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WO2017141132A1 - Hollow zeolite type catalysts with varying framework and zeolite topologies - Google Patents

Hollow zeolite type catalysts with varying framework and zeolite topologies Download PDF

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Publication number
WO2017141132A1
WO2017141132A1 PCT/IB2017/050654 IB2017050654W WO2017141132A1 WO 2017141132 A1 WO2017141132 A1 WO 2017141132A1 IB 2017050654 W IB2017050654 W IB 2017050654W WO 2017141132 A1 WO2017141132 A1 WO 2017141132A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
particle
hollow
shell
metal
Prior art date
Application number
PCT/IB2017/050654
Other languages
French (fr)
Inventor
Ugo RAVON
Original Assignee
Sabic Global Technologies B.V.
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Filing date
Publication date
Application filed by Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2017141132A1 publication Critical patent/WO2017141132A1/en

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    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • 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
    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/082—X-type faujasite
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • 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
    • 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
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base 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
    • 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
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size

Definitions

  • the invention generally concerns a non-MFI zeolite catalyst for chemical applications (e.g., hydrocarbon reforming reactions such as dry or steam reforming of methane).
  • the invention concerns a catalyst that includes a hollow zeolite particle having a zeolite framework type structure with a peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell.
  • Zeolites belong to a broader material category known as "molecular sieves" and are often referred as such. Zeolites have uniform, molecular-sized pores, and can be separated based on their size, shape, and polarity. For example, zeolites may have pore sizes ranging from about 0.3 nm to about 1 nm. The crystalline structure of zeolites can provide good mechanical properties and good thermal and chemical stability. Zeolites are microporous, possess regular pores and cavities, and have acidic behavior, which make them useful as catalysts or support material in commercial chemical processes (e.g., fluid catalytic cracking, alkylation, reforming, etc.). Many conventional zeolite catalysts include catalytic material.
  • the catalytic material can be smaller than the pores of the zeolite allowing the catalytic material to diffuse through the pore, which diminishes the stability of the catalyst.
  • Other problems associated with deactivation of zeolites containing catalytic material include poor dispersion of the catalytic material on the surface of the zeolite, and/or leaching of the catalytic material from the zeolite.
  • the solution of the present invention concerns a hollow zeolite particle having a zeolite type structure peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type framework.
  • the hollow zeolite particle of the present invention can have a single type of zeolite framework structure throughout the particle in that it is not a composite where two or more different materials (e.g., different zeolites, inert/non-catalytic materials (e.g., binders, fly ash, drugs, etc.)) constitute the particle.
  • the particle can be a pure non-MFI zeolite shell having the intra- particle hollow space.
  • the particles of the present invention can have: 1) any desired Si/Al ratio (1 to ⁇ ); 2) different framework and zeolite topologies; and/or 3) a shell with high surface area on both internal and external surfaces. The high surface area allows more than one type of reaction to occur on the same catalyst site.
  • a dehydrogenation of hydrocarbon reaction can occur on the internal surface and a hydrocarbon alkylation reaction can occur on the external surface of the hollow zeolite of the present invention.
  • the hollow zeolite particle of the present invention can be used to control dispersion of metal or metal oxide deposition inside the pore, and the size of the active material (metal or metal oxide) in the hollow surface and/or on the external surface of the zeolite particle.
  • the methods to make the hollow zeolite particle of the present invention provides an elegant manner to achieve simultaneously, macroporous and/or mesoporous and/or microporous channels that offer shape selectivity which could be interconnected to overcome mass transfer limitations.
  • a hollow zeolite particle having a zeolite type structure peripheral shell that defines and encloses an intra- particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type structure.
  • the hollow zeolite particle has a FAU X- type or Y-type framework peripheral shell, preferably a FAU-X type framework structure, more preferably a 13X-type structure peripheral shell as characterized by an X-ray diffraction pattern shown in FIG. 5.
  • Another hollow zeolite particle can have a MWW type structure, a *BEA type structure, a LTA type structure, a MOR type structure, an ITH type structure, a CHA type structure, a *MRE type structure, a MER type structure, or a VFI type structure peripheral shell.
  • the hollow particle can have at least a second intra-particle hollow space (e.g., 2, 3, 4, 5 hollow spaces) within the interior of the shell.
  • the intra-particle hollow space can have a diameter of 50% to 80% of the diameter of the particle.
  • the hollow particle can have a BET surface area of 140 cm 3 /g to 600 cm 3 /g and/or a diameter of 10 nanometers to 450 nanometers.
  • the framework of hollow zeolite particle can include pores having a diameter of 2 nanometers or less, preferably 0.1 nanometers to 0.5 nanometers.
  • Catalytic metal or oxides thereof can be included in the hollow zeolite particle.
  • the catalytic metal or oxide thereof can be positioned in the intra-particle hollow space, on the surface of the shell, embedded in the shell or any combination thereof.
  • Catalytic metal or metal oxides thereof can include Column 1 (e.g., lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs)) metal or oxides thereof or any alloy or combination thereof) , a Column 2 (e.g., magnesium (Mg), calcium (Ca), or barium (Ba)) metal, a transition (e.g., vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn)) metal, a post-transition (gallium (Ga), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi)) metal, a lan
  • a method to make the hollow zeolite particle described above can include (a) obtaining a synthesis mixture of a protonated zeolite and a templating agent and (b) heat treating the synthesis mixture to form a zeolite framework type structure peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell. Heat-treating in step (b) can remove aluminum ions from the protonated zeolite framework.
  • the templating agent can be a quaternary or a tertiary ammonium compound or a salt thereof, preferably tetramethylammonium hydroxide. In a particular aspect, the templating agent is metal free.
  • Heat-treating the synthesis mixture can include (i) heating the synthesis mixture to obtain a crystalline material, and (ii) calcining the crystalline material.
  • Heating in step (i) can include subjecting the solution to a temperature of 100 °C to 250 °C, preferably 150 °C to 200 °C, for 1 to 3 days, preferably 1 to 5 days under static conditions.
  • Calcining the crystalline material in step (ii) can include subjecting the crystalline material to a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C, for 3 to 10 hours, preferably 4 to 8 hours.
  • Obtaining a protonated form of the zeolite can include subjecting the zeolite to a cation exchange process to exchange cations with proton.
  • the calcined catalyst can be subjecting to reducing conditions to convert the metal oxide to the metal having a zero valence.
  • the protonated zeolite can be impregnated with a metal precursor.
  • a system can include (a) an inlet for a reactant feed; (b) a reaction zone (e.g., a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor) that is configured to be in fluid communication with the inlet, wherein the reaction zone includes the hollow zeolite particle of the present invention; and (c) an outlet configured to be in fluid communication with the reaction zone and configured to remove a product stream from the reaction zone.
  • the reaction zone can a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor.
  • a saturated hydrocarbon stream or a hydrocarbon stream having a boiling point of 340 °C or more at atmospheric pressure or both can be used as a reactant feed and/or the product stream can include alkylated hydrocarbons, gasoline, jet fuel, diesel, olefinic gases, or any combination thereof.
  • Methods of using the hollow zeolite particle described above in a chemical reaction are disclosed.
  • the method can include contacting the hollow zeolite particle of the present inventions with a reactant feed to catalyze a chemical reaction; and producing a product feed.
  • the chemical reaction can be an alkylation of an aromatic hydrocarbon reaction (e.g., alkylation of benzene with ethylene to produce ethylbenzene, alkylation of benzene with propylene to produce isopropylbenzene (cumene), etc.).
  • a hollow zeolite particle is described.
  • the hollow zeolite particle of embodiment 1 can have a zeolite type framework peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type framework.
  • Embodiment 2 is the hollow zeolite particle of embodiment 1, having a FAU X-type or Y-type structure peripheral shell.
  • Embodiment 3 is the hollow zeolite particle of embodiment 2, having a FAU X-type structure peripheral shell.
  • Embodiment 4 is the hollow zeolite particle of embodiment 3, wherein the FAU X-type structure peripheral shell is a 13 X-type structure peripheral shell.
  • Embodiment 5 is the hollow zeolite particle of embodiment 4, characterized by an X-ray diffraction (XRD) pattern shown in FIG. 5.
  • Embodiment 6 is the hollow zeolite particle of any one of embodiments 1 to 5, having a surface area of 140 cm 3 /g to 600 cm 3 /g.
  • Embodiment 7 is the hollow zeolite particle of any one of embodiments 1 to 6, including at least a second intra-particle hollow space within the interior of the shell.
  • Embodiment 8 is the hollow zeolite particle of any one of embodiments 1 to 7, having a diameter of 10 nanometers to 450 nanometers.
  • Embodiment 9 is the hollow zeolite particle of embodiment 8, wherein the intra-particle hollow space has a diameter of 50% to 80% of the diameter of the particle.
  • Embodiment 10 is the hollow zeolite particle of any one of embodiments 1 to 9, wherein the zeolite framework type peripheral shell includes pores having a diameter of 2 nanometers or less, preferably 0.1 nanometers to 0.5 nanometers.
  • Embodiment 11 is the hollow zeolite particle of any one of embodiments 1 to 10, wherein the thickness of the zeolite framework type peripheral shell is 5 nanometers to 20 nanometers.
  • Embodiment 12 is the hollow zeolite particle of any one of embodiments 1 to 11 that further includes a catalytic metal or oxide thereof.
  • Embodiments 13 is the hollow zeolite particle of embodiment 12, wherein the catalytic metal or oxide thereof is positioned in the intra-particle hollow space, on the surface of the shell, embedded in the shell or any combination thereof.
  • Embodiment 14 is the hollow zeolite particle of any one of embodiments 12 to 13, wherein the catalytic metal or metal oxide is a Column 1 metal, a Column 2 metal, a transition metal, a post- transition metal, a lanthanide metal, or any alloy or combination thereof.
  • Embodiment 15 is the hollow zeolite particle of embodiment 14, wherein the Column 1 metal is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) or oxides thereof or any alloy or combination thereof.
  • Embodiment 15 is the hollow zeolite particle of embodiment 14, wherein the Column 2 metal is magnesium (Mg), calcium (Ca), or barium (Ba) or oxides thereof or any alloy or combination thereof.
  • Embodiment 16 is the hollow zeolite particle of embodiment 14, wherein the transition metal is vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), or oxides or any alloy or combination thereof.
  • the transition metal is vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), or oxides or any alloy or combination thereof.
  • Embodiment 17 is the hollow zeolite particle of embodiment 14, wherein the post transition metal is gallium (Ga), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), or oxides thereof, or any alloy or combination thereof.
  • Embodiment 18 is the hollow zeolite particle of embodiment 14, wherein the lanthanide metal is lanthanum (La), ytterbium (Yb) or oxides thereof or any alloy or combination thereof.
