WO2019173287A1 - Porous composites and methods of making and using the same - Google Patents

Porous composites and methods of making and using the same Download PDF

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Publication number
WO2019173287A1
WO2019173287A1 PCT/US2019/020681 US2019020681W WO2019173287A1 WO 2019173287 A1 WO2019173287 A1 WO 2019173287A1 US 2019020681 W US2019020681 W US 2019020681W WO 2019173287 A1 WO2019173287 A1 WO 2019173287A1
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solution
titanium
ets
porous composite
halides
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PCT/US2019/020681
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French (fr)
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Xueyi ZHANG
Jay Thakkar
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The Penn State Research Foundation
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    • B01J35/30—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J35/23—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • 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
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/76—Iron group metals or copper

Definitions

  • C 4 - Cio especially C 4 -C6
  • commodity chemicals e.g. liquid transportation fuels
  • oligomerization of smaller alkenes especially ethylene, C2
  • a) oligomerization of ethylene carried over heterogeneous catalysts provides an environmentally friendly route for the direct generation of as desired oligomers (e.g. C4-C6) and b) ethylene as a raw material can be derived readily in abundance from various sources (e.g. bio-ethanol or by cracking of ethane obtained in abundance during natural gas extraction) (Finiels et ak, 2014, Catal. Sci. Technok, 4:2412-2426).
  • the oligomerization of smaller alkenes can be used to generate liquid fuels or their additives, free of aromatics and sulfur, in an environmentally friendly manner (based on process temperature and pressure) (Corma et ak, 2013, Journal of Catalysis, 300: 183-196).
  • micro- and mesoporous aluminosilicates such as zeolites (Sanati, et ak, 1999, Catalysis, 14:236-287; Corma et ak, Chapter 6, Catalysts for Fine Chemical Synthesis, Vol. 4, Microporous and Mesoporous Solid Catalysts, 2006 John Wiley & Sons, Ltd; Muraza, O., 2015, Ind. Eng. Chem. Res., 54:781-789; Finiels et al., 2014, Catal. Sci. Technol., 4:2412-2426; Heveling et al., 1988, Appl.
  • Zeolites are often used as catalysts in olefin oligomerization reactions despite problems associated with the oligomerization of smaller alkenes in the presence of conventional zeolites.
  • Zeolites are 3-D framework materials comprising comer sharing [Si0 4 ] and/or [AlCL] units which generate networks of microporous dimensions (Corma, A., 1995, Chem. Rev., 95:559-414).
  • the presence of trivalent Al 3+ in a tetrahedral geometry generates a -1 charge usually balanced by a cation or a proton (H + ); leading to the generation of a Bransted acid (BA) site (i.e. ⁇ — H + site) in zeolites.
  • BA Bransted acid
  • Oligomerization of ethylene on pure BA zeolites may occur via the formation of unstable 1° carbenium ions on BA sites and therefore requires higher reaction temperatures (T>250 °C) compared to C3+ oligomerizations (Sanati, et al., 1999, Catalysis, 14:236-287;
  • the present invention relates to a porous composite comprising nickel cations and a covalent framework of silicon, oxygen, and titanium atoms.
  • the framework of the porous composite comprises other metal or metalloid atoms selected from the group consisting of boron, aluminum, gallium, indium, thallium, calcium, copper, barium, zinc, iron, cobalt, nickel, lead, and combinations thereof.
  • the porous composite has a diameter of 450 to 550 nm. In one embodiment, the porous composite has a diameter of 0.5 to 10 nm. In one embodiment, the porous composite comprises mesoporous having a diameter of 2 to 10 nm.
  • the present invention also relates in part to an olefin reaction catalyst comprising the porous composite.
  • the present invention also relates in part to a method of making a porous composite, the method comprising the steps of mixing a solution comprising a metal silicate with a solution comprising a titanium source to form a combined solution; heating the combined solution at a temperature between about 150 °C and 250 °C to form a gel; and contacting the gel with a solution comprising a nickel salt.
  • the titanium source is selected from the group consisting of: titanium di chloride, titanium trichloride, titanium tetrachloride, titanium dibromide, titanium tribromide, titanium tetrabromide, titanium difluoride, titanium trifluoride, titanium tetrafluoride, titanium dioxide, titanium (II) oxide, titanium (III) oxide, titanium oxychloride, titanium oxybromide, titanium oxyfluoride, (NH4)2F 6 Ti, (NH ⁇ BmTi, and
  • the step of mixing the solution comprising the metal silicate and the solution comprising the titanium source further comprises the step of adding at least one metal or metalloid compound wherein the metal or metalloid compound is added to the solution comprising the metal silicate, the solution comprising the titanium source, or the combined solution of metal silicate and titanium source.
  • the metal or metalloid compound is selected from the group consisting of cobalt nitrate, nickel nitrate, gallium nitrate, boron nitrate, gallium (III) chloride, gallium (III) bromide, gallium (III) fluoride, boron (III) chloride, boron (III) bromide, boron (III) fluoride, nickel (II) bromide, nickel (II) chloride, nickel (II) fluoride, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) fluoride, sodium aluminate, aluminum chloride, aluminum bromide, aluminum fluoride, alumina, metakaolin, gallium oxides, and boron oxides.
  • the step of mixing the metal silicate solution and the titanium source further comprises the step of adding a surfactant selected from the group consisting of N,N-dimethyl-N-octadecyl-N-(3 -tri ethoxy silylpropyl) ammonium halides; N,N-di ethyl -N- octadecyl-N-(3-tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-butyl-N-(3- tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-hexyl-N-(3 -tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-octyl-N-(3-triethoxysilylpropyl) ammonium halides; N,N- dimethyl-N-de
  • trimethoxysilylpropyl) ammonium halides N,N-dimethyl-N-hexadecyl-N-(3- triethoxysilylpropyl) ammonium halides; N,N-dimethyl-N-octadecyl-N-(3
  • the step of contacting the gel with a solution of a nickel salt further comprises the steps of drying the gel at a temperature
  • the gel is contacted with a solution comprising an ammonium salt before it is dried. In some embodiments, the gel is contacted with a solution comprising a base before it is dried. In some embodiments, the gel is contacted with a solution comprising an ammonium salt and a solution comprising a base before it is dried.
  • the present invention further relates in part to a method for producing a hydrocarbon by oligomerizing an olefin at elevated temperature and pressure which comprises contacting an olefin with a porous composite catalyst comprising nickel cations and a covalent framework of silicon, oxygen, and titanium atoms.
  • said contacting of an olefin is carried out at a temperature less than 210 °C.
  • said contacting of an olefin is carried out at a pressure of at least 3 atm.
  • the catalyst is mixed with a support selected from the group consisting of activated carbon, alumina, silica, and ceramic.
  • the olefin oligomerization occurs in the gas phase.
  • the olefin is a C2 to C 4 olefin.
  • Figure l is a flowchart of an exemplary method for the fabrication of a porous composite material.
  • Figure 3 depicts SEM micrographs.
  • Figure 3A depicts a micrograph of ETS-10 nanoparticles.
