework type, preferably MCM-68, the method comprising crystallizing a reaction mixture comprising a source of water, a source of an oxide of a tetravalent element, Y, selected from at least one of silicon, tin, titanium, vanadium and germanium, optionally a source of a trivalent element, X, a source of an alkali or alkaline earth metal, M, and a source of organic cations, Q, having the following general structure: R1 -R3 -R2 ; where Rj and R? are the same or different, and where R-. or R 2 or both Ri and R 2 are an N-alkylpiperidinium group of the formula
• R 3 is an polymethylene group of the formula ( €3 ⁇ 4) radical, where n is from 4 to 6, or where R3 is a cyleoaikylene group having from 5 to 8 carbon atoms, and where R 4 is an aikyl group having 1 to 4 carbon atoms.
• An example of an organic cation, Q is a 3-hydroxy-l-(4-(l- methylpiperidin-l-iura-l- 3.)butyi)quinuclidm-l -ium dication of the formula
• Another example of an organic cation, Q is a 3 -hydroxy- 1 ⁇ (5-(1 - methylpiperidin-l-ium-l- l)pentyl)quinuclidin-l-ium dication of the formula
• Another example of an organic cation, Q is a 1 ,r-(butane-l,4- diyi)bis(l-methylpiperidin-l-ium dication of the formula
• Another example of an organic cation, Q is a l,l'-(pentane-l,5- diyi)bis(l-methyipiperidin-l-ium) dication of the formula
• Another example of an organic cation, Q is a l ,l'-(hexane-l,6- diyl)bis(l-methylpi eridin-l-ium) dication of the formula
• Another example of an organic cation, Q is a l,r-((3av,6a,.y)- octahydropentalene ⁇ 2,5-diyl)bis(l ⁇ methylpiperidin-l ⁇ ium) dication of the formula
• the source of the organic dication may be any salt not detrimental to the formation of the crystalli ne material of t he invention, for ex ample, t he halide or hydroxide salt.
• the molar ratio Q/YQ 2 in the reaction mixture may be in the range of from about 0.01 to about 1.0, such as from about 0.05 to about 0.7.
• the reaction mixture may comprise a source of an oxide of trivalent element, X, selected from at least one of aluminum, boron, gallium, iron, and chromium, such that, for example, the molar ratio Y0 2 /X 2 0 3 in the reaction mixture is in the range of from about 4 to about 200, such as from about 8 to about
• the reaction mixture can have the following molar composition:
• reaction mixture can have the following molar composition:
• the tetravalent element, Y comprises or is silicon
• the trivalent element, X comprises or is aluminum
• said alkali or alkaline earth metal, M is sodium and/or potassium.
• the reaction mixture may optionally comprise seeds of MSE framework type molecular sieve, for example, such that the molar ratio of seeds/YC in said reaction mixture is between about 0.001 and about 0.1.
• Crystal lizing may be conducted at a temperature between about 100°C and about 200°C for up to about 28 days, such as at a temperature between about 145°C and about 175°C for about 24 hours to about 170 hours.
• synthesized forms of a crystalline molecular sieve having the MSE framework type produced by embodiments described herein may contain within its pore structure cations, Q, as defined above.
• Zeolites produced by methods describe herein may be used in an organic conversion process comprising contacting an organic feed with a catalyst comprising a calcined form of the crystalline MSE framework type molecular sieve described herein.
• a catalyst comprising a calcined form of the crystalline MSE framework type molecular sieve described herein.
• R 2 is a quinuclidinium.
• R is an poiymethylene group of the formula (CH 2 ) n , where n is from 4 to 6, and where R 4 is an alkyl group having 1 to 4 carbon atoms.
• these dications include a 3-hydroxy-l-(4-(l-methylpiperidin-l-ium-l- yl)butyl)quinuclidin-l-ium dication of Formula (III) and a 3 -hydroxy- 1 -(5 -(1- methylpiperidin- 1 -ium- 1 -yl)pentyl)quinuclidin- 1 -ium dication of Formula (IV).
• Another compound provided according to aspects of the present invention is a 1,1 '-((3a5,6a$)-octahydropetitalene-2,5-diyl)bis(l -me hylpiper dm- 1 - ium) dication of Formula (VIII).
• Figure 1 is an X-ray diffraction pattern of MCM-68 produced using 1 , 1 , -((3a?;6a?)-octahydropentaiene-2,5-diyi)bis(l -methylpiperidin- 1 -ium) dications as the structure directing agent according to the process of Example 20.