  • Embodiment 19 is the hollow zeolite particle of any one of embodiments 1 and 5 to 19, having a MWW type structure, a *BEA type structure, a LTA type structure, a MOR type structure, an ITH type structure, a CHA type structure, a MRE type structure, a MFE type structure, or a VFI type structure peripheral shell.
  • Embodiment 21 is a method of making the hollow zeolite particle of any one of embodiments 1 to 20.
  • the method of embodiment 21 includes (a) obtaining a synthesis mixture of a protonated zeolite and a templating agent; and (b) heat treating the synthesis mixture to form a zeolite framework type structure peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell.
  • Embodiment 22 is the method of embodiment 21, wherein the templating agent is a quaternary or a tertiary ammonium compound or a salt thereof, preferably tetramethylammonium hydroxide.
  • Embodiment 23 is the method of any one of embodiments 21 to 22, wherein the templating agent is metal free.
  • Embodiment 24 is the method of any one of embodiments 21 to 23, wherein heat-treating the synthesis mixture includes (i) heating the synthesis mixture to obtain a crystalline material, and (ii) calcining the crystalline material.
  • Embodiment 25 is the method of embodiment 24, wherein heating in step (i) includes subjecting the solution to a temperature of 100 °C to 250 °C, preferably 150 °C to 200 °C, for 1 to 3 days, preferably 1 to 5 days under static conditions.
  • Embodiment 26 is the method of any one of embodiments 20 to 25, wherein step (ii) includes subjecting the crystalline material to a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C, for 3 to 10 hours, preferably 4 to 8 hours.
  • Embodiment 27 is the method of embodiment 26 that further includes drying the crystalline material at 90 °C to 110 °C for 8 to 12 hours prior to step (b).
  • Embodiment 28 is the method of any one of embodiments 20 to 27, wherein step (a) includes subjecting the zeolite to a cation exchange process to exchange cations with protons.
  • Embodiment 29 is the method of embodiment 28, wherein the cation is ammonium ion ( H 4 + ).
  • Embodiment 30 is the method of any one of embodiments 20 to 29, wherein heat-treating in step (b) removes aluminum ions from the protonated zeolite.
  • Embodiment 31 is the method of any one of embodiments 20 to 30, wherein the protonated zeolite is impregnated with a metal precursor material.
  • Embodiment 32 is a method of using the hollow zeolite particle of any one of embodiments 1 to 20 in a chemical reaction.
  • the method of embodiment 32 includes (a) contacting the hollow zeolite particle of any one of embodiments 1 to 20 with a reactant feed to catalyze a chemical reaction; and (b) producing a product feed.
  • Embodiment 33 is the method of embodiment 32, wherein the chemical reaction is a fluid catalytic cracking reaction, a hydrocracking reaction, or an alkylation reaction.
  • the alkylation reaction can be an alkylation of an aromatic hydrocarbon reaction such as alkylation of benzene with ethylene to produce ethylbenzene or alkylation of benzene with propylene to produce cumene.
  • Embodiment 34 is a system for producing a chemical product.
  • the system of embodiment 34 includes (a) an inlet for a reactant feed; (b) a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone includes the hollow zeolite particle of any one of embodiments 1 to 20; and (c) an outlet configured to be in fluid communication with the reaction zone and configured to remove a product stream from the reaction zone.
  • Embodiment 35 is the system of embodiment 34, wherein the reaction zone is a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor.
  • Embodiment 36 is the system of any one of embodiments 34 to 35, wherein the reactant feed is a saturated hydrocarbon stream or a hydrocarbon stream having a boiling point of 340 °C or more at atmospheric pressure or both.
  • Embodiment 37 is the system of any one of embodiments 34 to 36, wherein the product stream includes alkylated hydrocarbons, gasoline, jet fuel, diesel, olefinic gases, or any combination thereof.
  • intra-particle hollow space refers to a hollow space or void in within the interior surface of a zeolite shell.
  • FIG. 1A provides a non-limiting example of a particle of the present invention that includes a single intra-particle hollow space.
  • FIG. IB provides a non-limiting example of a particle of the present invention that includes two intra-particle hollow spaces.
  • inter-particle space refers to a space or void that is created when multiple particles are contacted with one another and spaces or voids are created between the outer surfaces of such particles.
  • FIG. 1C provides a non-limiting example of a plurality of particles of the present invention, each having a single intra-particle hollow space, that form inter-particle spaces or voids between the outer surfaces of such particles.
  • catalyst refers to a single hollow zeolite particle or a plurality of hollow zeolite particles positioned adjacent to each other in a catalytic bed and/or shaped into a form that can catalyze a chemical reaction.
  • FIGS. 1A-1C provide non-limiting examples of catalysts of the present invention.
  • nanostructure refers to an object or material in which at least one dimension of the object or material is equal to or less than 1000 nm (e.g., one dimension is 1 to 1000 nm in size).
  • the nanostructure includes at least two dimensions that are equal to or less than 1000 nm (e.g., a first dimension is 1 to 1000 nm in size and a second dimension is 1 to 1000 nm in size).
  • the nanostructure includes three dimensions that are equal to or less than 1000 nm (e.g., a first dimension is 1 to 1000 nm in size, a second dimension is 1 to 1000 nm in size, and a third dimension is 1 to 1000 nm in size).
  • the shape of the nanostructure can be of a wire, a particle (e.g., having a substantially spherical shape), a rod, a tetrapod, a hyper-branched structure, a tube, a cube, or mixtures thereof.
  • Nanostructures include particles having an average diameter size of 1 to 1000 nanometers. In a particular instance the nanostructure is a nanoparticle.
  • Particle size of the nanostructures or other particles can be measured using known techniques.
  • Non-limiting examples include transmission electron spectroscopy (TEM), scanning electron microscopy (SEM), preferably TEM.
  • the hollow zeolite nanoparticle of the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the hollow zeolite nanoparticle of the present invention are (1) a zeolite type framework peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type framework and (2) their use in catalyzing chemical reactions.
  • wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
  • a non-limiting example is 1 wt.% of M 1 means that a 100 gram sample of catalyst contains 0.01 grams of M 1 in its metallic form.
  • FIG. 1A is an illustration of an embodiment of cross-sectional view of a hollow zeolite with an intra-particle hollow space within the interior of the shell.
  • FIG. IB is an illustration of an embodiment of a cross-sectional view of a hollow zeolite with two intra-particle hollow spaces within the interior of the shell.
  • FIG. 1C is an illustration of an embodiment of a cross-sectional view of a plurality of zeolite particles, each having an intra-particle hollow space, that form inter- particle spaces between the outer surfaces of the particles.
  • FIG. 2A is an illustration of an embodiment of a cross-sectional view of a hollow zeolite with a nanostructure contacting the inner surface of the intra-particle hollow space within the interior of the shell.
  • FIG. 2B is an illustration of an embodiment of a cross-sectional view of a hollow zeolite with a nanostructure not contacting the inner surface of the intra-particle hollow space within the interior of the shell.
  • FIG. 2C is an illustration an embodiment of a cross-sectional view of a hollow zeolite with a plurality of nanostmctures in the intra-particle hollow space within the interior of the shell of the present invention.
  • FIG. 3 is an illustration of a method of making the hollow zeolite having an intra- particle hollow space within the interior of the shell of the present invention.
  • FIG. 4 is an illustration of a method of making the hollow zeolite with a nanostructure in the intra-particle hollow space within the interior of the shell of the present invention.
  • FIG. 5 shows X-ray diffraction patterns of a comparative FAU 13X- type zeolite particle (top) and a hollow FAU 13X type zeolite particle of the present invention (bottom).
  • FIG. 6 shows nitrogen isotherms of the comparative FAU 13X type zeolite particle (top isotherms) and a hollow FAU 13X type zeolite particle of the present invention (bottom isotherms).
  • the discovery is based on the premise to create an intra-particle hollow (void) space within the interior portion of a zeolite particle.
  • the hollow zeolite particle can include a catalytic material.
  • the catalytic material and the zeolite type can be selected for a desired result (e.g., catalytic metals can be included in the hollow to catalyze a given chemical reaction).
  • the method of making the hollow zeolite nanoparticle allows for creation of an intra-particle hollow space in the zeolite particle and/or tuning of the thickness and/or acidity of the zeolite shell surrounding the intra- particle hollow space.
  • the hollow zeolite structure of the present invention includes an intra-particle hollow space within the interior surface of the zeolite particle shell.
  • FIGS. 1A-1C are cross- sectional illustrations of hollow zeolite particle 10 having an intra-particle hollow space zeolite structure.
  • the hollow zeolite particle 10 has a zeolite-type framework peripheral shell 12 and intra-particle hollow space 14.
  • FIG. IB depicts the intra-particle hollow zeolite particle 10 having two intra-particle hollow spaces.
  • FIG. 1C depicts a catalyst that includes a plurality of the hollow zeolite particles 10.
  • the hollow zeolite particle 10 can have a surface area of 140 cm 3 /g to 600 cm 3 /g, 150 cm 3 /g to 500 cm 3 /g, 200 cm 3 /g to 400 cm 3 /g, or 140 cm 3 /g, 150 cm 3 /g, 200 cm 3 /g, 250 cm 3 /g, 300 cm 3 /g, 350 cm 3 /g, 400 cm 3 /g, 450 cm 3 /g, 500 cm 3 /g, 550 cm 3 /g, 600 cm 3 /g or any range or value there between and/or a diameter of 10 nanometers (nm) to 450 nm, 100 to 300 nm, 150 to 250 nm, or 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 400 nm, 450 nm or any range or value there between.
  • 10 nanometers (nm) to 450 nm 100 to 300 n
  • a volume space of the intra-particle hollow space 14 can be about 30 to 80%, 40 to 70%, or 50 to 60% of the zeolite particle volume or 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%), 80%) or any value or range there between.
  • the diameter of the intra-particle hollow space can be 50 to 80%, or 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any range or value there between of the diameter of the particle.
  • the zeolite shell 12 can be any porous zeolite or zeolite-like material devoid of zeolite material having a MFI-type structure.
  • the zeolite material can be a naturally occurring zeolite, a synthetic zeolite, a zeolite that have other materials in the zeolite framework (e.g., phosphorous), or combinations thereof.
  • X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) may be carried out to determine the properties of zeolite materials, including their crystallinity, size and morphology.
  • the network of such zeolites is made up of Si0 4 and A10 4 tetrahedra, which are joined via shared oxygen bridges.
  • the zeolite material can have secondary building blocks of 4, 5, 6, 8, 18, 4-1, 4-2, 4-4, 5-1, 5-2, 5-3, 6-1, 6-1 (1 :4), 6-2, 6-3, 6-6, 8-8, 1-4-1, 1-6-1, 2-6-2, or combinations thereof.
  • a zeolite having secondary building units of 6- 6 or 6-2 or 6 or 4-2 or 1-4-1 or 4 is used.
