Classifications

• • 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
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • 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
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/10—Heat treatment in the presence of water, e.g. steam
• • 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
  • C01B39/026—After-treatment
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/03—Particle morphology depicted by an image obtained by SEM
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

• This disclosure relates to a novel crystalline molecular sieve material, designated SSZ-1 12, its synthesis, and its use in catalytic and sorption processes.
• Zeolitic materials are known to have utility as sorbents and for various types of organic compound conversion reactions.
• Certain zeolitic materials are ordered, porous crystalline materials having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for sorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.
• U.S. Patent No. 4,851,204 discloses aluminophosphate molecular sieve AIPO-52 and its synthesis using tetraethylammonium cations and tripropylamine as an organic templating agent.
• the framework structure of AIPO-52 has been assigned the three-letter code AFT by the Structure Commission of the International Zeolite Association.
• an aluminosilicate molecular sieve of AFT framework type designated SSZ-1 12
• SSZ-1 12 has now been synthesized using a mixed-template approach as described herein.
• an aluminosilicate molecular sieve of AFT framework type designated SSZ-1 12.
• a method of synthesizing an aluminosilicate molecular sieve of AFT framework type comprising: (a) providing a reaction mixture comprising: (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 metal (M); (4) a source of a first organic template (Q1) comprising hexamethonium dications; (5) a source of a second organic template (Q2) comprising one or more of 1 -methyl-1 -alkylpyrrolidinium cations and 1 -methyl-1 -alkylpiperidinium cations, where each alkyl group is independently C1 -C5 alkyl; (6) a source of hydroxide ions; and (7) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminosilicate molecular sieve.
• an aluminosilicate molecular sieve of AFT framework type containing, within its pore structure, hexamethonium dications and one or more of 1 -methyl-1 -alkylpyrrolidinium cations and 1 -methyl-1 - alkylpiperidinium cations, where each alkyl group is independently C1 -C5 alkyl.
• a process for converting a feedstock comprising an organic compound to a conversion product which comprises contacting the feedstock at organic compound conversion conditions with a catalyst comprising an active form of the aluminosilicate molecular sieve disclosed herein.
• FIG. 1 compares the powder X-ray diffraction (XRD) patterns of the as- synthesized molecular sieve of Example 1 (top pattern) and a simulated powder XRD pattern for an ideal AFT framework type structure (bottom pattern).
• XRD powder X-ray diffraction
• FIG. 2 is a scanning electron micrograph (SEM) image of the as- synthesized molecular sieve of Example 1.
• frame type is used in the sense described in the "Adas ofZeo te Framework Types," Sixth Revised Edition, Elsevier (2007).
• aluminosilicate refers to a crystalline microporous solid including aluminum and silicon oxides within its framework.
• the aluminosilicate may be a "pure aluminosilicate” (i.e., absent other detectable metal oxides within the framework) or optionally substituted.
• the respective framework may contain boron, gallium, indium, germanium, hafnium, iron, tin, titanium, vanadium, zinc, zirconium, or other atoms substituted for one or more of the atoms not already contained in the parent framework.
• anhydrous form is employed herein to refer to a molecular sieve substantially devoid of both physically adsorbed and chemically adsorbed water.
• the aluminosilicate molecular sieve of the present disclosure may be synthesized by (a) providing a reaction mixture comprising (1) a source of silicon oxide; (2) a source of aluminum oxide; (3) a source of a Group 1 metal (M); (4) a source of a first organic template (Q1) comprising hexamethonium dications; (5) a source of a second organic template (Q2) comprising one or more of 1 -methyl-1 - alkylpyrrolidinium cations and 1 -methyl-1 -alkylpiperidinium cations, where each alkyl group is independently C1 -C5 alkyl; (6) a source of hydroxide ions; and (7) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminosilicate molecular sieve.
• the composition of the reaction mixture from which the molecular sieve is formed is identified
• Suitable sources of silicon oxide include colloidal silica, precipitated silica, fumed silica, alkali metal silicates and tetraalkyl orthosilicates.
• Suitable sources of aluminum oxide include hydrated alumina and water-soluble aluminum salts (e.g., aluminum nitrate).
• Combined sources of silicon oxide and aluminum oxide can additionally or alternatively be used and can include aluminosilicate zeolites (e.g., zeolite Y) and clays or treated clays (e.g., metakaolin).
• zeolites e.g., zeolite Y
• clays or treated clays e.g., metakaolin
• Examples of suitable Group 1 metals (M) include sodium and potassium.
• the metal is generally present in the reaction mixture as the hydroxide.
• the first organic template (Q1) comprises hexamethonium dications, represented by the following structure (1):
• the second organic template (Q2) comprises one or more of 1 -methyl- 1 -alkylpyrrolidinium cations and 1 -methyl-1 -alkylpiperidinium cations, represented by the following structures (2) and (3), respectively:
• R 1 and R 2 are independently C1 -C5 alkyl (e.g., C2-Q alkyl or C 3 -C 4 alkyl).