  • Figure 3B depicts a micrograph of micron-sized ETS particles.
  • Figure 3C depicts a micrograph of Ni-CIT-6.
  • Figure 3D depicts a micrograph of Ni- MOF-74.
  • Figure 4 depicts the percent conversion of several Ni 2+ -containing catalysts (Ni- ETS-10, Ni-CIT-6, and Ni-MOF-74 with time on stream for ethylene oligomerization reaction at 180 °C, 5 atm pressure, and 90gc2/(gcataiyst h) space velocity.
  • Figure 5 depicts different views of ETS-10.
  • Figure 5A represents the overall structure of ETS-10.
  • Figure 5B depicts another view of the overall structure of ETS-10, wherein cylinders represent micropores containing -Ti-O-Ti- chains.
  • Figure 5C depicts framework units in ETS-10.
  • Figure 5D depicts Ni 2+ ETS-10.
  • Figure 5E depicts another view of Ni 2+ -ETS-lO.
  • Figure 6 depicts a M 2+ exchanged zeolite.
  • Figure 7 depicts the role of Ni 2+ and H + sites during ethylene oligomerization.
  • Figure 8 depicts the incorporation of different metals into ETS-10.
  • Figure 8 A depicts exchanging K + ions with Ni 2+ ions to form Ni 2+ ETS-10.
  • Figure 8B depicts the substitution of tetrahedral Si in the ETS-10 framework with Co 2+ ions, forming M 2+ -Co ETS-10.
  • Figure 9 depicts the incorporation of trivalent elements into the ETS-10 framework.
  • Figure 9A depicts ETS-10 containing Al, B, and/or Ga.
  • Figure 9B depicts Ni 2+ -H + -Ga ETS-10.
  • Figure 10 depicts a cartoon of mesopores several templates used to create mesopores.
  • Figure 10A depicts the incorporation of mesopores into ETS-10.
  • Figure 10B depicts quaternary ammonium surfactants that have been traditionally used as templates in zeolites.
  • Figure 10C depicts a di quaternary ammonium surfactant that has been used as a template to make MFI zeolite nano-plates.
  • Figure 11 depicts powder XRD patterns of Ni 2+ containing catalysts used for exemplary ethylene oligomerization reactions.
  • Figure 12 depicts powder XRD patterns of as-synthesized Ni-MOF-74 and calcined Ni-CIT-6 and Ni-ETS-lO catalysts compared in this study.
  • Figure 13 comprising Figures 13A-B, consists of micrographs of crystalline ETS- 10.
  • Figure 13 A depicts a TEM of crystalline ETS-10 synthesized using a method described herein.
  • Figure 13B depicts an SEM of crystalline ETS-10 synthesized using a method described herein.
  • Figure 14 depicts a TEM image of ETS-10 particles and element maps of Ni-ETS-lO particles.
  • Figure 14A depicts a TEM image of ETS-10 particles synthesized using 3.4Na20 : 1.5 K2O : IT1O2 : 5.5SiC>2 : 6.95 HC1 : 140.7 H2O, where both 12- member rings and 18-member rings (from stacking faults) are visible in the TEM image.
  • Figure 14B depicts an HAADF element map ofNi(6.85 wt%)-ETS-l0 showing a uniform distribution of elements.
  • Figure 14C depicts an Si element map of Ni(6.85 wt%)-ETS-l0 showing a uniform distribution of elements.
  • Figure 14D depicts a Ti element map of Ni(6.85 wt%)-ETS-l0 showing a uniform distribution of elements.
  • Figure 14E depicts an Ni element map of Ni(6.85 wt%)-ETS-l0 showing a uniform distribution of elements.
  • Figure 15 depicts a TEM-EDS image of Ni 2+ -ETS-lO.
  • Figure 16 depicts the catalytic activity of different Ni 2+ containing heterogeneous catalysts as a function of time.
  • Figure 17 depicts the catalytic behavior of four Ni 2+ - containing catalysts (Ni-ETS-lO, Ni-CIT-6, and Ni-MOF-74) with time on stream (TOS).
  • Figure 17A depicts turnover frequency (TOF) based on total C2 consumed and total Ni loading.
  • Figure 17B depicts C 4 selectivity.
  • Figure 17C depicts C 4 oligomer product distribution (all C 4 alkenes normalized to 100%, averaged over the entire TOS range).
  • Figure 18 depicts the oligomeric isomer selectivities of four Ni 2+ -containing catalysts with time on stream for ethylene oligomerization reaction at 180 °C, 5 atm pressure, and 90 gc2/(gcataiyst h) space velocity.
  • Figure 18A depicts Ni(6.85 wt%)- ETS-10.
  • Figure 18B depicts Ni(3.90 wt%)-ETS-l0.
  • Figure 18C depicts Ni-CIT-6.
  • Figure 18D depicts Ni-MOF-74.
  • Figure 19 depicts the C6 selectivity of several Ni 2+ -containing catalysts (Ni-ETS- lO, Ni-CIT-6, and Ni-MOF-74) with time on stream.
  • the term“about” will be understood by persons of ordinary skill in the art and will vary to some extent depending on the context in which it is used. As used herein when referring to a measurable value such as an amount, a temporal duration, and the like, the term“about” is meant to encompass variations of ⁇ 20% or ⁇ 10%, more preferably ⁇ 5%, even more preferably ⁇ 1 %, and still more preferably ⁇ 0.1 % from the specified value, as such variations are appropriate to perform the disclosed methods.
  • range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range.
  • the porous composite comprises a covalent framework of silicon, oxygen, and titanium atoms with associated nickel cations.
  • the covalent framework comprises additional metal or metalloid atoms.
  • Exemplary metal or metalloid atoms include, but are not limited to, boron, aluminum, gallium, indium, thallium, calcium, copper, barium, zinc, iron, cobalt, nickel, lead, and combinations thereof.
  • the porous composite comprises Bruns ted Acid (BA) sites.
  • the BA sites comprise a metal or metalloid atom that generates a -1 charge which is balanced with a proton (H + ).
  • the ratio of total framework metal and metalloid atoms to silicon of the porous composite is 1 : 10. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :9. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :8. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :7. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :6. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :5. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :4. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :3. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :2. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 : 1.
  • the porous composite comprises additional elemental cations associated with the framework.
  • exemplary cations include, but are not limited to, cations of ammonium, sodium, lithium, potassium, calcium, barium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, boron, lead, aluminum, gallium, indium, thallium, and combinations thereof.
  • the ratio of total elemental cations to total framework metal or metalloid elements is 1 : 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.9: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.8: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.7: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.6: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.5: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.4: 1.
  • the ratio of total elemental cations to total framework metal or metalloid elements is 0.3: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.2: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.1 : 1.
  • the porous composite comprises a zeolite.