• DETAILED DESCRIPTION OF THE EMBODIMENTS
• Described herein is a method of synthesizing a crystal line molecular sieve having the MSE framework type, such as MCM-68, using Q cations as a structure directing agent . Also described herein is the use of the calcined form of the resultant MSE framework type crystalline molecular sieve as a catalyst in organic conversion reactions, such as in aromatic alkvlation and transalkvlation reactions and in the catalytic cracking of hydrocarbon feedstocks.
• MCM-68 is a synthetic porous single crystalline phase material that has a unique 3 -dimensional channel system comprising one 12-membered ring channel system and two 10-membered ring channel systems, in which the channels of each system extend perpendicular to the channels of the other systems and in which the 12-ring channels are generally straight and the 10-ring channels are generally tortuous (sinusoidal).
• the framework structure of MCM-68 has been assigned code MSE by the Structure Commission of the International Zeolite Association.
• MCM-68 has an X-ray diffraction (XRD) pattern which is distinguished from the patterns of other known as-synthesized and/or thermal ly treated crystalline materials by the lines listed in Table 1 below.
• XRD X-ray diffraction
• the two- dimensional diffraction patterns were integrated and converted to 1 -dimensional plots of 2 ⁇ versus intensity using the Bruker GADDs software.
• the interplanar (d-) spacings were calculated in Angstrom units, and the relative intensities of the lines, I/I 0 , adjusted as percentages of the intensity of the strongest line, I 0 , above background, were derived with the use of Materials Data, Inc., Jade software peak search algorithm.
• the intensities were uncorrected for Lorentz and polarization effects.
• crystallographic changes can include minor changes in unit cell parameters and/or changes in crystal symmetry, without a corresponding change in the structure. These minor effects, including changes in relative intensities, can additionally or alternately occur as a result of differences in cation content, framework composition, nature and degree of pore filling, crystal size and shape, preferred orientation, and thermal and/or hydrothermal history, inter alia.
• MCM-68 has a chemical composition involving the molar relationship: X2O3 :(n)Y0 2 , wherein X is a trivalent element selected from at least one of aluminum, boron, gallium, iron, and chromium, preferably at least including aluminum; Y is a tetravalent element selected from at least one of silicon, tin, titanium, vanadium, and germanium, preferably at least including silicon; and n is at least about 4, such as from about 4 to about 100,000, and can typically be from about 10 to about 1000, for example from about 10 to about 100,
• MCM-68 is generally thermally stable and, in the calcined form, can exhibit a relatively high surface area (e.g., about 660 m g with micropore volume of about 0.21 cc/g) and significant hydrocarbon sorption capacity, e.g. : n -Hexane sorption at -75 torr, -90°C - -10.8 wt%
• MCM-68 In its active, hydrogen form, MCM-68 can exhibit a relatively high acid activity, with an Alpha Value of about 900 to about 2000.
• the Alpha Test is described in U.S. Pat. No. 3,354,078; and in the Journal of Catalysis, 4, 527 (1965); 6, 278 (1966); and 61, 395 (1980), each incorporated herein by reference as to that description.
• the experimental conditions of the test used herein include a constant temperature of ⁇ 538°C and a variable flow rate, as described in detail in the Journal of Catalysis, 61, 395 (1980).
• MCM-68 has previously been synthesized using N,N,N ⁇ N'-tetraethylbicyclo[2.2.2]oct-7-ene-2,3 :5,6- dipyrrolidimum dications as the structure directing agent.
• the high cost of this structure directing agent has significantly hindered the commercial development of MCM-68.