  • a zeolite having a pentasil and/or 5-1 secondary building unit can possess different characteristics than a MFI zeolite (for example, structure, porosity, pore volume, thermal stability and the like) and is these zeolites are not considered a MFI framework type zeolite in the present invention.
  • Non-limiting examples of zeolites include ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ATN, ATO, ATS, ATT, ATV, AWO, AWW, *BEA, BIK, BOG, BPH, BRE, CAN, CAS, CFI, CGF, CGS, CHA, CHI, -CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, EUO, *EWT, FAU, FER, GIS, GME, GOO, HEU, IFR, ISV, ITE, ITH, ITG, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN,
  • the zeolite includes phosphorous to form an AIPOx structure.
  • AIPOx zeolites include AABW, AACO, AAEI, AAEL, AAEN, AAET, A AFG, AAFI, AAFN, AAFO, AAFR, AAFS, AAFT, AAFX, AAFY, AAHT, AANA, AAPC, AAPD, AAST, AATN, AATO, AATS, AATT, AATV, AAWO, AAWW, ABEA, ABIK, ABOG, ABPH, ABRE, ACAN, ACAS, ACFI, ACGF, ACGS, ACHA, ACHI, A-CLO, ACON, ACZP, AD AC, ADDR, ADFO, ADFT, ADOH, ADON, AEAB, AEDI, AEMT, AEPI, AERI, AESV, AEUO, A*EWT, AFAU, AFER, AGIS, AGME
  • Zeolites may be obtained from a commercial manufacturer such as Zeolyst (Valley Forge, Pennsylvania, U. S.A.).
  • Shell 12 can include at least 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.% 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.% or 99 wt.%, or 100 wt.%) of zeolite material.
  • the shell is porous and includes pores having a diameter of 2 nanometers or less, 0.1 nanometers to 0.5 nanometers, or 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 1.1 nm 1.2 nm, 1.3 nm, 1.4 nm, 1.5 nm, 1.6 nm, 1.7 nm, 1.8 nm, 1.9 nm, 2.0 nm or any value or range there between.
  • the thickness of the shell can be tuned.
  • the thickness can range from 5 to 20 nm, or 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 1 1 nm, 12 nm, 13 nm, 14 nm, 15 nm 16 nm, 17 nm, 18 nm, 19 nm, 20 nm or any range or value there between.
  • Shell 12 includes an inner surface 16 and outer surface 18.
  • Inner surface 16 forms the outer surface of the intra-particle hollow space 14.
  • Inner surface 16 and outer surface 18 are made of the same zeolite material, or a combination of zeolite materials.
  • FIG. 1C depicts a plurality of hollow zeolite particles 10 in combination with an inert surface 17.
  • Inert surface 17 can be a holder (e.g., tray, tube, etc.) or a material (e.g., binder, clays, polymeric material, etc.) that holds the hollow zeolite particles in position so that they can be used in a reaction zone.
  • inter-particle void 19 is formed.
  • the inert surface imparts structural integrity to the hollow zeolite particle. Since the zeolite is pure silicalite zeolite and/or substantially inert, the inter-particle void spaces between the hollow zeolite particles 10 will have no activity or substantially no activity.
  • the hollow zeolite particle can include catalytic material.
  • the catalytic material can be a metal nanostructure contained within the intra-particle hollow space that is present in the zeolite.
  • FIGS. 2 A through 2C are cross-sectional illustrations of catalyst material 20 having an encapsulated metal nanostructure/hollow zeolite structure.
  • the catalyst material 20 has a zeolite shell 12, a catalytic (e.g., metal, bimetallic or trimetallic) nanostructure 22 and intra-particle hollow space 14.
  • a portion of the nanostructure 22 e.g., M 1 , M 1 and M 2 and/or M 3
  • the intra-particle hollow space 14 can be formed by removal of a portion of the zeolite core during the making of the catalyst material.
  • the catalytic nanostructure 22 contacts a portion of the inner wall of hollow space 14.
  • the catalytic nanostructure 22 does not contact the walls of the intra- particle hollow space 14.
  • multiple catalytic nanostructures 22 are in the intra-particle hollow space 14 with some catalytic nanostructures touching the inner wall of the intra-particle hollow space.
  • 1% to 99%, 10% to 80%, 20% to 70%, 30%) to 60%), 40%) to 50% or any range or value there between of the nanostructures fills the intra-particle hollow space 14.
  • a diameter of the catalytic nanostructure 14 can range from 1 nm to 100 nm, preferably 1 nm to 50 nm, or more preferably 1 nm to 5 nm or any value or range there between. In some embodiments, 1 to 100 nm, preferably 1 to 30 nm, more preferably 3 to 15 nm, most preferably ⁇ 10 nm with a size distribution having a standard deviation of ⁇ 20%>.
  • the pore size of the resulting catalyst is the same or similar to the pore size of the starting zeolite. Diameters of the catalytic nanostructure and pore size of the catalyst can be determined using transmission electron microscopy (TEM) and Barrett- Joy ner-Halenda (BJH) methods known in the art.
  • TEM transmission electron microscopy
  • BJH Barrett- Joy ner-Halenda
  • Catalytic nanostructure(s) 22 can include one or more active (catalytic) metals to promote a desired chemical reaction (e.g., hydrocarbon cracking, alkylation, isomerization, etc.).
  • the chemical reaction can be an alkylation reaction such as an alkylation of an aromatic hydrocarbon reaction (e.g., alkylation of benzene with ethylene to produce ethylbenzene or alkylation of benzene with propylene to produce cumene).
  • the nanostructure(s) 22 can include one or more catalytic metals or metal oxides from Column 1 metal, a Column 2 metal, a transition metal, a post-transition metal, a lanthanide metal, or any alloy or combination thereof.
  • Non-limiting examples of metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), gallium (Ga), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), lanthanum (La), ytterbium (Yb).
  • the transition and post-transition metals can be obtained as a metal nitrate, a metal amine, a metal chloride, a metal coordination complex, a metal sulfate, a metal phosphate hydrate, metal complex, or any combination thereof.
  • metal precursor compounds include, nickel nitrate hexahydrate, nickel chloride, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, cobalt phosphate hydrate, or ruthenium chloride, diammonium hexachorouthenate, hexammineruthenium trichloride, pentaammineruthenium dichloride, etc.
  • These metals or metal compounds can be purchased from any chemical supplier such as Sigma-Aldrich (St. Louis, Missouri, USA), Alfa-Aeaser (Ward Hill, Massachusetts, USA), and Strem Chemicals (Newburyport, Massachusetts, USA).
  • the amount of catalytic nanostructure depends, inter alia, on the use of the catalysts in the desired chemical reaction.
  • the amount of catalytic metal present in the particle(s) in the hollow ranges from 0.01 to 100 parts by weight of catalyst per 100 parts by weight of catalyst, from 0.01 to 5 parts by weight of catalyst per 100 parts by weight of catalyst.
  • M 1 , M 1 and M 2 are each 1 to 20 weight % of the total weight of the catalytic nanostructure.
  • a molar amount of each metal ⁇ e.g., M 1 , M 1 and M 2 or M 1 , M 2 , and M 3 ) in the nanostructure 22 can range from 1 to 95 molar %, or 10 to 80 molar%, 50 to 70 molar% of the total moles of the catalytic nanostructure.
  • An average particle size of the catalytic nanoparticle, or oxides thereof, can be 1 to 100 nm, preferably 1 to 30 nm, more preferably 0.7 to 10 nm, most preferably ⁇ 10 nm with a size distribution having a standard deviation of ⁇ 20%.
  • FIG. 3 is a schematic of an embodiment of a method to make the hollow shell zeolite material.
  • the zeolite material 32 can be obtained either through a commercial source ⁇ e.g., Sigma-Aldrich®, USA) or prepared using known methods for making zeolites and calcined in air ⁇ e.g., 6 hours at 500 °C) to remove the cationic component ⁇ e.g., H 4 + ) to form the protonated (H + ) form of the zeolite material 34.
  • the protonated (active) zeolite material 34 can be contacted (suspended) with an aqueous solution of a templating agent (e.g., a quaternary ammonium compound, tertiary ammonium compound, or tetramethyl ammonium hydroxide) and the resulting suspension can be subjected to a dissolution-recrystallization process to produce the zeolite composite material 36 having hollow 14.
  • a templating agent e.g., a quaternary ammonium compound, tertiary ammonium compound, or tetramethyl ammonium hydroxide
  • the dissolution-recrystallization process under hydrothermal conditions can include techniques of heating aqueous solutions of the aqueous templated zeolite suspension at high vapor pressures.
  • the suspension can be heated to 100 °C to 250 °C, preferably 150 °C to 200 °C, for 12 to 36 hours, preferably 18 to 30 hours under autogenous pressure.
  • Dissolution-recrystallization can be performed in a pressure vessel, such as an autoclave, by a temperature-difference method, temperature-reduction method, or a metastable-phase technique.
  • a pressure vessel such as an autoclave
  • the hollow space is formed in the zeolite framework through dissolution of some of the silicon core by the templating agent.
  • the removed silica species can recrystallize on the outer surface upon cooling.
  • the resulting metal -zeolite composite material 36 can be heated in the presence of air (e.g., calcined) to remove the template and any organic residues to form hollow zeolite material 10.
  • Calcination conditions can include a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C and a time of 3 to 10 hours, preferably 4 to 8 hours.
  • the catalysts can be prepared by processes known to those having ordinary skill in the art, for example the catalytic material (metal nanostructure) can be prepared by any one of the methods comprising liquid-liquid blending, solid-solid blending, or liquid-solid blending (e.g., any of precipitation, co-precipitation, impregnation, complexation, gelation, crystallization, microemulsion, sol-gel, solvothermal, dissolution-recrystallization, hydrothermal, sonochemical, or combinations thereof).
  • the metal nanostructure can be encapsulated in the hollow zeolite particle such that it is present in the intra-particle hollow space. The method can also allow for control of the size the metal nanostructure.
  • the metal nanostructure size is larger than the pore size of the zeolite, the metal nanostructure cannot diffuse out of the zeolite so they remain inside the intra-particle hollow space of the zeolite created. Thus, the particle cannot grow or sinter, and hence size is maintained (i.e., sintering is prevented). Moreover, because the size of the metal nanostructure is reduced, the formation of coke can be inhibited. Furthermore, the methods used to prepare the catalysts of the present invention allow tuning of the size of metallic nanostructures as well as the type of metals that can be used.
  • FIG. 4 is a schematic of an embodiment of a method to make the encapsulated metal nanoparticle/hollow shell zeolite material.
  • the zeolite material 32 can be obtained either through a commercial source and heated as described above to obtain the active zeolite material 34.
  • an aqueous solution of the M 1 precursor material e.g., a nickel precursor
  • a M 2 precursor material e.g., ruthenium or cobalt precursors
  • optionally a M 3 precursor material can be contacted with the zeolite material 34 to allow impregnation of the zeolite material with the precursor materials 42.