  • zeolites include, but are not limited to, faujasites, such as zeolites X and Y, mordenite, zeolite beta, ZSM-3, ZSM-5, ZSM-l l, ZSM-12, ZSM-18, ZSM-20, ZSM-34, ZSM-38, ZSM-48, ferrierite, gmelinite, zeolite L, zeolite omega, offretite, NU-87, MCM-22, MCM-41, MCM-48, MCM-36, MCM-56, SSZ-24, Ni-Y, Ni-X, Ni-Beta, SBA-15, ETS-4, AM-6, SSZ-31, ETS-10, ETAS-10, ETBS-10, ETGS-10, TS-l, TS-2, MFI, MEL, MTW, EUO, MTT, HEU, FER, TON, CHA, ERI, KFI, LEV
  • the porous composite comprises pores having diameters between 0.001 nm and 100 nm. In one embodiment, the porous composite comprises micropores having average diameters ⁇ 2 nm. In one embodiment, the micropores are between 0 and 1.25 nm. In one embodiment, the micropores are between 0 and 1 nm. In one embodiment, the micropores are between 0.25 and 1 nm. In one embodiment, the micropores are between 0.3 and 0.85 nm. In one embodiment, the porous composite comprises mesopores having average diameters of 2 - 50 nm. In one embodiment, the mesopores are between 40 and 50 nm. In one embodiment, the mesopores are between 30 and 40 nm.
  • the mesopores are between 20 and 30 nm. In one embodiment, the mesopores are between 10 and 20 nm. In one embodiment, the mesopores are between 2 and 10 nm. In one embodiment, the porous composite comprises macropores having average diameters greater than 50 nm. In one embodiment, the diameter of the macropores is between 50 and 60 nm. In one embodiment, the diameter of the macropores is between 60 and 70 nm. In one embodiment, the diameter of the macropores is between 70 and 80 nm. In one embodiment, the diameter of the macropores is between 80 and 90 nm. In one embodiment, the diameter of the macropores is between 90 and 100 nm. In one embodiment, the diameter of the macropores is greater than 100 nm. In some embodiments, the porous composite comprises pores having various diameters disclosed herein.
  • the porous composite can be formed into any shape known in the art.
  • the porous composite is formed into pellets.
  • Exemplary pellet shapes include, but are not limited to, oblong, tapered, square, rectangular, cylindrical, triangular, and spherical.
  • the porous composite is formed into sheets or plates. Exemplary sheets include, but are not limited to, nanosheets, nanoplates, microsheets, and microplates.
  • the porous composite has an amorphous shape.
  • the porous composite has a diameter between 0.5 and 600 nm. In one embodiment, the porous composite has a diameter between 50 and 600 nm. In one embodiment, the porous composite has a diameter between 100 and 600 nm. In one
  • the porous composite has a diameter between 150 and 600 nm. In one
  • the porous composite has a diameter between 200 and 600 nm. In one
  • the porous composite has a diameter between 250 and 600 nm. In one
  • the porous composite has a diameter between 300 and 600 nm. In one
  • the porous composite has a diameter between 350 and 600 nm. In one
  • the porous composite has a diameter between 400 and 600 nm. In one
  • the porous composite has a diameter between 450 and 600 nm. In one
  • the porous composite has a diameter between 450 and 550 nm.
  • the porous composite has a diameter between 0.5 and 10 nm. In one embodiment, the porous composite has a diameter between 0.5 and 9 nm. In one embodiment, the porous composite has a diameter between 0.5 and 8 nm. In one embodiment, the porous composite has a diameter between 0.5 and 7 nm. In one embodiment, the porous composite has a diameter between 0.5 and 6 nm. In one embodiment, the porous composite has a diameter between 0.5 and 5 nm. In one embodiment, the porous composite has a diameter between 0.5 and 4 nm. In one embodiment, the porous composite has a diameter between 0.5 and 3 nm. In one embodiment, the porous composite has a diameter between 1 and 3 nm. In one embodiment, the porous composite has a diameter between 1.5 and 2.5 nm.
  • the invention relates to a method of producing a porous composite material.
  • Exemplary process 100 is shown in Figure 1.
  • a solution comprising a metal silicate and a solution comprising a transition metal source is provided.
  • the metal silicate solution and the solution of the transition metal source are mixed.
  • the combined solution is heated to form a gel.
  • the gel is contacted with a solution of a nickel salt.
  • the silicate may comprise any metal silicate known to those of skill in the art.
  • Exemplary metal silicates include, but are not limited to silicates with the following formulas: (Na2Si0 2 )n0, Al 2 C>3*Si0 2 , Al 2 C>3*2Si0 2* 2H 2 0, Al 2 0 3* 2Si0 2 , 3Al 2 0 2* 2Si0 2 ,
  • the solution of metal silicate comprises an aqueous solution.
  • the metal silicate solution has an acidic pH.
  • Exemplary chemicals used to make a metal silicate solution having an acidic pH include, but are not limited to, hydrochloric acid, sulfuric acid, acetic acid, citric acid, nitric acid, perchloric acid, hydrobromic acid, and phosphoric acid.
  • the metal silicate solution has a basic pH.
  • Exemplary chemicals used to make a metal silicate solution having a basic pH include, but are not limited to, sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, ammonium hydroxide, and aluminum hydroxide.
  • the metal silicate solution has a neutral pH.
  • the transition metal source may comprise any inorganic source of transition metal.
  • exemplary transition metal sources include, but are not limited to, transition metal halides (such as metal dichlorides, trichlorides, tetrachlorides, dibromides, tribromides, tetrabromides, difluorides, trifluorides, and tetrafluorides), transition metal sulfates (such metal sulfates, metal (II) sulfates, and metal (III) sulfates), transition metal oxides (such metal dioxides, metal (II) oxides, and metal (III) oxides), transition metal oxyhalides (such as metal oxychlorides, oxybromides, and oxyfluorides), diammonium hexahalide transition metal salts (such as (NH4) 2 F 6 Pt, (NH BGdT ⁇ , (NH OEMh), and the like.
  • the transition metal source is a titanium source.
  • step 120 the solution comprising the metal silicate is mixed with the solution comprising the transition metal source.
  • the solution comprising the transition metal source is added to the solution comprising the metal silicate.
  • the solution comprising the transition metal source is added dropwise to the solution comprising the metal silicate. In one embodiment, the solution comprising the transition metal source is added all at once to the solution comprising the metal silicate. In one
  • the solution comprising the metal silicate solution is added to the solution comprising the transition metal source. In one embodiment, the solution comprising the metal silicate is added dropwise to the solution comprising the transition metal source. In one embodiment, the solution comprising the metal silicate is added all at once to the solution comprising the transition metal source. In one embodiment, the addition occurs at room temperature. In one embodiment, the solution comprising the metal silicate is heated to a temperature between 30 °C and 100 °C. In one embodiment, the solution comprising the transition metal source is heated to a temperature between 30 °C and 100 °C. In one
  • the solution comprising the metal silicate is cooled to a temperature between 13 °C and -78 °C. In one embodiment, the solution comprising the transition metal source is cooled to a temperature between 13 °C and -78 °C. In one embodiment, the solution comprising the metal silicate is stirred during the addition. In one embodiment, the solution comprising the transition metal source is stirred during the addition. In one embodiment, the mixture is stirred after the solutions of metal silicate and transition metal source are combined. In one embodiment, the solution comprising the metal silicate is shaken during the addition. In one embodiment, the solution comprising the transition metal source is shaken during the addition. In one
  • the mixture is shaken after the solutions of metal silicate and transition metal source are combined.