• Examples of the second organic template (Q2) include 1 -methyl-1 -butylpyrrolidinium cations, 1 -methyl-1 -propylpiperidinium cations, and combinations thereof.
• Suitable sources of Q1 and Q2 are the hydroxides and/or other salts of the relevant quaternary ammonium compounds.
• the reaction mixture may also contain seeds of a molecular sieve material, such as SSZ-1 12 from a previous synthesis, desirably in an amount of from 0.01 to 10,000 ppm (e.g., from 100 to 5000 ppm) by weight of the reaction mixture.
• a molecular sieve material such as SSZ-1 12 from a previous synthesis
• the molecular sieve reaction mixture can be supplied by more than one source. Also, two or more reaction components can be provided by one source.
• reaction mixture can be prepared either batch wise or
• Crystal size, morphology and crystallization time of the molecular sieve described herein can vary with the nature of the reaction mixture and the synthesis conditions.
• Crystallization of the molecular sieve from the above reaction mixture can be carried at either static or stirred conditions in a suitable reactor vessel, such as, for example, polypropylene jar or Teflon-lined or stainless steel autoclaves, at a temperature of from 125°C to 200°C for a time sufficient for crystallization to occur at the temperature used (e.g., from 24 to 480 hours, or 48 to 240 hours).
• a suitable reactor vessel such as, for example, polypropylene jar or Teflon-lined or stainless steel autoclaves, at a temperature of from 125°C to 200°C for a time sufficient for crystallization to occur at the temperature used (e.g., from 24 to 480 hours, or 48 to 240 hours).
• Crystallization is typically carried out in a closed system under autogenous pressure.
• the solid product is recovered from the reaction mixture by standard mechanical separation techniques such as centrifugation or filtration.
• the crystals are water-washed and then dried to obtain the as-synthesized molecular sieve crystals.
• the drying step can be performed at atmospheric pressure or under vacuum.
• the drying step is typically performed at a temperature of less than 200°C.
• the recovered crystalline molecular sieve product contains within its pore structure at least a portion of the structure directing agents used in the synthesis.
• any cations in the as-synthesized molecular sieve can be replaced in accordance with techniques well known in the art by ion exchange with other cations.
• Suitable replacing cations include metal ions, hydrogen ions, hydrogen precursor (e.g., ammonium ions), and combinations thereof.
• Preferred replacing cations may include those which tailor the catalytic activity for certain organic or inorganic conversion reactions. These may include hydrogen, rare earth metals, and metals of Groups 2-15 of the Periodic Table of Elements.
• the as-synthesized molecular sieve prepared as described herein may be subjected to subsequent treatment to remove part or all of the organic templates used in its synthesis.
• This can be conveniently effected by thermal treatment in which the as-synthesized material can be heated to a temperature of at least 370°C for at least 1 minute and generally not longer than 24 hours. While sub-atmospheric and/or super-atmospheric pressures can be employed for the thermal treatment, atmospheric pressure may be desired for reasons of convenience.
• the thermal treatment can be performed at a temperature up to 925°C.
• the organic templates can be removed by treatment with ozone (see, e.g., A.N. Parikh et ai., Micropor.
• the organic- depleted product especially in its metal, hydrogen and ammonium forms, is particularly useful in catalytic applications.
• the organic-depleted molecular sieve in its hydrogen form is referred to herein as the "active form" of the molecular sieve, with or without metal function present.
• molecular sieve SSZ-1 12 has a chemical composition, in terms of molar ratios, as set forth in Table 2:
• the as-synthesized form of the molecular sieve may have molar ratios different from the molar ratios of reactants of the reaction mixture used to prepare the as-synthesized form. This result may occur due to incomplete incorporation of 100% of the reactants of the reaction mixture into the crystals formed (from the reaction mixture).
• molecular sieve SSZ-1 12 has a chemical composition comprising the following molar relationship:
• AI2O3 (n)Si0 2 wherein n has a value of in a range of 5 to 50 (e.g., 10 to 50, 5 to 25, 10 to 25, 5 to 20, 10 to 20, 5 to 15, or 10 to 15).
• the as-synthesized and calcined forms of SSZ-1 12 have characteristic powder X-ray diffraction patterns, which in the as-synthesized form of the molecular sieve, includes at least the lines listed in Table 3 below and which, in the calcined form of the molecular sieve, includes at least the peaks listed in Table 4 below.
• the powder XRD patterns provided are based on a relative intensity scale in which the strongest line in the XRD pattern is assigned a value of 100:
• the powder XRD patterns provided are based on a relative intensity scale in which the strongest line in the XRD pattern is assigned a value of 100:
• the powder XRD patterns presented herein were collected by standard techniques.
• the radiation was CuKa radiation.
• Minor variations in the diffraction pattern can result from variations in the mole ratios of the framework species of the sample due to changes in lattice constants. In addition, sufficiently disordered materials and/or small crystals will affect the shape and intensity of peaks, leading to significant peak broadening. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation. Calcination can also cause minor shifts in the XRD pattern. Notwithstanding these minor perturbations, the basic crystal lattice structure remains unchanged.