  • the amount of solution of metal precursor material is the same or substantially the same as the pore volume of the zeolite material.
  • the impregnated zeolite material can be dried to obtain a catalytic impregnated zeolite material 44. Drying conditions can include heating the impregnated zeolite material from 30 °C to 100 °C, preferably 40 °C to 60 °C, for 4 to 24 hours.
  • the impregnated zeolite material 44 can be contacted (suspended) with an aqueous solution of a templating agent (e.g., a quaternary ammonium hydroxide compound) and the resulting suspension is subjected to a dissolution-recrystallization process to produce the encapsulated nanoparticle/zeolite composite material 46 having metal nanostructures 42 positioned in hollow 14.
  • a templating agent e.g., a quaternary ammonium hydroxide compound
  • the zeolite is subjected to a vacuum prior to impregnation (e.g., 100 to 300 °C for 6 h under 10 "6 bar) to facilitate metal diffusion through the pores.
  • the dissolution-recrystallization process under hydrothermal conditions can include techniques of heating aqueous solutions of the aqueous templated zeolite suspension at high vapor pressures.
  • the suspension is heated to 100 °C to 250 °C, preferably 150 °C to 200 °C, for 12 to 36 hours, preferably 18 to 30 hours under autogenous pressure.
  • Dissolution-recrystallization can be performed in a pressure vessel, such as an autoclave, by a temperature-difference method, temperature-reduction method, or a metastable-phase technique.
  • the hollow is formed in the zeolite framework through dissolution of some of the silicon core by the templating agent.
  • the removed silica species can recrystallize on the outer surface upon cooling.
  • the metal precursors can form a catalytic (e.g., metallic, bimetallic, or trimetallic) nanostructure in the intra-particle hollow space. Since the catalytic nanostructures are too large to migrate through the microporous zeolite walls, they remain in the intra-particle hollow space. In some instances, small nanostructures come together and form a larger nanostructure or a single nanostructure in the intra-particle hollow space.
  • the resulting metal -zeolite composite material 46 can be heated in the presence of air (e.g., calcined) to remove the template and any organic residues to form encapsulated catalytic nanostructure/ hollow zeolite material 10.
  • Calcination conditions can include a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C and a time of 3 to 10 hours, preferably 4 to 8 hours.
  • the encapsulated catalytic nanostructure/ hollow zeolite material 42 can be subjected to conditions sufficient to reduce the metals to their lowest valence and form catalytic nanostructure 2. Without wishing to be bound by theory, it is believed that treating the metal nanostructure with hydrogen can generate larger metal particles from smaller metal oxide particles in the hollow zeolite.
  • the method includes contacting a reactant feed of a hydrocarbon with any one of the hollow zeolites and/or catalytic nanostructure/hollow zeolite catalyst materials 10 and 20 discussed above and/or throughout this specification under sufficient conditions to produce a desired chemical product.
  • the reactant feed can be saturated hydrocarbon stream and/or a hydrocarbon stream having a boiling point of 340 °C or more at atmospheric pressure.
  • the product stream can include alkylated hydrocarbons (e.g., ethylbenzene, cumene), gasoline, jet fuel, diesel, olefinic gases, or any combination thereof.
  • carbon formation or coking and/or sintering can be reduced or inhibited occur when the catalyst 22 is subjected to the reaction conditions.
  • the method can further include isolating, separating and/or storing the produced product mixture.
  • a method for producing alkyl aromatic hydrocarbons is described.
  • the method can include contacting any one of the catalysts described above or throughout the specification with an aromatic hydrocarbon and an olefin in a reaction zone under reaction conditions sufficient to produce an alkyl aromatic compound.
  • Reaction conditions can include a temperature of about 150 °C to about 400 °C, a pressure of about 5 bar to 70 bar and/or a gas hourly space velocity (GHSV) ranging from about 1000 to about 100,000 h "1 .
  • GHSV gas hourly space velocity
  • the catalyst can be contacted with benzene and ethylene to produce ethylbenzene, or the catalyst can be contacted with benzene and propylene to produce cumene.
  • the hollow zeolites of the present invention can be used in a system for production of chemical products (e.g., ethylbenzene, cumene, etc.).
  • the system can include an inlet for a reactant feed, a reaction zone that is configured to be in fluid communication with the inlet, and an outlet configured to be in fluid communication with the reaction zone and configured to remove a product stream from the reaction zone.
  • the reaction zone can include the hollow zeolite particle of the present invention described above and in the Example section.
  • the reaction zone can be a continuous flow reactor selected from a fixed- bed reactor, a fluidized reactor, or a moving bed reactor.
  • the system is a fluid catalytic cracking system (FCC) or an alkylation reaction system (e.g., to produce ethylbenzene from benzene and ethylene or to produce cumene from benzene and propylene).
  • FCC fluid catalytic cracking system
  • alkylation reaction system e.g., to produce ethylbenzene from benzene and ethylene or to produce cumene from benzene and propylene.
  • 13X zeolite (Sigma-Aldrich®) was calcined at 500 °C under air to remove the H 4 + cation and produce the activated (protonated) zeolite.
  • X-ray diffraction (Characterization of Hollow FAU 13X Type Zeolite Material) [0059] X-ray diffraction (XRD): XRD patterns were collected with Empyrean X-ray diffractometer from PANalytical (the Netherlands) using a nickel-filtered CuKa X-ray source, a convergence mirror and a PIXcelld detector. The scanning rate was 0.01 degrees over the range between 5 degrees and 80 degrees at 2 theta ( ⁇ ).
  • FIG. 5 shows XRD diffraction patterns of the comparative FAU-13X type zeolite (top) and hollow FAU-13X type zeolite of the present invention (bottom). From comparison of the two patterns it was determined that the crystal structure remained intact and that the relative peak intensities of the 2 patterns were different. The difference in peak intensities was attributed to a de- alumination process that occurred during the synthesis of the hollow zeolite.

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Abstract

Hollow zeolite particles are disclosed. The hollow zeolite particle can have a zeolite type framework peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI- type framework. Methods of making and using the hollow zeolite particle are also described.

Description

HOLLOW ZEOLITE TYPE CATALYSTS WITH VARYING FRAMEWORK AND
ZEOLITE TOPOLOGIES
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 62/296,699 filed February 18, 2016, and U.S. Provisional Patent Application No. 62/378,460 filed August 23, 2016. The entire contents of each of the above-referenced disclosures are specifically incorporated herein by reference without disclaimer.
BACKGROUND OF THE INVENTION
A. Field of the Invention
[0002] The invention generally concerns a non-MFI zeolite catalyst for chemical applications (e.g., hydrocarbon reforming reactions such as dry or steam reforming of methane). In particular, the invention concerns a catalyst that includes a hollow zeolite particle having a zeolite framework type structure with a peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell.
B. Description of Related Art
[0003] Zeolites belong to a broader material category known as "molecular sieves" and are often referred as such. Zeolites have uniform, molecular-sized pores, and can be separated based on their size, shape, and polarity. For example, zeolites may have pore sizes ranging from about 0.3 nm to about 1 nm. The crystalline structure of zeolites can provide good mechanical properties and good thermal and chemical stability. Zeolites are microporous, possess regular pores and cavities, and have acidic behavior, which make them useful as catalysts or support material in commercial chemical processes (e.g., fluid catalytic cracking, alkylation, reforming, etc.). Many conventional zeolite catalysts include catalytic material. These catalysts suffer from deactivation, stability, and leaching of the catalytic material. By way of example, the catalytic material can be smaller than the pores of the zeolite allowing the catalytic material to diffuse through the pore, which diminishes the stability of the catalyst. Other problems associated with deactivation of zeolites containing catalytic material include poor dispersion of the catalytic material on the surface of the zeolite, and/or leaching of the catalytic material from the zeolite. [0004] Several recent disclosures have focused on improving the activity and life of reforming catalysts by using MFI-type zeolites that include catalytic material. The attempts have focused on reducing the particle size of the catalytic metal, using promoters in the catalyst matrix, or encapsulating the catalytic metal in a metal oxide by forming core@shell type structures. (See, for example, Li et al., Chem. Commun. 2013, 49; Li, Ph.D. Thesis, L'Universite Claude Bernard Lyon 1, HAL Id: tel-1163661, June 2015, and Dai et al., J. Materials of Chemistry A, 2015, 3, 16461-16468).
[0005] Other attempts to improve the stability and activity of non-MFI type zeolite catalysts include making composite type materials that include the zeolite as a component of the composite. These composite shells are aggregations of several zeolite particles with inter- particle hollow spaces in the shell. By way of example, U.S. Patent No. 4,546,090 to Olson et al. discloses composite material that includes a shell made from powdered zeolitic material and matrix material {e.g., clay, a binder, or other inorganic materials). In another example, Chinese Patent No. 1202966 C describes a zeolite crystallized around a fly ash hollow microsphere (mullite) to produce a zeolite/mullite hollow composite having. In yet another example, Japanese Patent Application Publication No. 2009-269788 describes a composite hollow material that includes a drug/*BEA-type aggregate zeolite shell with inter-particle aggregates.
[0006] Despite all of the currently available research on hollow zeolite catalysts, many of the resulting non-MFI type zeolites are composite structures that can be inefficient to produce on a commercial scale. Further, the composite materials can have adverse effects on pore size, reactant and product diffusion into and out of the materials, can ultimately reduce catalytic efficiency, or can contribute to deactivation of the catalyst.
SUMMARY OF THE INVENTION
[0007] A solution to the problems associated with the costs, deactivation, synthesis, and degradation of non-MFI type zeolites has been discovered. In particular, the solution of the present invention concerns a hollow zeolite particle having a zeolite type structure peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type framework. The hollow zeolite particle of the present invention can have a single type of zeolite framework structure throughout the particle in that it is not a composite where two or more different materials (e.g., different zeolites, inert/non-catalytic materials (e.g., binders, fly ash, drugs, etc.)) constitute the particle. The particle can be a pure non-MFI zeolite shell having the intra- particle hollow space. The particles of the present invention can have: 1) any desired Si/Al ratio (1 to∞); 2) different framework and zeolite topologies; and/or 3) a shell with high surface area on both internal and external surfaces. The high surface area allows more than one type of reaction to occur on the same catalyst site. For example, a dehydrogenation of hydrocarbon reaction can occur on the internal surface and a hydrocarbon alkylation reaction can occur on the external surface of the hollow zeolite of the present invention. Furthermore, the hollow zeolite particle of the present invention can be used to control dispersion of metal or metal oxide deposition inside the pore, and the size of the active material (metal or metal oxide) in the hollow surface and/or on the external surface of the zeolite particle. The methods to make the hollow zeolite particle of the present invention provides an elegant manner to achieve simultaneously, macroporous and/or mesoporous and/or microporous channels that offer shape selectivity which could be interconnected to overcome mass transfer limitations.