  • the shaking is provided using an orbital shaker.
  • the step of mixing the silicate solution with the transition metal source further comprises step 122, wherein at least one metal or metalloid compound is added to the mixture.
  • metal or metalloid compounds include, but are not limited to, cobalt nitrate, nickel nitrate, chromium (III) nitrate, gallium nitrate, boron nitrate, manganese (II) nitrate, iron (III) chloride, iron (III) bromide, iron (III) fluoride, gallium (III) chloride, gallium (III) bromide, gallium (III) fluoride, boron (III) chloride, boron (III) bromide, boron (III) fluoride, nickel (II) bromide, nickel (II) chloride, nickel (II) fluoride, copper (II) chloride, copper (II) bromide, copper (II) fluoride, cobalt (II) chloride, cobalt (II)
  • the metal or metalloid compound is added to the solution comprising the transition metal source. In one embodiment, the metal or metalloid compound is added to the solution comprising the metal silicate. In one embodiment, the metal or metalloid compound is added after the solution comprising the metal silicate and the solution comprising the transition metal source are combined.
  • the step of mixing the silicate solution with the transition metal source further comprises step 124, wherein a surfactant is added to the combined solution.
  • a surfactant is added to the combined solution.
  • the surfactant may comprise a cationic, anionic, or neutral surfactant, as would be understood by one of skill in the art. In one embodiment, the surfactant is neutral.
  • Exemplary neutral surfactants include, but are not limited to, alkyl- polyethylene oxides (such as those related to the TERGITOL® l5-S-m products or the BRIJ® series of surfactants), alkyl-phenyl polyethylene oxides (such as IGEPAL® RC surfactants or the TRITON® X series of surfactants), polyethylene oxide (PEO) polypropylene oxide (PPO) block co-polymers (such as the PLEIRONIC® series of surfactants), primary amines (such as propylamine or iso-propylamine, diamines (such as diaminopentane, diaminohexane and diaminododecane), and organosilanes (such as 3- (N-allylamino)propyltrimethoxysilane; O- allyloxy(polyethyleneoxy)-trimethylsilane; N-(2-aminoethyl)-3-aminopropylmethyl-
  • Methylphenyldimethoxysilane Methyl [2-(3-trimethoxysilylpropylamino)-ethylamino]-3- propionate (65% in methanol); 7-Oct-l-enyltrimethoxysilane; Phenethyltrimethoxysilane; N- Phenylaminopropyltrimethoxysilane; Phenyldimethylethoxysilane; Phenyltriethoxysilane;
  • Phenyltrimethoxysilane Phenylvinyldiethoxysilane; N-[3-(triethoxysilyl)propyl]-4, 5-dihydro- imidazole; 2-(Trimethoxysilyl)ethyl-2 -Pyridine;
  • Triphenylsilanol Vinyldimethylethoxysilane; Vinylmethyldiethoxysilane; Vinyltriethoxysilane; Vinyltrimethoxysilane; 3-Cyanopropyldimethylmethoxysilane; 3 -Cyanopropyltri ethoxy silane; (3-Cyclopentadienylpropyl)triethoxysilane; Diphenyldimethoxysilane; Diphenylsilanediol; Diphenylvinylethoxysilane; (Mercaptomethyl)dimethylethoxysilane;
  • Phenyl dimethyl ethoxy sil ane Pheny ltri ethoxy sil ane ;
  • Triphenylsilanol Vinyldimethylethoxysilane; Vinylmethyldiethoxysilane; Vinyltriethoxysilane; Vinyltrimethoxysilane. N-(trimethoxysilylpropyl)ethylene-diamine, triacetic acid, trisodium salt; 4- Aminobutyldimethylmethoxy silane; 4- Aminobutyltri ethoxy silane (95%); N-(2-aminoethyl)-3- aminopropylmethyldi-methoxysilane; EhNCEhCEhCEhSiOEt 3- aminopropyldimethylethoxy silane; 3 -Aminopropylmethyldi ethoxy silane; 3- Aminopropyldiisopropylethoxysilane; 3 -Aminopropyltri ethoxy silane; 3- Aminopropyltrimethoxysilane; N-(triethoxysilylpropyl)urea
  • the surfactant comprises a cationic surfactant.
  • the cationic surfactant comprises a quaternary ammonium salt.
  • Exemplary quaternary ammonium cations include, but are not limited to, tetra n-propyl ammonium, tetra n- butyl ammonium, tetraethyl ammonium, tetramethyl ammonium, methyl tri-n-butyl ammonium, triethyl methyl ammonium, n-hexyl trimethyl ammonium, trimethyl ammonium, benzyl triethyl ammonium, n-dodecyl trimethyl ammonium, benzyl tri-n-propyl ammonium, tetra n-pentyl ammonium, ethyl pyridinium, diethyl piperidinium, tetra-n-hexyl ammonium, tetra-n-oc
  • the cationic surfactant comprises a quaternary phosphonium salt.
  • Exemplary quaternary phosphonium cations include, but are not limited to, tetra n-propyl phosphonium, tetra n-butyl phosphonium, tetraethyl phosphonium, tetramethyl phosphonium, methyl tri-n-butyl phosphonium, triethyl methyl phosphonium, n-hexyl trimethyl phosphonium, trimethyl phosphonium, benzyl triethyl phosphonium, n-dodecyl trimethyl phosphonium, benzyl tri-n-propyl phosphonium, tetra n-pentyl phosphonium, tetra-n-hexyl phosphonium, tetra-n-octyl phosphonium, tetra-n-dodecyl phosphon
  • the counter ion of the quaternary ammonium salt may be any suitable species, but typically is hydroxide, halide, or the like.
  • the cationic surfactant comprises a quaternary ammonium salt containing an organosilane.
  • exemplary quaternary ammonium cations containing an organosilane include, but are not limited to, N,N-dimethyl-N-tetradecyl-N-(3
  • trimethoxysilylpropyl) ammonium halides N,N-dimethyl-N-octadecyl-N-(3- trimethoxysilylpropyl) ammonium; N,N-dimethyl-N-octadecyl-N-(3 -tri ethoxy silylpropyl) ammonium (Ni et ah, 2016, J.
  • the cationic surfactant is a diquatemary diammonium salt.
  • Exemplary diquatemary diammonium cations include, but are not limited to, N, N, N, N', N', N',- hexamethyl-8,l l-[4.3.3.0]dodecane diammonium (U.S. Pat. No.
  • the surfactant is an anionic surfactant.
  • the anionic surfactant is not limited, and can be any surfactant having an anionic functional group, as would be understood by one of skill in the art.
  • Exemplary anionic surfactants include, but are not limited to, sodium dodecyl sulfate, dodecyl-p-benzenesulfonic acid, alkylphosphoric acid salts and fatty acids.