• the present method of synthesizing M CM-68 employs as the structure directing agent cations having the following general structure: R1 -R3-R2 , where R ⁇ and R 2 are the same or different, and where R] or R 2 or both
• R 3 is a polymethyiene group of the formula (CH 2 ) , where n is from 4 to 6, or where R 3 is a cylcoalkylene group having from 5 to 8 carbon atoms, and where R 4 is an alkyl group having 1 to 4 carbon atoms,
• Preferred dications can include 3-hydroxy-l-(4-(l -methylpiperidin- 1- ium- 1 -yl)butyi)quinuclidin- 1 -ium, 3 -hydroxy- 1 -(5 -( 1 -methylpiperidin- 1 -ium- 1 - yl)pentyl)quinuclidin- 1 -ium, 1 , 1 '-(butane- 1 ,4-diyl)bis( 1 -methylpiperidin- 1 -ium), 1 , 1 '-(pentane- 1 ,5-diyi)bis( 1 -methy [piperidm- 1 -ium), 1 , 1 '-(hexane- 1 ,6-diyl)bis( 1 - methylpiperidin- 1 -ium), and 1 , -((3as',6as')-octahydropentaiene-2,5-diy
• [ ⁇ 039] 1 , 1 '-(hexane- 1 ,6-diyl)bis( 1 -methylpiperidin- 1 -ium) dications have been used to direct the synthesis of the zeolite IZM-2 (see, e.g., PCX Publication No. WO 2010/015732 and U.S. Patent Application Publication No. 2010/0272624), and l,r-(pentane-i ,5-diyl)bis(l -methylpiperidin-l -ium) dications have been used to direct the synthesis of the zeolite IZM-3 (see, e.g., PCT Publication No.
• a reaction mixture comprising a source of water, a source of an oxide of a tetravalent element, Y, selected from at least one of silicon, tin, titanium, vanadium, and germanium, a source of an oxide of trivalent element, X, selected from at least one of aluminum, boron, gallium, iron, and chromium, a source of an alkali or alkaline earth metal , M, together with a source of Q cations.
• the composition of the reaction mixture can be controlled so that the molar ratio Q/YO 2 in said reaction mixture is in the range from about 0.01 to about 1 , such as from about 0.05 to about 0.5. More specifically, the reaction mixture can have a composition, in terms of mole ratios of oxides, within the following ranges: eactants Useful Preferred
• the reaction mixture may optionally also comprise seeds of MSE framework type molecular sieve, such as MCM-68, for example, such that the weight ratio of seeds/Y0 2 in the reaction mixture can be between about 0.001 and about 0.3, such as between about 0.01 and about 0.08 or between about 0.01 and about 0.05.
• MCM-68 MSE framework type molecular sieve
• the tetravalent element, Y may comprise or be silicon
• the trivalent element, X may comprise or be aluminum
• the alkali or alkaline earth metal, M may comprise at least one of sodium and potassium.
• the alkali or alkaline earth metal, M comprises potassium
• the molar ratio of Na to the total metal M may be from 0 to about 0.9, for example, from 0 to about 0.5.
• Suitable sources of silicon oxide that can be used to produce the reaction mixture described above can include, but are not limited to, colloidal silica, precipitated silica, potassium silicate, sodium silicate, fumed silica, and the like, as well as combinations thereof.
• Suitable sources of aluminum oxide can include, but are not limited to, hydrated aluminum oxides, such as boehmite, gibbsite, and pseudoboehmite, especially gibbsite, as well as oxygen-containing aluminum salts, such as aluminum nitrate, and the like, as well as combinations thereof
• Suitable sources of alkali metal can include sodium and/or potassium hydroxide.
• Suitable sources of dication structure directing agents can include any salts of these dications which are not detrimental to the formation of the crystal line material MCM-68, for example, halides (e.g., iodides) and/or hydroxides.
• crystallization to produce the desired MCM-68 can be conducted under either static or stirred conditions in a suitable reactor vessel, such as for example, polypropylene jars or stainless steel autoclaves optionally lined with Teflon®, e.g., at a temperature between about 100°C and about 200°C for up to about 28 days, such as at a temperature between about 145 C C and about 175°C for about 24 hours to about 170 hours. Thereafter, the crystals can be separated from the liquid and recovered.
• a suitable reactor vessel such as for example, polypropylene jars or stainless steel autoclaves optionally lined with Teflon®, e.g., at a temperature between about 100°C and about 200°C for up to about 28 days, such as at a temperature between about 145 C C and about 175°C for about 24 hours to about 170 hours.
• the product of the synthesis reaction can advantageously comprise or be a crystalline molecular sieve having the MSE framework type and containing within its pore structure the dication structure directing agent.
• the resultant as- synthesized material can have an X-ray diffraction pattern distinguishable from the patterns of other known as-synthesized or thermal iy treated crystalline materi als, such as having the lines listed in Table 2 below. Table 2.
• As-synthesized crystalline molecular sieve containing dications within its pore structure can normally be activated before use in such a manner as to substantially remove the organic structure directing agent from the molecular si eve, leaving acti ve catalytic sites within the microporous channels of the molecular sieve open for contact with a feedstock.