[0008] In a particular aspect of the present invention, there is disclosed a hollow zeolite particle having a zeolite type structure peripheral shell that defines and encloses an intra- particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type structure. In particular, the hollow zeolite particle has a FAU X- type or Y-type framework peripheral shell, preferably a FAU-X type framework structure, more preferably a 13X-type structure peripheral shell as characterized by an X-ray diffraction pattern shown in FIG. 5. Another hollow zeolite particle can have a MWW type structure, a *BEA type structure, a LTA type structure, a MOR type structure, an ITH type structure, a CHA type structure, a *MRE type structure, a MER type structure, or a VFI type structure peripheral shell. The hollow particle can have at least a second intra-particle hollow space (e.g., 2, 3, 4, 5 hollow spaces) within the interior of the shell. The intra-particle hollow space can have a diameter of 50% to 80% of the diameter of the particle. The hollow particle can have a BET surface area of 140 cm3/g to 600 cm3/g and/or a diameter of 10 nanometers to 450 nanometers. The framework of hollow zeolite particle can include pores having a diameter of 2 nanometers or less, preferably 0.1 nanometers to 0.5 nanometers. Catalytic metal or oxides thereof can be included in the hollow zeolite particle. The catalytic metal or oxide thereof can be positioned in the intra-particle hollow space, on the surface of the shell, embedded in the shell or any combination thereof. Catalytic metal or metal oxides thereof can include Column 1 (e.g., lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs)) metal or oxides thereof or any alloy or combination thereof) , a Column 2 (e.g., magnesium (Mg), calcium (Ca), or barium (Ba)) metal, a transition (e.g., vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn)) metal, a post-transition (gallium (Ga), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi)) metal, a lanthanide (lanthanum (La), ytterbium (Yb)) metal, or any alloy or combination thereof.
[0009] In another aspect, a method to make the hollow zeolite particle described above can include (a) obtaining a synthesis mixture of a protonated zeolite and a templating agent and (b) heat treating the synthesis mixture to form a zeolite framework type structure peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell. Heat-treating in step (b) can remove aluminum ions from the protonated zeolite framework. The templating agent can be a quaternary or a tertiary ammonium compound or a salt thereof, preferably tetramethylammonium hydroxide. In a particular aspect, the templating agent is metal free. Heat-treating the synthesis mixture can include (i) heating the synthesis mixture to obtain a crystalline material, and (ii) calcining the crystalline material. Heating in step (i) can include subjecting the solution to a temperature of 100 °C to 250 °C, preferably 150 °C to 200 °C, for 1 to 3 days, preferably 1 to 5 days under static conditions. Calcining the crystalline material in step (ii) can include subjecting the crystalline material to a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C, for 3 to 10 hours, preferably 4 to 8 hours. Obtaining a protonated form of the zeolite can include subjecting the zeolite to a cation exchange process to exchange cations with proton. The calcined catalyst can be subjecting to reducing conditions to convert the metal oxide to the metal having a zero valence. In some embodiments, the protonated zeolite can be impregnated with a metal precursor.
[0010] Systems for producing a chemical product are also described. A system can include (a) an inlet for a reactant feed; (b) a reaction zone (e.g., a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor) that is configured to be in fluid communication with the inlet, wherein the reaction zone includes the hollow zeolite particle of the present invention; and (c) an outlet configured to be in fluid communication with the reaction zone and configured to remove a product stream from the reaction zone. The reaction zone can a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor. A saturated hydrocarbon stream or a hydrocarbon stream having a boiling point of 340 °C or more at atmospheric pressure or both can be used as a reactant feed and/or the product stream can include alkylated hydrocarbons, gasoline, jet fuel, diesel, olefinic gases, or any combination thereof.
[0011] Methods of using the hollow zeolite particle described above in a chemical reaction (e.g., fluid catalytic cracking reaction, a hydrocracking reaction, an alkylation of an aromatic hydrocarbon reaction, etc.) are disclosed. The method can include contacting the hollow zeolite particle of the present inventions with a reactant feed to catalyze a chemical reaction; and producing a product feed. In some particular, instances the chemical reaction can be an alkylation of an aromatic hydrocarbon reaction (e.g., alkylation of benzene with ethylene to produce ethylbenzene, alkylation of benzene with propylene to produce isopropylbenzene (cumene), etc.).
[0012] Also disclosed in the context of the present invention are thirty-seven embodiments. In a first embodiment, a hollow zeolite particle is described. The hollow zeolite particle of embodiment 1 can have a zeolite type framework peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type framework. Embodiment 2 is the hollow zeolite particle of embodiment 1, having a FAU X-type or Y-type structure peripheral shell. Embodiment 3 is the hollow zeolite particle of embodiment 2, having a FAU X-type structure peripheral shell. Embodiment 4 is the hollow zeolite particle of embodiment 3, wherein the FAU X-type structure peripheral shell is a 13 X-type structure peripheral shell. Embodiment 5 is the hollow zeolite particle of embodiment 4, characterized by an X-ray diffraction (XRD) pattern shown in FIG. 5. Embodiment 6 is the hollow zeolite particle of any one of embodiments 1 to 5, having a surface area of 140 cm3/g to 600 cm3/g. Embodiment 7 is the hollow zeolite particle of any one of embodiments 1 to 6, including at least a second intra-particle hollow space within the interior of the shell. Embodiment 8 is the hollow zeolite particle of any one of embodiments 1 to 7, having a diameter of 10 nanometers to 450 nanometers. Embodiment 9 is the hollow zeolite particle of embodiment 8, wherein the intra-particle hollow space has a diameter of 50% to 80% of the diameter of the particle. Embodiment 10 is the hollow zeolite particle of any one of embodiments 1 to 9, wherein the zeolite framework type peripheral shell includes pores having a diameter of 2 nanometers or less, preferably 0.1 nanometers to 0.5 nanometers. Embodiment 11 is the hollow zeolite particle of any one of embodiments 1 to 10, wherein the thickness of the zeolite framework type peripheral shell is 5 nanometers to 20 nanometers. Embodiment 12 is the hollow zeolite particle of any one of embodiments 1 to 11 that further includes a catalytic metal or oxide thereof. Embodiments 13 is the hollow zeolite particle of embodiment 12, wherein the catalytic metal or oxide thereof is positioned in the intra-particle hollow space, on the surface of the shell, embedded in the shell or any combination thereof. Embodiment 14 is the hollow zeolite particle of any one of embodiments 12 to 13, wherein the catalytic metal or metal oxide is a Column 1 metal, a Column 2 metal, a transition metal, a post- transition metal, a lanthanide metal, or any alloy or combination thereof. Embodiment 15 is the hollow zeolite particle of embodiment 14, wherein the Column 1 metal is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) or oxides thereof or any alloy or combination thereof. Embodiment 15 is the hollow zeolite particle of embodiment 14, wherein the Column 2 metal is magnesium (Mg), calcium (Ca), or barium (Ba) or oxides thereof or any alloy or combination thereof. Embodiment 16 is the hollow zeolite particle of embodiment 14, wherein the transition metal is vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), or oxides or any alloy or combination thereof. Embodiment 17 is the hollow zeolite particle of embodiment 14, wherein the post transition metal is gallium (Ga), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), or oxides thereof, or any alloy or combination thereof. Embodiment 18 is the hollow zeolite particle of embodiment 14, wherein the lanthanide metal is lanthanum (La), ytterbium (Yb) or oxides thereof or any alloy or combination thereof. Embodiment 19 is the hollow zeolite particle of any one of embodiments 1 and 5 to 19, having a MWW type structure, a *BEA type structure, a LTA type structure, a MOR type structure, an ITH type structure, a CHA type structure, a MRE type structure, a MFE type structure, or a VFI type structure peripheral shell.
[0013] Embodiment 21 is a method of making the hollow zeolite particle of any one of embodiments 1 to 20. The method of embodiment 21 includes (a) obtaining a synthesis mixture of a protonated zeolite and a templating agent; and (b) heat treating the synthesis mixture to form a zeolite framework type structure peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell. Embodiment 22 is the method of embodiment 21, wherein the templating agent is a quaternary or a tertiary ammonium compound or a salt thereof, preferably tetramethylammonium hydroxide. Embodiment 23 is the method of any one of embodiments 21 to 22, wherein the templating agent is metal free. Embodiment 24 is the method of any one of embodiments 21 to 23, wherein heat-treating the synthesis mixture includes (i) heating the synthesis mixture to obtain a crystalline material, and (ii) calcining the crystalline material. Embodiment 25 is the method of embodiment 24, wherein heating in step (i) includes subjecting the solution to a temperature of 100 °C to 250 °C, preferably 150 °C to 200 °C, for 1 to 3 days, preferably 1 to 5 days under static conditions. Embodiment 26 is the method of any one of embodiments 20 to 25, wherein step (ii) includes subjecting the crystalline material to a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C, for 3 to 10 hours, preferably 4 to 8 hours. Embodiment 27 is the method of embodiment 26 that further includes drying the crystalline material at 90 °C to 110 °C for 8 to 12 hours prior to step (b). Embodiment 28 is the method of any one of embodiments 20 to 27, wherein step (a) includes subjecting the zeolite to a cation exchange process to exchange cations with protons. Embodiment 29 is the method of embodiment 28, wherein the cation is ammonium ion ( H4 +). Embodiment 30 is the method of any one of embodiments 20 to 29, wherein heat-treating in step (b) removes aluminum ions from the protonated zeolite. Embodiment 31 is the method of any one of embodiments 20 to 30, wherein the protonated zeolite is impregnated with a metal precursor material.
[0014] Embodiment 32 is a method of using the hollow zeolite particle of any one of embodiments 1 to 20 in a chemical reaction. The method of embodiment 32 includes (a) contacting the hollow zeolite particle of any one of embodiments 1 to 20 with a reactant feed to catalyze a chemical reaction; and (b) producing a product feed. Embodiment 33 is the method of embodiment 32, wherein the chemical reaction is a fluid catalytic cracking reaction, a hydrocracking reaction, or an alkylation reaction. In particular instances, the alkylation reaction can be an alkylation of an aromatic hydrocarbon reaction such as alkylation of benzene with ethylene to produce ethylbenzene or alkylation of benzene with propylene to produce cumene.
[0015] Embodiment 34 is a system for producing a chemical product. The system of embodiment 34 includes (a) an inlet for a reactant feed; (b) a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone includes the hollow zeolite particle of any one of embodiments 1 to 20; and (c) an outlet configured to be in fluid communication with the reaction zone and configured to remove a product stream from the reaction zone. Embodiment 35 is the system of embodiment 34, wherein the reaction zone is a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor. Embodiment 36 is the system of any one of embodiments 34 to 35, wherein the reactant feed is a saturated hydrocarbon stream or a hydrocarbon stream having a boiling point of 340 °C or more at atmospheric pressure or both. Embodiment 37 is the system of any one of embodiments 34 to 36, wherein the product stream includes alkylated hydrocarbons, gasoline, jet fuel, diesel, olefinic gases, or any combination thereof.