  • the surfactant is a templating or directing agent. In one embodiment, the surfactant controls the size of the pores formed in the porous composite. In one embodiment, the surfactant controls the diameter of the porous composite. In one embodiment, the length of the alkyl chains in the surfactant affect the pore sizes in the porous composite. In one embodiment, the length of the alkyl chains in the surfactant affect the diameter of the porous composite.
  • the step of mixing the silicate solution with the transition metal source further comprises step 126 wherein a templating agent is added to the combined solution.
  • a templating agent include, but are not limited to, porous carbon (such as activated charcoal and carbon nanotubes), organic polymers (such as poly(methyl methacrylate), starch, and latex), organic small molecules (such as tetraethylene glycol, triethanolamine, triisopropanolamine, triethylene glycol, sulfolane, and diethylglycoldibenzoate), and inorganic salts (such as Mg(OH) 2 and CaCCb).
  • porous carbon such as activated charcoal and carbon nanotubes
  • organic polymers such as poly(methyl methacrylate), starch, and latex
  • organic small molecules such as tetraethylene glycol, triethanolamine, triisopropanolamine, triethylene glycol, sulfolane, and diethylglycoldibenzoate
  • inorganic salts
  • the templating agent controls the size of the pores formed in the porous composite. In one embodiment, the templating agent controls the diameter of the porous composite.
  • the combined solution is heated to form a gel.
  • the reaction mixture is heated to a temperature between 100 °C and 300 °C. In one embodiment, the reaction mixture is heated to a temperature between 120 °C and 290 °C. In one embodiment, the reaction mixture is heated to a temperature between 140 °C and 280 °C. In one embodiment, the reaction mixture is heated to a temperature between 160 °C and 270 °C. In one embodiment, the reaction mixture is heated to a temperature between 180 °C and 260 °C. In one embodiment, the reaction mixture is heated to a temperature between 200 °C and 240 °C. In one embodiment, the reaction mixture is heated to a temperature between 200 °C and 230 °C. In one embodiment, the reaction mixture is heated under atmospheric pressure. In one embodiment, the reaction mixture is heated under elevated pressure. In one embodiment, the reaction mixture is heated under pressures of 0.5 to 30.0 atm. In one embodiment, the reaction mixture is heated under reduced pressure.
  • the gel formed upon heating is filtered to remove liquids.
  • the gel is washed with water.
  • the gel is washed with an organic solvent.
  • organic solvents include, but are not limited to, hexane, pentane, diethyl ether, dichloromethane, benzene, toluene, chloroform, acetone, and ethyl acetate.
  • the gel is dried to form a solid.
  • the gel is dried at room temperature.
  • the gel is dried at an elevated temperature.
  • the gel is dried at a lower temperature.
  • the gel or dried solid is contacted with a solution comprising a transition metal salt.
  • the transition metal salt may comprise any source of transition metal.
  • Exemplary transition metals include, but are not limited to, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and mercury.
  • the transition metal salt is a nickel salt.
  • the solution of nickel salt is an aqueous solution.
  • nickel salts include, but are not limited to, nickel (II) chloride, nickel (III) chloride, nickel (II) bromide, nickel (III) bromide, nickel (II) fluoride, nickel (III) fluoride, nickel
  • contacting the gel or dried solid with a solution comprising a transition metal salt further comprises step 142, wherein the gel or dried solid is contacted with a solution of an inorganic ammonium salt to form an ammonium ion-exchanged porous composite.
  • inorganic ammonium salts include, but are not limited to, ammonium nitrate, ammonium chloride, ammonium bromide, and ammonium acetate.
  • the ammonium ion-exchanged porous composite is dehydrated to form a protonated porous composite.
  • the porous composite is dehydrated by heating to a temperature between 100 °C and 800 °C.
  • the porous composite is dehydrated by heating to a temperature between 200 °C and 700 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 300 °C and 600 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 400 °C and 500 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 475 °C and 525 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 490 °C and 510 °C.
  • the step of contacting the gel or dried solid with a solution comprising a transition metal salt further comprises step 144, wherein the gel or dried solid is contacted with a solution of base.
  • the solution is an aqueous solution.
  • the solution is an organic solution.
  • Exemplary organic solvents used in the solution include, but are not limited to, hexane, pentane, diethyl ether, dichloromethane, benzene, toluene, chloroform, acetone, and ethyl acetate.
  • the solution of base comprises an inorganic base.
  • Exemplary inorganic bases include, but are not limited to, potassium hydroxide, sodium hydroxide, calcium hydroxide, and ammonium hydroxide.
  • the solution of base comprises an organic base.
  • Exemplary organic bases include, but are not limited to, arginine, lysine, histidine, and tetraalkylammonium hydroxides.
  • the gel or dried solid is contacted with the solution of base at a temperature between 0 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 10 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 20 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 30 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 40 °C and 100 °C.
  • the gel or dried solid is contacted with the solution of base at a temperature between 50 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 60 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 70 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 70 °C and 90 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 75 °C and 85 °C. In step 150, the porous composite is dried. In one embodiment, the porous composite is calcined.
  • the porous composite is both dried and calcined. In one embodiment, the porous composite is dried at an elevated temperature. In one embodiment, the porous composite is dried at a temperature between 20 °C and 200 °C. In one embodiment, the porous composite is dried at a temperature between 30 °C and 190 °C. In one embodiment, the porous composite is dried at a temperature between 40 °C and 180 °C. In one embodiment, the porous composite is dried at a temperature between 50 °C and 170 °C. In one embodiment, the porous composite is dried at a temperature between 60 °C and 160 °C. In one embodiment, the porous composite is dried at a temperature between 70 °C and 150 °C.
  • the porous composite is dried at a temperature between 80 °C and 140 °C. In one embodiment, the porous composite is dried at a temperature between 90 °C and 130 °C. In one embodiment, the porous composite is dried at a temperature between 90 °C and 120 °C. In one embodiment, the porous composite is dried at a temperature between 95 °C and 115 °C.
  • the porous composite is calcined. In one embodiment, the porous composite is calcined at a temperature between 400 °C and 550 °C. In one embodiment, the porous composite is calcined at a temperature between 410 °C and 540 °C. In one embodiment, the porous composite is calcined at a temperature between 420 °C and 530 °C. In one embodiment, the porous composite is calcined at a temperature between 430 °C and 520 °C. In one embodiment, the porous composite is calcined at a temperature between 440 °C and 510 °C. In one embodiment, the porous composite is calcined at a temperature between 450 °C and 500 °C.
  • the present invention relates in part to a method of reacting an olefin starting material in the presence of a porous composite of the present invention.
  • exemplary reactions involving olefins include, but are not limited to, olefin isomerization, olefin alkylation, olefin addition, olefin dimerization, olefin oligomerization, olefin polymerization, olefin aromatization, olefin cracking, and olefin hydrocracking.
  • the porous composite is used as a catalyst in an olefin oligomerization reaction.
  • the olefin starting material is a C2-C6 olefin.