• the activation process can typically be accomplished by heating the molecular sieve at a temperature from about 200°C to about 800°C for an appropriate period of time in the presence of an oxygen-containing gas.
• the original sodium and/or potassium cations of the as-synthesized material can be replaced in accordance with techniques well known in the art, at least in part, e.g., by ion exchange with other cations, which can include, but are not limited to metal ions, hydrogen ions, hydrogen ion precursors, e.g., ammonium ions, and the like, and mixtures thereof.
• Particularly preferred exchange cations when present, can include those that can tai lor the catalytic activity for certain hydrocarbon conversion reactions (e.g., hydrogen, rare earth metals, and metals of Groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, and 13 of the Periodic Table of the Elements.
• the crystalline molecular sieve produced by the present process can be used to catalyze a wide variety of organic compound conversion processes including many of present commercial/industrial importance.
• Examples of chemical conversion processes effectively catalyzed by the crystalline material of this invention, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, can include those requiring a catalyst with acid activity. Specific examples can include, but are not limited to:
• reaction conditions optionally including one or more of a temperature from about 10°C to about 25Q°C, a pressure from about 0 psig to about 500 psig (about 3.5 MPag), a total weight hourly space velocity (WHSV) from about 0.5 h 3 to about 100 hr "1 , and an aromatic/olefin mole ratio from about 0.1 to about 50;
• reaction conditions optionally including one or more of a temperature from about 10°C to about 25Q°C, a pressure from about 0 psig to about 500 psig (about 3.5 MPag), a total weight hourly space velocity (WHSV) from about 0.5 h 3 to about 100 hr "1 , and an aromatic/olefin mole ratio from about 0.1 to about 50;
• reaction conditions optionally including one or more of a temperature from about 250°C to about 500°C, a pressure from about 0 psig to 500 psig (about 3.5 MPag), a total WHSV from about 0.5 hr 1 to about 50 hr "1 , and an aromatic/olefin mole ratio from about 1 to about 50;
• transaikylation of aromatics in gas or liquid phase, e.g., transaikylation of polyethylbenzenes and/or polyisopropylbenzenes with benzene to produce ethyibenzene and/or cumene respectively, with reaction conditions optionally including one or more of a temperature from about 100°C to about 500°C, a pressure from about 1 psig (about 7 kPag) to about 500 psig (about 3.5 MPag), and a WHSV from about 1 hr "1 to about 10,000 hr " 1 ;
• reaction conditions optionally including one or more of a temperature from about 200°C to about 760°C, a pressure from about 1 atm (about 0 psig) to about 60 atm (about 5.9 MPag), a WHSV from about 0.1 hr "1 to about 20 hr " , and a liydroge iydrocarbon mole ratio from 0 (no added hydrogen) to about 50;
• reaction conditions optionally including one or more of a temperature from about 200°C to about 760°C, a pressure from about 1 atm (about 0 psig) to about 60 aim (about 5.9 MPag), a WHSV from about 0.1 hr " 1 to about 20 hr " 1 , and a hydrogen to hydrocarbon mole ratio from 0 (no added hydrogen) to about 50;
• reaction conditions optionally including one or more of a temperature from about 200°C to about 540°C, a pressure from about 100 kPaa to about 7 MPaa, a WHSV from about 0.1 hr "1 to about 50 hr "1 , and a hydrogen/hydrocarbon mole ratio from 0 (no added hydrogen) to about 10;
• reaction of paraffins with aromatics e.g., to form alkylaromatics and light gases, with reaction conditions optionally including one or more of a temperature from about 260°C to about 375°C, a pressure from about 0 psig to about 1000 psig (about 6.9 MPag), a WHSV from about 0.5 hr 3 to about 10 hr and a hydrogen hydrocarbon mole ratio from 0 (no added hydrogen) to about 10;
• paraffin isomerizatioii to provide branched paraffins with reaction conditions optionally including one or more of a temperature from about 200°C to about 315°C, a pressure from about 100 psig (about 690 kPag) to about 1000 psig (about 6.9 MPag), a WHSV from about 0.5 hr "1 to about 10 hr "1 , and a hydrogen to hydrocarbon mole ratio from about 0.5 to about 10;
• reaction conditions optionally including one or more of a temperature from about -20°C to about 350°C, a pressure from about 0 psig to about 700 psig (about 4.9 MPag), and a total olefin WHSV from about 0.02 hr "1 to about 10 hr "1 ;
• dewaxing of paraffinic feeds with reaction conditions optionally including one or more of a temperature from about 200°C to about 450 C C, a pressure from about 0 psig to about 1000 psig (about 6.9 MPag), a WHSV from about 0.2 hr "1 to about 10 hr "1 , and a hydrogen/hydrocarbon mole ratio from about 0.5 to about 10;
• (k) cracking of hydrocarbons with reaction conditions optionally including one or more of a temperature from about 300°C to about 700°C, a pressure from about 0.1 aim (about 10 kPag) to about 30 aim (about 3 MPag), and a VVBSV from about 0.1 hr "1 to about 20 hr "1 ;
• reaction conditions optionally including one or more of a temperature from about 250°C to about 750°C, an olefin partial pressure from about 30 kPa to about 300 kPa, and a WHSV from about 0.5 hr "1 to about 500 hr " 1 ;
• a hydrocarbon trap e.g. , pre-catalytic converter adsorbent for cold start emissions in motor vehicles.