[0016] The following includes definitions of various terms and phrases used throughout this specification.
[0017] The phrase "intra-particle hollow space" refers to a hollow space or void in within the interior surface of a zeolite shell. FIG. 1A provides a non-limiting example of a particle of the present invention that includes a single intra-particle hollow space. FIG. IB provides a non-limiting example of a particle of the present invention that includes two intra-particle hollow spaces.
[0018] The phrase "inter-particle space" refers to a space or void that is created when multiple particles are contacted with one another and spaces or voids are created between the outer surfaces of such particles. FIG. 1C provides a non-limiting example of a plurality of particles of the present invention, each having a single intra-particle hollow space, that form inter-particle spaces or voids between the outer surfaces of such particles.
[0019] The term "catalyst" refers to a single hollow zeolite particle or a plurality of hollow zeolite particles positioned adjacent to each other in a catalytic bed and/or shaped into a form that can catalyze a chemical reaction. FIGS. 1A-1C provide non-limiting examples of catalysts of the present invention.
[0020] The term "nanostructure" refers to an object or material in which at least one dimension of the object or material is equal to or less than 1000 nm (e.g., one dimension is 1 to 1000 nm in size). In a particular aspect, the nanostructure includes at least two dimensions that are equal to or less than 1000 nm (e.g., a first dimension is 1 to 1000 nm in size and a second dimension is 1 to 1000 nm in size). In another aspect, the nanostructure includes three dimensions that are equal to or less than 1000 nm (e.g., a first dimension is 1 to 1000 nm in size, a second dimension is 1 to 1000 nm in size, and a third dimension is 1 to 1000 nm in size). The shape of the nanostructure can be of a wire, a particle (e.g., having a substantially spherical shape), a rod, a tetrapod, a hyper-branched structure, a tube, a cube, or mixtures thereof. "Nanostructures" include particles having an average diameter size of 1 to 1000 nanometers. In a particular instance the nanostructure is a nanoparticle.
[0021] Particle size of the nanostructures or other particles can be measured using known techniques. Non-limiting examples include transmission electron spectroscopy (TEM), scanning electron microscopy (SEM), preferably TEM.
[0022] The term "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
[0023] The term "substantially" and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
[0024] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.
[0025] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.
[0026] The use of the words "a" or "an" when used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims, or the specification, may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."
[0027] The words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
[0028] The hollow zeolite nanoparticle of the present invention can "comprise," "consist essentially of," or "consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase "consisting essentially of," in one non-limiting aspect, a basic and novel characteristic of the hollow zeolite nanoparticle of the present invention are (1) a zeolite type framework peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type framework and (2) their use in catalyzing chemical reactions.
[0029] The terms "wt.%", "vol.%", or "mol.%" refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. A non-limiting example is 1 wt.% of M1 means that a 100 gram sample of catalyst contains 0.01 grams of M1 in its metallic form.
[0030] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.
[0032] FIG. 1A is an illustration of an embodiment of cross-sectional view of a hollow zeolite with an intra-particle hollow space within the interior of the shell.
[0033] FIG. IB is an illustration of an embodiment of a cross-sectional view of a hollow zeolite with two intra-particle hollow spaces within the interior of the shell. [0034] FIG. 1C is an illustration of an embodiment of a cross-sectional view of a plurality of zeolite particles, each having an intra-particle hollow space, that form inter- particle spaces between the outer surfaces of the particles.
[0035] FIG. 2A is an illustration of an embodiment of a cross-sectional view of a hollow zeolite with a nanostructure contacting the inner surface of the intra-particle hollow space within the interior of the shell.
[0036] FIG. 2B is an illustration of an embodiment of a cross-sectional view of a hollow zeolite with a nanostructure not contacting the inner surface of the intra-particle hollow space within the interior of the shell.
[0037] FIG. 2C is an illustration an embodiment of a cross-sectional view of a hollow zeolite with a plurality of nanostmctures in the intra-particle hollow space within the interior of the shell of the present invention.
[0038] FIG. 3 is an illustration of a method of making the hollow zeolite having an intra- particle hollow space within the interior of the shell of the present invention.
[0039] FIG. 4 is an illustration of a method of making the hollow zeolite with a nanostructure in the intra-particle hollow space within the interior of the shell of the present invention.
[0040] FIG. 5 shows X-ray diffraction patterns of a comparative FAU 13X- type zeolite particle (top) and a hollow FAU 13X type zeolite particle of the present invention (bottom).
[0041] FIG. 6 shows nitrogen isotherms of the comparative FAU 13X type zeolite particle (top isotherms) and a hollow FAU 13X type zeolite particle of the present invention (bottom isotherms).
[0042] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and may herein be described in detail. The drawings may not be to scale.
DETAILED DESCRIPTION OF THE INVENTION
[0043] A discovery has been made that avoids problems associated with deactivation of zeolite type catalysts that do not have MFI-type framework structure. The discovery is based on the premise to create an intra-particle hollow (void) space within the interior portion of a zeolite particle. The hollow zeolite particle can include a catalytic material. The catalytic material and the zeolite type can be selected for a desired result (e.g., catalytic metals can be included in the hollow to catalyze a given chemical reaction). The method of making the hollow zeolite nanoparticle allows for creation of an intra-particle hollow space in the zeolite particle and/or tuning of the thickness and/or acidity of the zeolite shell surrounding the intra- particle hollow space.
[0044] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.
A. Catalyst Structure and Materials
1. Hollow Zeolite Particle and Zeolite Material
[0045] The hollow zeolite structure of the present invention includes an intra-particle hollow space within the interior surface of the zeolite particle shell. FIGS. 1A-1C are cross- sectional illustrations of hollow zeolite particle 10 having an intra-particle hollow space zeolite structure. The hollow zeolite particle 10 has a zeolite-type framework peripheral shell 12 and intra-particle hollow space 14. FIG. IB depicts the intra-particle hollow zeolite particle 10 having two intra-particle hollow spaces. FIG. 1C depicts a catalyst that includes a plurality of the hollow zeolite particles 10. The hollow zeolite particle 10 can have a surface area of 140 cm3/g to 600 cm3/g, 150 cm3/g to 500 cm3/g, 200 cm3/g to 400 cm3/g, or 140 cm3/g, 150 cm3/g, 200 cm3/g, 250 cm3/g, 300 cm3/g, 350 cm3/g, 400 cm3/g, 450 cm3/g, 500 cm3/g, 550 cm3/g, 600 cm3/g or any range or value there between and/or a diameter of 10 nanometers (nm) to 450 nm, 100 to 300 nm, 150 to 250 nm, or 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 400 nm, 450 nm or any range or value there between. A volume space of the intra-particle hollow space 14 can be about 30 to 80%, 40 to 70%, or 50 to 60% of the zeolite particle volume or 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%), 80%) or any value or range there between. The diameter of the intra-particle hollow space can be 50 to 80%, or 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any range or value there between of the diameter of the particle.
[0046] The zeolite shell 12 can be any porous zeolite or zeolite-like material devoid of zeolite material having a MFI-type structure. The zeolite material can be a naturally occurring zeolite, a synthetic zeolite, a zeolite that have other materials in the zeolite framework (e.g., phosphorous), or combinations thereof. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) may be carried out to determine the properties of zeolite materials, including their crystallinity, size and morphology. The network of such zeolites is made up of Si04 and A104 tetrahedra, which are joined via shared oxygen bridges. An overview of the known structures may be found, for example, in W. M. Meier, D. H. Olson and Ch. Baerlocher, "Atlas of Zeolite Structure Types", Elsevier, 5th edition, Amsterdam 2001. The zeolite material can have secondary building blocks of 4, 5, 6, 8, 18, 4-1, 4-2, 4-4, 5-1, 5-2, 5-3, 6-1, 6-1 (1 :4), 6-2, 6-3, 6-6, 8-8, 1-4-1, 1-6-1, 2-6-2, or combinations thereof. In a particular instance, a zeolite having secondary building units of 6- 6 or 6-2 or 6 or 4-2 or 1-4-1 or 4 is used. It should be understood that a zeolite having a pentasil and/or 5-1 secondary building unit can possess different characteristics than a MFI zeolite (for example, structure, porosity, pore volume, thermal stability and the like) and is these zeolites are not considered a MFI framework type zeolite in the present invention. Non-limiting examples of zeolites include ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ATN, ATO, ATS, ATT, ATV, AWO, AWW, *BEA, BIK, BOG, BPH, BRE, CAN, CAS, CFI, CGF, CGS, CHA, CHI, -CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, EUO, *EWT, FAU, FER, GIS, GME, GOO, HEU, IFR, ISV, ITE, ITH, ITG, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN, MAZ, MEI, MEL, MEP, MER, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAT, NES, NON, OFF, OSI, PAR, PAU, PHI, RHO, RON, RSN, RTE, RTH, RUT, SAO, SAT, SBE, SBS, SBT, SFF, SGT, SOD, STF, STI, STT, TER, THO, TON, TSC, VET, VFI, VNI, VSV, WIE, WEN, YUG and ZON structures and mixed structures of two or more of the abovementioned structures. In some embodiments, the zeolite includes phosphorous to form an AIPOx structure. Non-limiting examples of AIPOx zeolites include AABW, AACO, AAEI, AAEL, AAEN, AAET, A AFG, AAFI, AAFN, AAFO, AAFR, AAFS, AAFT, AAFX, AAFY, AAHT, AANA, AAPC, AAPD, AAST, AATN, AATO, AATS, AATT, AATV, AAWO, AAWW, ABEA, ABIK, ABOG, ABPH, ABRE, ACAN, ACAS, ACFI, ACGF, ACGS, ACHA, ACHI, A-CLO, ACON, ACZP, AD AC, ADDR, ADFO, ADFT, ADOH, ADON, AEAB, AEDI, AEMT, AEPI, AERI, AESV, AEUO, A*EWT, AFAU, AFER, AGIS, AGME, AGOO, AHEU, AIFR, AISV, AITE, AITH, AITG, AJBW, AKFI, ALAU, ALEV, ALIO, ALOS, ALOV, ALTA, A LTL, A LTN, AMAZ, AMEI, AMEL, AMEP, AMER, AMFS, AMON, AMOR, AMSO, AMTF, AMTN, AMTT, AMTW, AMWW, ANAT, ANES, ANON, AOFF, AOSI, APAR, APAU, APHI, ARHO, ARON, ARSN, ARTE, ARTH, ARUT, AS AO, AS AT, ASBE, ASBS, ASBT, ASFF, ASGT, ASOD, ASTF, ASTI, ASTT, ATER, ATHO, ATON, ATSC, AVET, AVFI, AVNI, AVSV, AWIE, AWEN, AYUG and AZON structures and mixed structures of two or more of the abovementioned structures. In particular embodiments, the zeolite is a porous zeolite in pure silica (Si/Al=∞) form or with a small amount of Al, for example, a FAU type structure (including X and Y structures), a MWW type structure, a *BEA type structure, a LTA type structure, a MOR type structure, an ITH type structure, a CHA type structure, a MER type structure, a MFE type structure, or a VFI type structure zeolites. Zeolites may be obtained from a commercial manufacturer such as Zeolyst (Valley Forge, Pennsylvania, U. S.A.). Shell 12 can include at least 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.% 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.% or 99 wt.%, or 100 wt.%) of zeolite material. The shell is porous and includes pores having a diameter of 2 nanometers or less, 0.1 nanometers to 0.5 nanometers, or 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 1.1 nm 1.2 nm, 1.3 nm, 1.4 nm, 1.5 nm, 1.6 nm, 1.7 nm, 1.8 nm, 1.9 nm, 2.0 nm or any value or range there between. Depending on the application, the thickness of the shell can be tuned. The thickness can range from 5 to 20 nm, or 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 1 1 nm, 12 nm, 13 nm, 14 nm, 15 nm 16 nm, 17 nm, 18 nm, 19 nm, 20 nm or any range or value there between. Shell 12 includes an inner surface 16 and outer surface 18. Inner surface 16 forms the outer surface of the intra-particle hollow space 14. Inner surface 16 and outer surface 18 are made of the same zeolite material, or a combination of zeolite materials.