  • the olefin starting material is a C2-C6 olefin. In one embodiment, the olefin starting material is a C2-C5 olefin. In one embodiment, the olefin starting material is a C2-C4 olefin. In one embodiment, the olefin starting material is a C2-C3 olefin.
  • Exemplary olefins include, but are not limited to, ethylene (C2), propylene (C3), 1 -butene (C 4 ), trans-2-butene (C 4 ), cis-2-butene (C 4 ), isobutene (C 4 ), l-pentene (C5), cis-2-pentene (C5), trans- 2-pentene (C5) and (2E)-4-methyl-2-pentene (C6).
  • the porous composite is used as a catalyst in an olefin oligomerization reaction.
  • the olefin is oligomerized to form an unbranched product.
  • the olefin is oligomerized to form a branched product.
  • the olefin is oligomerized to form a mixture of branched and unbranched products.
  • the oligomerization reaction produces a higher molecular weight olefin.
  • Exemplary higher molecular weight olefins include, but are not limited to, olefins containing four carbons, olefins containing six carbons, olefins containing eight carbons, olefins containing ten carbons, olefins containing twelve carbons, olefins containing fourteen carbons, olefins containing sixteen carbons, and combinations and/or mixtures thereof.
  • the higher molecular weight olefin is a liquid fuel.
  • higher molecular weight olefin is a liquid fuel additive.
  • the olefin is contacted with the porous composite in a chemical reactor.
  • the reactor is a tank.
  • the reactor is a tubular or pipe reactor.
  • the reactor is a packed bed reactor.
  • the reactor is a fluidized bed reactor.
  • the olefin is contacted with the porous composite in a continuous process.
  • the olefin is contacted with the porous composite in a batch process.
  • the olefin is contacted with the porous composite in the gas phase.
  • the olefin is contacted with the porous composite in the liquid phase.
  • the olefin is contacted with the porous composite in the solid phase.
  • the porous composite is mixed with a support.
  • exemplary supports include, but are not limited to, silica, alumina, ceramic, or activated carbon.
  • the ratio of porous composite to support is 1 :500. In one embodiment, the ratio of the porous composite to support is 1 :450. In one embodiment, the ratio of porous composite to support is 1 :400. In one embodiment, the ratio of porous composite to support is 1 :350. In one embodiment, the ratio of porous composite to support is 1 :300. In one embodiment, the mass ratio of porous composite to support is 1 :250. In one embodiment, the mass ratio of porous composite to support is 1 :200. In one embodiment, the mass ratio of porous composite to support is 1 : 150. In one embodiment, the mass ratio of porous composite to support is 1 : 100.
  • the oligomerization reaction takes place in air. In one embodiment, the oligomerization reaction takes place in the presence of an inert gas. Exemplary inert gases include, but are not limited to, helium, nitrogen, and argon. In one embodiment, the oligomerization reaction occurs under atmospheric pressure. In one embodiment, the
  • oligomerization reaction occurs under pressures higher than atmospheric pressure. In one embodiment, the oligomerization reaction occurs under pressures lower than atmospheric pressure. In one embodiment, the oligomerization reaction occurs between 1 atm and 40 atm. In one embodiment, the oligomerization reaction occurs between 1 atm and 35 atm. In one embodiment, the oligomerization reaction occurs between 1 atm and 30 atm. In one
  • the oligomerization reaction occurs between 1 atm and 25 atm. In one
  • the oligomerization reaction occurs between 1 atm and 20 atm. In one
  • the oligomerization reaction occurs between 1 atm and 15 atm. In one
  • the oligomerization reaction occurs between 1 atm and 10 atm. In one
  • the oligomerization reaction occurs between 2 atm and 9 atm. In one embodiment, the oligomerization reaction occurs between 3 atm and 8 atm. In one embodiment, the oligomerization reaction occurs between 4 atm and 7 atm. In one embodiment, the oligomerization reaction occurs between 4 atm and 6 atm. In one embodiment, the oligomerization reaction occurs between 4.5 and 5.5 atm.
  • the oligomerization reaction is performed at room temperature. In one embodiment, the oligomerization reaction is performed at an elevated temperature. In one embodiment, the oligomerization reaction occurs between 50 °C and 300 °C. In one embodiment, the oligomerization reaction occurs between 75 °C and 275 °C. In one embodiment, the oligomerization reaction occurs between 100 °C and 250 °C. In one embodiment, the oligomerization reaction occurs between 125 °C and 225 °C. In one embodiment, the oligomerization reaction occurs between 150 °C and 200 °C. In one embodiment, the oligomerization reaction occurs between 175 °C and 200 °C. In one embodiment, the oligomerization reaction occurs between 175 °C and 190 °C.
  • Microporous ETS-10 was synthesized using an optimized synthesis system of 3.4Na20 : l.5K 2 0 : IT1O2 : 5.5SiC>2 : 7.0 HC1 : 144H 2 0, modified from Lv et al. to reduce oxide impurities generated as by-products (Lv et al., 2004, Micro. Meso. Mat., 76: 113-122).
  • a first mixture is prepared by dissolving sodium silicate solution (S1O2, Na 2 0, and H2O), NaOH, and KOH in deionized water by stirring the combined components for 10 minutes.
  • a second mixture is prepared by dissolving T1O2 in deionized water under stirring for 10 minutes. The two mixtures are combined under stirring for 30 minutes to produce a slurry gel. The gel is placed in a Teflon-lined autoclave and heated to 200 or 230 °C. After 72 hours, the solids are filtered off, washed with deionized water, and dried at 100 °C.
  • Cobalt incorporated microporous ETS-10 was synthesized by modifying the molar ratio of reactant chemicals (3.4Na 2 0 : l.5K 2 0 : lTi0 2 : 5.5Si0 2 : 0.3 Co(N0 3 ) 2 : 7.0 HC1 : 144H 2 0) and using similar synthesis procedure as above where the Co(NCb) 2 is combined with Ti0 2 prior to mixing this solution with the sodium silicate solution.
  • Mesoporous ETS-10 was synthesized using a synthesis system of 3.7Na 2 0 : l.3K 2 0 : l.OTiCh : 6.7Si0 2 : 0.6TPOAB : 163H 2 0 (Hu et al., 2017, RSC Adv., 7:41204-41209).
  • 10.0 mL of an aqueous NaOH solution (5.38 M) and 9.4 mL of an aqueous KOH solution (4.75 M) are added to 17.8 mL of water glass. The mixture is stirred until it is cooled to room temperature.
  • Mesoporous ETS-10 was alternatively synthesized from microporous ETS-10. Mesopores were generated by contacting ETS-10 with a solution of 1.0 mol/L NaOH at 80 °C for two hours. The product was then washed with distilled water.
  • Cobalt incorporated mesoporous ETS-10 was synthesized with the addition of cobalt nitrate by a similar synthesis procedure described above.
  • the synthesis procedure is identical to that of mesoporous ETS-10 except that 3 mL of a cobalt nitrate aqueous solution (1.1 M) is added to the reaction mixture with the TPOAB (Hu et al., 2017, RSC Adv., 7:41204-41209).