• MCM-68 may be used as an additive component in conjunction with a conventional cracking catalyst, such as a large pore molecular sieve having a pore size greater than about 7 Angstroms.
• the molecular sieve produced by the present process may be desirable to incorporate with another material resistant to the temperatures and other conditions employed in organic conversion processes.
• Such materials can include active and inactive materials and synthetic or naturally occurring zeolites, as well as inorganic materials such as clays, silica, and/or metal oxides such as alumina. The latter may be naturally occurring and/or in the form of gelatinous precipitates/gels including mixtures of silica and metal oxides.
• Use of a material in conjunction with the molecular sieve produced by the present process i.e., combined therewith and/or present during synthesis of the new crystal), which is active, can tend to change the conversion capability and/or selectivity of the catalyst in certain organic conversion processes.
• Inactive materials suitably tend to serve merely as diluents, e.g. , to control the amount of conversion in a given process so that products can be obtained economically and orderly, for instance without employing too many other means for controlling the rate of reaction.
• inventive materials may be incorporated into naturally occurring clays, e.g. , bentonite and/or kaolin, to improve the crush strength of the catalyst under commercial operating conditions.
• Said materials i.e. , clays, oxides, etc.
• Naturally occurring clays that can be composited with the molecular sieve produced by the present process can include, but are not limited to, the montmoriilonite and kaolin families, which include the subbentonites and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays and/or others in which the main mineral constituent can be halloysite, kaolmite, dickite, nacrite, and/or anauxite. Such clays can be used in the raw state as originally mined and/or initially subjected to calcination, acid treatment, and/or chemical modification.
• Binders useful for compositing with the molecular sieve produced by the present process can additionally or alternately include inorganic oxides, such as silica, zirconia, titania, magnesia, beryliia, alumina, and mixtures thereof.
• the molecular sieve produced by the present process can be composited with a porous matrix material such as s lica-alumina, silica-magnesia, siliea-zirconia, sifica-thoria, silica-beryllia, silica-titania, and/or ternary compositions such as silica-aiumina-thoria, silica-alumina-zirconia silica- alumina-magnesia, and silica-magnesia-zirconia.
• a porous matrix material such as s lica-alumina, silica-magnesia, siliea-zirconia, sifica-thoria, silica-beryllia, silica-titania, and/or ternary compositions such as silica-aiumina-thoria, silica-alumina-zirconia silica- alumina-magnesia, and silic
• the relative proportions of finely divided crystalline molecular sieve material and inorganic oxide matrix vary widely, with the crystal content ranging from about 1% to about 90% by weight and more usual ly, particularly when the composite is prepared in the form of beads or e trudates, ranging from about 2% to about 80% by weight of the composite.
• the present invention can include one or more of the following embodiments.
• Embodiment 1 A method of synthesizing a crystalline molecular sieve having an MSE framework type, the method comprising crystallizing a reaction mixture comprising a source of water, a source of an oxide of a tetravalent element, Y, selected from at least one of silicon, tin, titanium, vanadium, and germanium, optionally a source of a trivalent element, X, a source of an alkali or alkaline earth metal, M, and a source of organic cations, Q, having the following general structure: R -R3-R2 . , where i and R 2 are the same or different, and where i or R 2 or both Ri and R 2 are an N-alkylpiperidinium group of the formula
• R-. or R 2 or both R 3 and R 2 are a quinuclidinium group of the formula
• R 3 is a polymethyiene group of the formula (CH 2 ) n , where n is from 4 to 6, or where R3 is a cylcoalkylene group having from 5 to 8 carbon atoms, and where R 4 is an alkyl group having 1 to 4 carbon atoms, for example a methyl group,
• Embodiment 2 The method of embodiment 1, wherein i and R 2 are both an N-alkylpiperidinium group of the formula
• Embodiment 3 The method of embodiment 1, wherein R.j is an N ⁇ alkylpiperidmium group of the formula
• n 4 or 5.