• Molecular sieve SSZ-1 12 can be used for separating mixtures of molecular species, removing contaminants through ion exchange and catalyzing various organic or inorganic compound conversion reactions.
• Separation of molecular species can be based either on the molecular size (kinetic diameter) or on the degree of polarity of the molecular species.
• the separation process may comprise contacting at least two components with SSZ-1 12 to generate at least one separated component.
• Molecular sieve SSZ-1 12 may be used as a catalyst to catalyze a wide variety of organic or inorganic conversion processes including many of present commercial/industrial importance.
• organic and inorganic conversion processes that may be catalyzed by SSZ-1 12 can include alkylation, cracking, hydrocracking, isomerization, oligomerization, conversion of organic oxygenates (e.g., methanol and/or dimethyl ether) to olefins (e.g., ethylene, propylene), synthesis of monoalkylamines and dialkylamines, and the catalytic reduction of nitrogen oxides (NOx).
• organic oxygenates e.g., methanol and/or dimethyl ether
• olefins e.g., ethylene, propylene
• NOx nitrogen oxides
• SSZ-1 12 with another component resistant to the temperatures and other conditions employed in organic conversion processes.
• Such components 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 either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and other metal oxides.
• Use of a material in conjunction with SSZ- 1 12 i.e., combined therewith or present during synthesis of the crystalline material, which can be in its active state) can tend to change the level of conversion and/or selectivity of the catalyst in certain organic conversion processes.
• Inactive materials can suitably serve as diluents (e.g., to control the amount of conversion in a given process) so that products can be obtained in an economic and orderly manner, such as without employing other means for controlling the rate of reaction.
• These 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.
• These materials i.e., clays, oxides, etc.
• binders for the catalyst It can be desirable to provide a catalyst having good crush strength, because, in commercial use, it can be desirable to prevent/limit the catalyst from breaking down into powder-like materials (fines).
• These clay and/or oxide binders can be employed, e.g., solely to improve the crush strength of the catalyst.
• Naturally occurring clays that can be composited with SSZ-1 12 can include the montmorillonite and kaolin families, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, as well as others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, 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 SSZ-1 12 can additionally or alternately include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
• inorganic oxides such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
• SSZ- 1 12 can be composited with a porous matrix material, such as silica-alumina, silica- magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina- magnesia, silica-magnesia-zirconia, and mixtures or combinations thereof.
• a porous matrix material such as silica-alumina, silica- magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina- magnesia, silica-magnesia-zir
• the relative proportions of SSZ-1 12 and inorganic oxide matrix may vary widely, with the SSZ-1 12 content typically ranging from 1 to 90 wt. % (e.g., 2 to about 80 wt. %), based on the total composite weight.
• FIG. 1 compares the powder XRD patterns of the as-synthesized product (top pattern) and a simulated powder XRD pattern for an ideal AFT framework type structure (bottom pattern). As shown, the powder XRD pattern of the product is consistent with the product being a pure AFT framework type molecular sieve.
• a SEM image of the product is shown in FIG. 2 and indicates a uniform field of crystals.
• the product had a S1O2/AI2O3 molar ratio of 13.79, as determined by Inductively Coupled Plasma - Mass Spectrometry (ICP-MS).
• Powder XRD indicated that the product was a pure AFT framework type molecular sieve.
• the product had a S1O2/AI2O3 molar ratio of 13.75, as determined by ICP-MS.
• Powder XRD indicated that the product was a pure AFT framework type molecular sieve.
• the product had a S1O2/AI2O3 molar ratio of 13.00, as determined by ICP-MS.
• the product had a S1O2/AI2O3 molar ratio of 12.76, as determined by ICP-MS.
• the micropore volume of the ammonium-exchanged product was measured using nitrogen physisorption and the data analyzed via the B.E.T. method.
• the molecular sieve exhibited a micropore volume of 0.23 cm 3 /g.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Geology (AREA)
• Inorganic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
• Catalysts (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=63965720

Family Applications (1)

Country Status (7)

Cited By (1)

Families Citing this family (6)

Citations (3)

Family Cites Families (16)

• 2018
  • 2018-10-04 JP JP2020505908A patent/JP7138697B2/ja active Active
  • 2018-10-04 US US16/151,506 patent/US10343927B2/en active Active
  • 2018-10-04 KR KR1020207014760A patent/KR102610289B1/ko active Active
  • 2018-10-04 EP EP18793012.8A patent/EP3700863B1/en active Active
  • 2018-10-04 ES ES18793012T patent/ES2901685T3/es active Active
  • 2018-10-04 CN CN201880047072.8A patent/CN110914195B/zh active Active
  • 2018-10-04 WO PCT/IB2018/057710 patent/WO2019082004A1/en not_active Ceased

Patent Citations (3)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events