  • the synthesis system for mesoporous ETS-10 incorporating cobalt is 3.7Na 2 0 : l.3K 2 0 : l.0TiO 2 : 6.7Si0 2 : 0.6TPOAB : O. I8C0O : 163H 2 0
  • microporous and mesoporous ETS-10 nano-plates follows the respective synthesis of microporous and mesoporous ETS-10 with normal diameters (i.e. about 500 nm).
  • a diquaternary ammonium surfactant, Ci8H37-N + (CH3)2-C6Hi2-N + (CH3)2-C6Hi3, is added the mixture of metal silicate and titanium source, leading to the formation of zeolite nano- plates having diameters of about 2 nm.
  • Microporous nanoparticle ETS-10 was synthesized using the conventional hydrothermal method based on a previous report (Lv et al., 2004, Microporous Mesoporous Mater., 76: 113-122).
  • NaOH EMD Millipore
  • KOH EMD Millipore
  • Ti0 2 P25, Acros Organics
  • sodium silicate solution (25.5-28.5% Si0 2 , 7.5-8.5% Na 2 0; EMD Millipore
  • 37 wt% HC1 aqueous solution (Sigma-Aldrich) were used without further purification.
  • the gel was then heated in a convection oven at 230 °C for 72 hours.
  • the solid precipitate was recovered, washed with DI water until the pH of the supernatant was 9-10, and dried at 100 °C.
  • Micron-sized ETS-10 particles were synthesized according to the synthesis method based on a previous report (SEM images in Figure 3B) (Rocha et al., 1998, Microporous Mesoporous Mater., 23:253 -263; Casado et al., 2009, Mater. Res. Bull., 44: 1225- 1231).
  • Mesoporous ETS-10 was synthesized using a synthesis system of 3.7Na 2 0 : l.3K 2 0 : l.0TiO 2 : 6.7Si0 2 : 0.6TPOAC1 : 160H 2 O : 0.39 HAcAc, modified from Hu et al. and Xiang et al. (Hu et al., 2017, RSC Adv., 7:41204-41209; Xiang et al., 2015, ChemCatChem., 7:521-525).
  • the TiCb and acetylacetone solution mixture (pre-stirred at room temperature) was combined with NaOH, KOH and sodium silicate solution mixture at ambient temperature in a dropwise manner while stirring at 500 rpm.
  • the thick gel formed at the end was stirred for 60 minutes before addition of N,N-dimethyl-N-octadecyl-N-(3- trimethoxysilylpropyl)ammonium chloride solution.
  • the final gel was further stirred for 120 minutes before heating in a convection oven at 230 °C for 72 hours.
  • the solid precipitate was recovered, washed with DI water until the pH of the supernatant is 9-10, dried at 100 °C, and calcined in air at 500 °C for 5 hours.
  • O.IO6AI2O3 7.1HC1 : 141.25H 2 0, 3.4Na 2 0 : l.5K 2 0 : IT1O2 : 5.266Si0 2 : O.P7B2O3 : 7HC1 : 140.77H2O, 3.4Na 2 0 : l.5K 2 0 : IT1O2 : 5.29Si0 2 : 0.l05Ga 2 C> 3 : 6.95HC1 : 140.4H 2 O, or 3.4Na 2 0 : l.5K 2 0 : IT1O2 : 5.3Si0 2 : O. IC02O3 : 7HC1 : 139.64H 2 0, respectively.
  • Ni 2+ loading Two different ion-exchange procedures were used to obtain different levels of Ni 2+ loading. After ion-exchange with Ni 2+ , three samples with Ni/Ti molar ratios of 0.36, 0.35 and 0.56 were obtained, corresponding to Ni mass percentages of 3.90%, 4.12% and 6.85 %, respectively.
  • the as-synthesized ETS-10 was stirred in a 0.25 mol/L Ni(N0 3 )2 aqueous solution for 18 hours at ambient temperature (or for 3 hours at 80 °C twice for higher Ni 2+ loading), washed with DI water, and calcined at 500 °C for 5 hours (Thakkar et ah, 2018, ChemCatChem., 10:4234-4237).
  • ETS-10 particles with size greater than ⁇ 2.5 pm were also synthesized in order to study the effect of crystallite size on the activity of catalyst in ethylene oligomerization reaction (Ni(4. l2 wt%, 2.5 pm)-ETS-l0) (Rocha et al., 1998, Microporous Mesoporous
  • Ni-CIT-6 and Ni-MOF-74 were also used in order to compare the catalytic outcomes from Ni-ETS-lO.
  • Ni-CIT-6 (Deimund et al., 2014, ACS Catal., 4:4189-4195) and Ni-MOF-74 (Mlinar et al., 2014, ACS Catal. 4:717-721) were synthesized and pretreated using previous reported methods.
  • TEM, STEM, and STEM-EDS images of the synthesized ETS-10 catalysts were taken using FEI Talos F200X instrument at 200kV.
  • SEM images of the ETS-10 catalyst synthesized via Method 1 were obtained on FEI Helios NanoLab 660 FESEM at 5kV.
  • SEM images of the ETS-10 catalyst synthesized via Method 2 were taken using FEI Helios NanoLab 660 FESEM and Thermo Fisher Scios 2 at 2 kV.
  • Bruker Esprit software was used to collect the element maps. Physical adsorption analysis on non-ion exchanged ETS-10 degassed at 180 °C for 4 hrs was performed using Nz gas at -196 °C.
  • ICP-AES analysis was performed on a Ni 2+ -ETS-lO sample made via Method 1 using Perkin-Elmer Optima 5300 instrument. Elemental analysis (ICP) on catalysts made via Method 2 was performed by Galbraith Laboratories, Inc.
  • a down flow, packed bed, high pressure, isothermal, stainless steel reaction unit was built for testing the catalysts for ethylene oligomerization reaction in continuous gas phase mode.
  • Pre-calcined 50 mg catalysts were diluted with pre-calcined (1000 °C, 24 hours) 13.5 gm silica gel (125-149 pm) to obtain a total bed length of 15 cm and bed volume of 11 cm 3 .
  • Isothermal catalyst bed temperature was maintained and monitored throughout the reaction duration using temperature controllers. Heated flow lines were used to eliminate condensation of large oligomeric reaction products.
  • the catalysts were pretreated in helium flow at 5 seem, 180 °C overnight before performing the reactions at 180 °C and 5 atm ethylene absolute pressure. Reaction products were quantified continuously at regular intervals using an online gas chromatograph - FID
  • a packed-bed reactor was used for testing the catalysts for ethylene oligomerization reaction in an isothermal, continuous gas flow mode.
  • Pre-calcined 50 mg catalyst (125-149 pm) was diluted with pre-calcined (1000 °C, 24 hours) 13.5 g silica gel (125- 149 pm) to obtain a total bed length of 15 cm and bed volume of 11 cm 3 in order to eliminate local hot spots and temperature gradients.