• Embodiment 5 The method of any one of the previous embodiments, wherein said reaction mixture comprises a source of an oxide of trivalent element, X, selected from at least one of aluminum, boron, gal lium, iron and chromium.
• X an oxide of trivalent element
• Embodiment 6 The method of embodiment 5, wherein a molar ratio YO2 X2O3 n sa reaction mixture is in a range from about 4 to about 200, for example from about 8 to about 120.
• Embodiment 7 The method of embodiment 5 or embodiment 6, wherein the reaction mixture has the fol lowing molar composition:
• Embodiment 8 The method of any one of embodiments 5-7, wherein the reaction mixture has the following molar composition:
• Embodiment 9 The method of any one of the previous embodiments, wherein said tetravalent element, Y, is silicon and said trivalent element, X, is aluminum.
• Embodiment 10 The method of any one of the previous embodiments, wherem said alkali or alkaline earth metal, M, is potassium.
• Embodiment 1 1 .
• Embodiment 12 The method of any one of the previous embodiments, wherein the crystallizing is conducted at a temperature between about 100°C and about 200°C for up to about 28 days, for example between about 145°C and about 175°C for between about 24 hours and about 170 hours.
• Embodiment 13 The method of any one of the previous embodiments, wherem Q is a 3-hydroxy-l-(4-(l-methylpiperidin-l-ium-l-yl)butyl)quinuclidm-l- ium dication of the formula
• metbylpiperidm-l-ium metbylpiperidm-l-ium
• R ? is a quinuclidinium group of the formula
• R ⁇ is a polymethylene group of the formula ( €3 ⁇ 4) « > where n is from 4 to 6, and where R4 is an alkyl group having 1 to 4 carbon atoms.
• Embodiment 16 A dication of embodiment 15, which is a 3-hydroxy- 1 -(4-( 1 -methyipiperidin- 1 -ium- 1 -y l)butyl)quinuciidin- 1 -ium dication of Formula (III) or a 3-hydroxy ⁇ l ⁇ (5-(l -methyipiperidin- 1 -ium-1 -yl )pentyl)quinuclidin-l -ium dication of Formula (IV).
• Embodiment 17 A l,r-((3as,6a5)-octahydiOpentaiene-2,5-diyi)bis(l- methylpiperidm- 1 -ium) dication.
• dimethylformamide (-500 mL) was added slowly to a solution of 1 ,4- dibromobutane (-269.9 g) in anhydrous dimethyl form amide (-250 mL) over the course of about 24 hours under a nitrogen atmosphere with rapid stirring. Stirring of the solution was continued for a further -48 hours.
• the reaction mixture was then passed through a D-frit (-10-20 microns) to separate any solid l,l '-(butane- l,4-diyl)bis(l -methylpiperidin-l -ium) bromide impurity.
• Example 7 Synthesis of l, ⁇ (bota!ie-l,4-diyI) is(l-iBethyfplperidlii-l-mm)
• triacetoxyborohydride (-21.64 g) was added and the mixture was stirred at room temperature for about one day.
• Aqueous sodium hydroxide (-25 g, -25 wt%) was then added and the solution extracted with petroleum ether (3 x -100 mL). The organic extracts were combined and washed with de ionized water (2 x -150 mL) and saturated sodium ch loride (2 x -150 mL). The resulting solid product was filtered and after drying the product (-5.71 g, -32%) was confirmed to be
• Example 14 Synthesis of l,l'-((3a ⁇ f,6as) ⁇ octahydropentalene-2,5-diyl)bis(l- methy lpiperidin - 1 -i um) i odid e
• a gei was prepared by mixing together deionized water (-2 ⁇ _), aqueous CAB-O-SPERSE 2017A (-162 ⁇ , -17 wt%), aqueous 3-hydroxy-l-(5- (1 -methylpiperidin- 1 -ium- 1 -yi)pentyl)quinuclidin- 1 -ium hydroxide (-189 ⁇ , ⁇ , -25.1 wt%), aqueous potassium hydroxide (-42 _u.L, -17.5 wt%), and aqueous aluminum nitrate (-64 xL, -15 wt%).