[0047] A plurality of the hollow zeolite particles 10 can be used to together to form a catalytic material 15. FIG. 1C depicts a plurality of hollow zeolite particles 10 in combination with an inert surface 17. Inert surface 17 can be a holder (e.g., tray, tube, etc.) or a material (e.g., binder, clays, polymeric material, etc.) that holds the hollow zeolite particles in position so that they can be used in a reaction zone. When two or more hollow zeolite particles 10 are positioned next to each other, inter-particle void 19 is formed. In some instances, the inert surface imparts structural integrity to the hollow zeolite particle. Since the zeolite is pure silicalite zeolite and/or substantially inert, the inter-particle void spaces between the hollow zeolite particles 10 will have no activity or substantially no activity.
2. Catalytic Material [0048] The hollow zeolite particle can include catalytic material. The catalytic material can be a metal nanostructure contained within the intra-particle hollow space that is present in the zeolite. FIGS. 2 A through 2C are cross-sectional illustrations of catalyst material 20 having an encapsulated metal nanostructure/hollow zeolite structure. The catalyst material 20 has a zeolite shell 12, a catalytic (e.g., metal, bimetallic or trimetallic) nanostructure 22 and intra-particle hollow space 14. In some embodiments, a portion of the nanostructure 22 (e.g., M1, M1 and M2 and/or M3) can be deposited on the surface of the zeolite (not shown). As discussed in detail below, the intra-particle hollow space 14 can be formed by removal of a portion of the zeolite core during the making of the catalyst material. As shown in FIG. 2 A, the catalytic nanostructure 22 contacts a portion of the inner wall of hollow space 14. As shown in FIG. 2B, the catalytic nanostructure 22 does not contact the walls of the intra- particle hollow space 14. As shown in FIG. 2C, multiple catalytic nanostructures 22 are in the intra-particle hollow space 14 with some catalytic nanostructures touching the inner wall of the intra-particle hollow space. In certain aspects, 1% to 99%, 10% to 80%, 20% to 70%, 30%) to 60%), 40%) to 50% or any range or value there between of the nanostructures fills the intra-particle hollow space 14. A diameter of the catalytic nanostructure 14 can range from 1 nm to 100 nm, preferably 1 nm to 50 nm, or more preferably 1 nm to 5 nm or any value or range there between. In some embodiments, 1 to 100 nm, preferably 1 to 30 nm, more preferably 3 to 15 nm, most preferably < 10 nm with a size distribution having a standard deviation of ± 20%>. The pore size of the resulting catalyst is the same or similar to the pore size of the starting zeolite. Diameters of the catalytic nanostructure and pore size of the catalyst can be determined using transmission electron microscopy (TEM) and Barrett- Joy ner-Halenda (BJH) methods known in the art.
[0049] Catalytic nanostructure(s) 22 can include one or more active (catalytic) metals to promote a desired chemical reaction (e.g., hydrocarbon cracking, alkylation, isomerization, etc.). In particular instances, the chemical reaction can be an alkylation reaction such as an alkylation of an aromatic hydrocarbon reaction (e.g., alkylation of benzene with ethylene to produce ethylbenzene or alkylation of benzene with propylene to produce cumene). The nanostructure(s) 22 can include one or more catalytic metals or metal oxides from Column 1 metal, a Column 2 metal, a transition metal, a post-transition metal, a lanthanide metal, or any alloy or combination thereof. Non-limiting examples of metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), vanadium (V), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), gallium (Ga), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), lanthanum (La), ytterbium (Yb). Many of the metals can be obtained from metal precursor compounds. For example, the transition and post-transition metals can be obtained as a metal nitrate, a metal amine, a metal chloride, a metal coordination complex, a metal sulfate, a metal phosphate hydrate, metal complex, or any combination thereof. Examples of metal precursor compounds include, nickel nitrate hexahydrate, nickel chloride, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, cobalt phosphate hydrate, or ruthenium chloride, diammonium hexachorouthenate, hexammineruthenium trichloride, pentaammineruthenium dichloride, etc. These metals or metal compounds can be purchased from any chemical supplier such as Sigma-Aldrich (St. Louis, Missouri, USA), Alfa-Aeaser (Ward Hill, Massachusetts, USA), and Strem Chemicals (Newburyport, Massachusetts, USA).
[0050] The amount of catalytic nanostructure depends, inter alia, on the use of the catalysts in the desired chemical reaction. In some embodiments, the amount of catalytic metal present in the particle(s) in the hollow ranges from 0.01 to 100 parts by weight of catalyst per 100 parts by weight of catalyst, from 0.01 to 5 parts by weight of catalyst per 100 parts by weight of catalyst. M1, M1 and M2 are each 1 to 20 weight % of the total weight of the catalytic nanostructure. A molar amount of each metal {e.g., M1, M1 and M2 or M1, M2, and M3) in the nanostructure 22 can range from 1 to 95 molar %, or 10 to 80 molar%, 50 to 70 molar% of the total moles of the catalytic nanostructure. An average particle size of the catalytic nanoparticle, or oxides thereof, can be 1 to 100 nm, preferably 1 to 30 nm, more preferably 0.7 to 10 nm, most preferably < 10 nm with a size distribution having a standard deviation of ± 20%.
B. Preparation of the Hollow Zeolite Particle
[0051] The catalysts of the present invention can be prepared by processes known to those having ordinary skill in the art as well as the process described in the Examples. FIG. 3 is a schematic of an embodiment of a method to make the hollow shell zeolite material. In method 30, step 1, the zeolite material 32 can be obtained either through a commercial source {e.g., Sigma-Aldrich®, USA) or prepared using known methods for making zeolites and calcined in air {e.g., 6 hours at 500 °C) to remove the cationic component {e.g., H4 +) to form the protonated (H+) form of the zeolite material 34. In step 2, the protonated (active) zeolite material 34 can be contacted (suspended) with an aqueous solution of a templating agent (e.g., a quaternary ammonium compound, tertiary ammonium compound, or tetramethyl ammonium hydroxide) and the resulting suspension can be subjected to a dissolution-recrystallization process to produce the zeolite composite material 36 having hollow 14. The dissolution-recrystallization process under hydrothermal conditions can include techniques of heating aqueous solutions of the aqueous templated zeolite suspension at high vapor pressures. In a particular embodiment, the suspension can be heated to 100 °C to 250 °C, preferably 150 °C to 200 °C, for 12 to 36 hours, preferably 18 to 30 hours under autogenous pressure. Dissolution-recrystallization can be performed in a pressure vessel, such as an autoclave, by a temperature-difference method, temperature-reduction method, or a metastable-phase technique. Without wishing to be bound by theory, it is believed that during the dissolution-recrystallization process, the hollow space is formed in the zeolite framework through dissolution of some of the silicon core by the templating agent. The removed silica species can recrystallize on the outer surface upon cooling. In step 3, the resulting metal -zeolite composite material 36 can be heated in the presence of air (e.g., calcined) to remove the template and any organic residues to form hollow zeolite material 10. Calcination conditions can include a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C and a time of 3 to 10 hours, preferably 4 to 8 hours.
C. Preparation Encapsulated Nanoparticle/Hollow Zeolite Material
[0052] The catalysts can be prepared by processes known to those having ordinary skill in the art, for example the catalytic material (metal nanostructure) can be prepared by any one of the methods comprising liquid-liquid blending, solid-solid blending, or liquid-solid blending (e.g., any of precipitation, co-precipitation, impregnation, complexation, gelation, crystallization, microemulsion, sol-gel, solvothermal, dissolution-recrystallization, hydrothermal, sonochemical, or combinations thereof). The metal nanostructure can be encapsulated in the hollow zeolite particle such that it is present in the intra-particle hollow space. The method can also allow for control of the size the metal nanostructure. Without wishing to be bound by theory it is believed that because the metal nanostructure size is larger than the pore size of the zeolite, the metal nanostructure cannot diffuse out of the zeolite so they remain inside the intra-particle hollow space of the zeolite created. Thus, the particle cannot grow or sinter, and hence size is maintained (i.e., sintering is prevented). Moreover, because the size of the metal nanostructure is reduced, the formation of coke can be inhibited. Furthermore, the methods used to prepare the catalysts of the present invention allow tuning of the size of metallic nanostructures as well as the type of metals that can be used.