• the starting gel had the following molar ratios
• SDA is the 3-hydroxy-l ⁇ (5-(l-rnethylpiperidin-l-ium-l- yl)pentyl.)qumuclidm-l.-ium structure directing agent.
• the mixture was stirred until homogenous and then reacted at autogenous pressure at about 160°C for about 7 days in an air oven with tumbling.
• the product was centrifuged, washed three times with deionized water, dried, and then subjected to powder X-ray diffraction analysis.
• the X-ray diffraction pattern showed the product to be pure MCM-68 zeolite.
• a gel was prepared by mixing together deionized water (-24 ⁇ ), UltraSilTM precipitated silica (-44 mg, -92.7 wt%), aqueous 3-hydroxy- 1 -(5-(l ⁇ methylpiperidin- 1 -ium- 1 -yl)pentyl)qumuclidin- 1 -ium hydroxide (-256 ⁇ ,, -25.1 wt%), aqueous potassium hydroxide (-56 ⁇ , -17.5 wt%), and aqueous aluminum nitrate (-86 ⁇ , -15 wt%).
• the starting gel had the following molar ratios
• a gel was prepared by mixing together deionized water ( ⁇ 5 uL), aqueous LUDOX SM-30 (-97 ⁇ , -30.1 wt%), aqueous 3 -hydroxy- 1 -(5 -(1 - methylpiperidin-l-ium- l-yl)pentyl)quinuclidin- l-ium hydroxide (-223 uL, -25.1 wt%), aqueous potassium hydroxide (-49 ⁇ , -17.5 wt%), and aqueous aluminum nitrate (-75 ⁇ , - 15 wt%).
• the starting gel had the following molar ratios
• a gel was prepared by mixing together deionized water (-6 iiL), aqueous LUDOX SM-30 (-105 ⁇ , -30.4 wt%), aqueous 1 '-(butane- 1 , 4- diyl)bis(l-methylpiperidin-l-ium) hydroxide (- 158 ⁇ , -20.9 wt%), aqueous sodium hydroxide (—162 ⁇ , -10 wt%), and aqueous aluminum nitrate (-20 iiL, -15 wt%).
• the starting gel had the following molar ratios
• a gel was prepared by mixing together deionized water (-5 ⁇ .), aqueous LUDOX SM-30 (-70 ⁇ , -30.4 wt%), aqueous l ,l'-((3as,6as)- octahydropentalene-2, 5 ⁇ diyl)bis( 1 -methyipiperidin- 1 -ium) hydroxide (-255 ⁇ , -5.62 wt%), aqueous potassium hydroxide (-35 ⁇ , -17.5 wt%), aqueous aluminum nitrate (-90 ⁇ ,, -1 wt%), and aqueous hydrochloric acid (-19 ⁇ , -20 wt%).
• the starting gel had the following molar ratios
• a series of gels were prepared in a manner similar to Examples 16 to 20 above, but having the molar ratios indicated in Table 3 below.
• the gels were prepared by mixing together deionized water, a Silica Source, aqueous SDA hydroxide, aqueous sodium or potassium hydroxide, aqueous potassium bromide, aqueous aluminum nitrate, and aqueous hydrochloric acid.
• Formula III corresponds to 3-hydroxy-l-(4-(l- methylpiperidin- 1 -ium- 1 -yl)butyl)quinuclidin- 1 -ium hydroxide.
• Formula IV corresponds to 3 -hydroxy- 1 -(5 -( ! -metbylpiperidin- 1 -ium- 1 -yl)pentyl)quin uclidin- l-ium hydroxide.
• Formula V corresponds to l,r-(butane-l,4 ⁇ diyl)bis(l- methylpiperidin-l-ium) hydroxide.
• Formula VI corresponds to l,l'-(pentane-l,5- diyl)bis(l-methylpiperidm-l-ium) hydroxide.
• Formula VII corresponds to ⁇ , - (hexane-1 ,6-diyl)bis(l-methylpiperidin-l-ium) hydroxide.
• Formula VIII corresponds to 1 , 1 '-((3as,6as)-octahydropentalrae-2, ⁇

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