[0053] FIG. 4 is a schematic of an embodiment of a method to make the encapsulated metal nanoparticle/hollow shell zeolite material. In method 40, step 1, the zeolite material 32 can be obtained either through a commercial source and heated as described above to obtain the active zeolite material 34. In step 2, an aqueous solution of the M1 precursor material (e.g., a nickel precursor), a M2 precursor material (e.g., ruthenium or cobalt precursors), and optionally a M3 precursor material can be contacted with the zeolite material 34 to allow impregnation of the zeolite material with the precursor materials 42. The amount of solution of metal precursor material is the same or substantially the same as the pore volume of the zeolite material. The impregnated zeolite material can be dried to obtain a catalytic impregnated zeolite material 44. Drying conditions can include heating the impregnated zeolite material from 30 °C to 100 °C, preferably 40 °C to 60 °C, for 4 to 24 hours. In step 3, the impregnated zeolite material 44 can be contacted (suspended) with an aqueous solution of a templating agent (e.g., a quaternary ammonium hydroxide compound) and the resulting suspension is subjected to a dissolution-recrystallization process to produce the encapsulated nanoparticle/zeolite composite material 46 having metal nanostructures 42 positioned in hollow 14. In some embodiments, the zeolite is subjected to a vacuum prior to impregnation (e.g., 100 to 300 °C for 6 h under 10"6 bar) to facilitate metal diffusion through the pores. The dissolution-recrystallization process under hydrothermal conditions can include techniques of heating aqueous solutions of the aqueous templated zeolite suspension at high vapor pressures. In a particular embodiment, the suspension is heated to 100 °C to 250 °C, preferably 150 °C to 200 °C, for 12 to 36 hours, preferably 18 to 30 hours under autogenous pressure. Dissolution-recrystallization can be performed in a pressure vessel, such as an autoclave, by a temperature-difference method, temperature-reduction method, or a metastable-phase technique. Without wishing to be bound by theory, it is believed that during the dissolution-recrystallization process, the hollow is formed in the zeolite framework through dissolution of some of the silicon core by the templating agent. The removed silica species can recrystallize on the outer surface upon cooling. During the hydrothermal process, the metal precursors can form a catalytic (e.g., metallic, bimetallic, or trimetallic) nanostructure in the intra-particle hollow space. Since the catalytic nanostructures are too large to migrate through the microporous zeolite walls, they remain in the intra-particle hollow space. In some instances, small nanostructures come together and form a larger nanostructure or a single nanostructure in the intra-particle hollow space. In step 4, the resulting metal -zeolite composite material 46 can be heated in the presence of air (e.g., calcined) to remove the template and any organic residues to form encapsulated catalytic nanostructure/ hollow zeolite material 10. Calcination conditions can include a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C and a time of 3 to 10 hours, preferably 4 to 8 hours. In step 5, the encapsulated catalytic nanostructure/ hollow zeolite material 42 can be subjected to conditions sufficient to reduce the metals to their lowest valence and form catalytic nanostructure 2. Without wishing to be bound by theory, it is believed that treating the metal nanostructure with hydrogen can generate larger metal particles from smaller metal oxide particles in the hollow zeolite.
D. Use of Hollow Zeolite and/or Catalytic Nanostructure Hollow Zeolite
[0054] Also disclosed is a method of producing a chemical product. The method includes contacting a reactant feed of a hydrocarbon with any one of the hollow zeolites and/or catalytic nanostructure/hollow zeolite catalyst materials 10 and 20 discussed above and/or throughout this specification under sufficient conditions to produce a desired chemical product. The reactant feed can be saturated hydrocarbon stream and/or a hydrocarbon stream having a boiling point of 340 °C or more at atmospheric pressure. The product stream can include alkylated hydrocarbons (e.g., ethylbenzene, cumene), gasoline, jet fuel, diesel, olefinic gases, or any combination thereof. In particular instances, carbon formation or coking and/or sintering can be reduced or inhibited occur when the catalyst 22 is subjected to the reaction conditions. The method can further include isolating, separating and/or storing the produced product mixture.
[0055] In a particularly preferred embodiment, a method for producing alkyl aromatic hydrocarbons is described. The method can include contacting any one of the catalysts described above or throughout the specification with an aromatic hydrocarbon and an olefin in a reaction zone under reaction conditions sufficient to produce an alkyl aromatic compound. Reaction conditions can include a temperature of about 150 °C to about 400 °C, a pressure of about 5 bar to 70 bar and/or a gas hourly space velocity (GHSV) ranging from about 1000 to about 100,000 h"1. In preferred aspects, the catalyst can be contacted with benzene and ethylene to produce ethylbenzene, or the catalyst can be contacted with benzene and propylene to produce cumene.
[0056] The hollow zeolites of the present invention can be used in a system for production of chemical products (e.g., ethylbenzene, cumene, etc.). The system can include an inlet for a reactant feed, a reaction zone that is configured to be in fluid communication with the inlet, and an outlet configured to be in fluid communication with the reaction zone and configured to remove a product stream from the reaction zone. The reaction zone can include the hollow zeolite particle of the present invention described above and in the Example section. The reaction zone can be a continuous flow reactor selected from a fixed- bed reactor, a fluidized reactor, or a moving bed reactor. In some embodiments, the system is a fluid catalytic cracking system (FCC) or an alkylation reaction system (e.g., to produce ethylbenzene from benzene and ethylene or to produce cumene from benzene and propylene).
EXAMPLES
[0057] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters, which can be changed or modified to yield essentially the same results.
Example 1
(Synthesis of Hollow FAU 13X Type Zeolite Material)
[0058] 13X zeolite (Sigma-Aldrich®) was calcined at 500 °C under air to remove the H4 + cation and produce the activated (protonated) zeolite. The activated 13X zeolite (1 g) was dispersed with tetramethyl ammonium hydroxide (TMAOH, 12 mL, AZ® 326 MIF developer, Microchemical, GmbH, Germany). The mixture was transferred into Teflon-lined autoclave and heated at 100 °C under static conditions for 5 days. The material was recovered by centrifugation and washed 3 times with water to remove the excess of template and sodium hydroxide by-product. After drying the material at 100 °C under air for 10 h, the zeolite was calcined 6 h at 500 °C under air to remove the tetramethyl ammonium material trapped into the zeolite pore.
Example 2
(Characterization of Hollow FAU 13X Type Zeolite Material) [0059] X-ray diffraction (XRD): XRD patterns were collected with Empyrean X-ray diffractometer from PANalytical (the Netherlands) using a nickel-filtered CuKa X-ray source, a convergence mirror and a PIXcelld detector. The scanning rate was 0.01 degrees over the range between 5 degrees and 80 degrees at 2 theta (Θ). FIG. 5 shows XRD diffraction patterns of the comparative FAU-13X type zeolite (top) and hollow FAU-13X type zeolite of the present invention (bottom). From comparison of the two patterns it was determined that the crystal structure remained intact and that the relative peak intensities of the 2 patterns were different. The difference in peak intensities was attributed to a de- alumination process that occurred during the synthesis of the hollow zeolite.
[0060] Isothermal Analysis: Nitrogen adsorption/desorption isotherms of comparative calcined FAU-13X type zeolite and hollow FAU-13X type zeolite of the present invention were collected at 77 K using a Micromeritics® ASAP 2010 instrument (Micromeritics®, USA) were obtained. Before the measurement, approximately 100 mg of sample was degassed under vacuum (10"6 bar) at 350 °C for 10 hours. FIG. 6 shows the N2 Isotherm of the comparative calcined FAU-13X type zeolite (top curves) and hollow FAU-13X type zeolite of the present invention (bottom curves). From comparison of the data, it was determined that the surface area of the FAU-13X type zeolite of the present invention decreased. This decrease was attributed to the de-alumination during the synthesis process. Hysteresis of FAU-13X type zeolite of the present invention at about 0.48 to 0.5 P/P0 small hysteresis was observed, which is in agreement with the formation of an intra-particle hollow space in the zeolite.

Claims

A hollow zeolite particle having a zeolite type framework peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell does not have a MFI-type framework.
The hollow zeolite particle of claim 1, having a FAU X-type or Y-type structure peripheral shell.
The hollow zeolite particle of claim 2, having a FAU X-type structure peripheral shell.
The hollow zeolite particle of claim 3, wherein the FAU X-type structure peripheral shell is a 13 X-type structure peripheral shell.
The hollow zeolite particle of claim 4, characterized by an X-ray diffraction (XRD) pattern shown in FIG. 5.
The hollow zeolite particle of any one of claims 1 to 5, having a surface area of 140 cm3/g to 600 cm3/g.
The hollow zeolite particle of any one of claims 1 to 6, comprising at least a second intra-particle hollow space within the interior of the shell.
The hollow zeolite particle of any one of claims 1 to 7, having a diameter of 10 nanometers to 450 nanometers.
The hollow zeolite particle of claim 8, wherein the intra-particle hollow space has a diameter of 50% to 80% of the diameter of the particle.
The hollow zeolite particle of any one of claims 1 to 9, wherein the zeolite framework type peripheral shell comprises pores having a diameter of 2 nanometers or less, preferably 0.1 nanometers to 0.5 nanometers.
The hollow zeolite particle of any one of claims 1 to 10, wherein the thickness of the zeolite framework type peripheral shell is 5 nanometers to 20 nanometers.
The hollow zeolite particle of any one of claims 1 to 11, further comprising a catalytic metal or oxide thereof.
13. The hollow zeolite particle of claim 12, wherein the catalytic metal or oxide thereof is positioned in the intra-particle hollow space, on the surface of the shell, embedded in the shell or any combination thereof.
14. The hollow zeolite particle of any one of claims 12 to 13, wherein the catalytic metal or metal oxide is a Column 1 metal, a Column 2 metal, a transition metal, a post- transition metal, a lanthanide metal, or any alloy or combination thereof.
15. A method of making the hollow zeolite particle of any one of claims 1 to 14, the
method comprising: a) obtaining a synthesis mixture of a protonated zeolite and a templating agent; and b) heat treating the synthesis mixture to form a zeolite framework type structure
peripheral shell that defines and encloses an intra-particle hollow space within the interior of the shell.
16. The method of claim 15, wherein the templating agent is a quaternary or a tertiary ammonium compound or a salt thereof, preferably tetramethylammonium hydroxide.
17. The method of any one of claims 15 to 16, wherein the templating agent is metal free.
18. The method of any one of claims 25 to 17, wherein heat treating the synthesis mixture comprises:
(i) heating the synthesis mixture to obtain a crystalline material; and
(ii) calcining the crystalline material.
19. A method of using the hollow zeolite particle of any one of claims 1 to 14 in a
chemical reaction, the method comprising: a) contacting the hollow zeolite particle of any one of claims 1 to 14 with a
reactant feed to catalyze a chemical reaction; and b) producing a product feed.
20. The method of claim 19, wherein the chemical reaction is an alkylation reaction comprising contacting the hollow zeolite particle of any one of claims 1 to 14 with an aromatic hydrocarbon and an olefin in a reaction zone under reaction conditions sufficient to produce the alkyl aromatic compound, preferably wherein (a) the alkyl aromatic compound is ethylbenzene, the aromatic hydrocarbon is benzene, and the olefin is ethylene or (b) the alkyl aromatic compound is cumene, the aromatic hydrocarbon is benzene, and the olefin is propylene.
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WO2018023128A1 (en) * 2016-07-29 2018-02-01 Ohio State Innovation Foundation Topical compositions and methods of using thereof
JP2019043825A (en) * 2017-09-06 2019-03-22 太平洋セメント株式会社 Inorganic particle
JP7114231B2 (en) 2017-09-06 2022-08-08 太平洋セメント株式会社 inorganic particles
WO2019220237A1 (en) * 2018-05-18 2019-11-21 Sabic Global Technologies B.V. Core/shell zeolite materials with hollow zeolite particles, their preparation and catalytic use in single step alkylation+dehydrogenation
CN116328818A (en) * 2023-03-10 2023-06-27 浙江大学 Carrier modified catalyst and preparation method and application thereof

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