  • Isothermal catalyst bed temperature was maintained and monitored throughout the reaction duration using temperature controllers. Heated flow lines (170 °C) were used to eliminate condensation of large oligomeric reaction products.
  • the catalysts were treated in-situ in helium flow at 180 °C for 16 hours before performing the reactions.
  • ETS-10 catalysts were additionally pretreated in-situ under dynamic vacuum (2 mmHg absolute) for 12 hours at 450 °C before helium treatment.
  • the reactions were carried out at 180 °C, 5 atm ethylene pressure and 90 gc2/(gcataiysth) space velocity (conversion ⁇ 1% for all catalysts, Figure 4). Reaction products, rates, and selectivities were quantified continuously using an online gas chromatograph.
  • the present invention relates in part to novel porous materials formed using the methods described herein and the use of these porous materials as olefin oligomerization catalysts.
  • the instant invention is in part based on the formation of a titanosilicate zeolite (known as ETS-10) with controlled dimensions, pore size, and placement of Ni 2+ and H + sites.
  • ETS-10 titanosilicate zeolite
  • This novel zeolite composition results in a catalyst with improved stability activity and product selectivity.
  • Zeolites, including nickel (Ni 2+ ) containing zeolites are promising heterogeneous catalysts for ethylene oligomerization because their large pore sizes, their tunable structure, and chemical environment of their active sites (i.e. coordinatively unsaturated Lewis Acidic [LA] Ni 2+ cations), provide the exclusive opportunity to precisely design the active sites and to control and optimize reaction rate and selectivity of these reactions (Zhang et al., 2012, Science
  • porous catalysts provide the much needed mechanical and thermal stability in the desired reaction temperature range (T ⁇ 200 °C), are regenerable, and can be utilized in gas-phase continuous reaction conditions without the requirement of a pyrophoric co-catalyst (e.g.
  • ETS-10 is notable in that it has properties that make it amenable to optimization in order to overcome the problems in the field of olefin oligomerization.
  • the 3-D structure of ETS-10 a) consists of -O-Ti-O-Ti-O- chains distributed uniformly, b) has large 12 member (7.6 ⁇ X 4.9 ⁇ ) and aperiodic 18 member (14.3 A X 7.6 ⁇ ) ring pores, c) is thermally stable up to 650 °C, d) is easily modifiable (e.g.
  • Each [T ⁇ q ⁇ ] unit generates a -2 charge (due to Ti 4+ ) that are open for cation exchange with divalent cations, such as Ni 2+ , for ion exchange and water treatment applications (Oleksiienko et ak, 2017, Chem. Eng. J., 317:570-585; Popa et al., 2012,
  • Ni 2+ is a divalent cation it requires a combination of two nearby Al atoms in conventional zeolites for charge balance and ion exchange ( Figure 6) (Deimund et ak, 2014, ACS Catak, 4:4189-4195). While increasing Al content in zeolite increases the probability to obtain two nearby Al atoms (consecutively increasing Ni 2+ exchange and catalytic activity), it also simultaneously generates an uncontrolled large amount of isolated Al atoms (BA sites responsible for side reactions, decreasing product selectivity) (Deimund et ak, 2014, ACS Catak, 4:4189-4195). These Ni 2+ containing
  • the present invention relates to the improvement of an ETS-10 catalyst in order to increase the selectivity to C 4 formed during olefin oligomerization reactions.
  • mesopores are incorporated into ETS-10 framework ( Figure 10A) while still maintaining its crystallinity (Donk et al., 2003, Catalysis Reviews, 45:297-319).
  • Mesopores can be built into the ETS-10 framework by utilizing a surfactant, N,N- dimethyl-N-octadecyl-N-(3-triethyoxysilylpropyl) ammonium bromide, as a mesopore template (Figure 10B) (Ni et al., 2016, J. Porous Mater., 23:423-429; Xiang et al, 2015, ChemCatChem, 7:521 - 525). Varying the carbon chain length in the above mesopore template generates mesopores of varying pore size. Therefore, templates of different chain lengths can be used to synthesize mesoporous crystalline ETS-10 of variable pore sizes.
  • a surfactant N,N- dimethyl-N-octadecyl-N-(3-triethyoxysilylpropyl) ammonium bromide
  • Mesopores can also be built into the ETS-10 framework by contacting ETS-10 with a solution of base, wherein the concentration of the base can be used to control the mesopore size.
  • a basic buffer solution can also be used to maintain the pH value during the dissolution process.
  • ETS-10 structure which may benefit its catalytic activity and can be studied.
  • One modification that may improve the catalyst is the generation of BA sites.
  • ETS-10 does not have an isolated -1 charge suitable for generation of a BA site, therefore an isolated -1 charge would need to be generated. This can be done by incorporating trivalent elements like Al, Ga and B in the framework (Lv et al., 2007, Micro. Meso. Mat., 101 :355-362) ( Figure 9A-B).
  • BA sites may lower the reaction temperatures (T ⁇ 200 °C) for the ethylene oligomerization reaction ( Figure 7) while tuning the active site (i.e. Ni 2+ and H + ) concentration can further improve the catalyst stability, activity, and product selectivity.
  • ETS-10 nano-plates having a diameter of around 2 nm.
  • structure directing agents or templates as normally is the case with synthesis of aluminosilicates (e.g. MFI) (Yang et al., 2001, Micro. Meso. Mat., 46: 1-11; Pavel et al., 2004, Micro. Meso. Mat., 71 :77-85; Turta et al., 2008, Micro. Meso.
  • Ni-ETS-lO gas phase ethylene oligomerization reaction in continuous mode on Ni 2+ exchanged ETS-10
  • Zeolite CIT-6 has *BEA topology, but contains Zn 2+ heteroatoms, where the framework Zn atoms generate a -2 charge per Zn (Deimund et al., 2014, ACS Catal., 4:4189-4195) and MOF-74 (Mlinar et al., 2014, ACS Catal., 4:717-721).
  • the -2 charge can be used for loading Ni 2+ for oligomerization, similar to ETS-10 (Deimund et al.,
  • Ni- MOF-74 contains a significant amount of coordinatively unsaturated Ni 2+ which can potentially be utilized for the ethylene oligomerization reaction (Mlinar et al., 2014, ACS Catal., 4:717- 721).
  • the present invention relates to the synthesis and catalytic behaviors of Ni-ETS- lO.
  • a template-free and fluoride-free synthetic method that produces ETS-10 without the impurities commonly seen in other systems is presented.
  • Ni-ETS-lO was found to be more active for ethylene oligomerization and has shown higher stability and higher selectivity to C 4 than the other microporous catalysts (Ni-CIT-6 and Ni-MOF-74) compared in this study.
  • Powder XRD patterns of the synthesized Ni 2+ -ETS-lO titanosilicate and other conventional zeolites Ni 2+ -CIT-6, Ni 2+ -MCM-4l and Ni 2+ -H + -MCM-4l match those reported in literature ( Figure 11) (Hulea et al., 2004, J. Cata., 225:213-222; Lv et al., 2004, Micro. Meso. Mater., 76: 113-122; Deimund et al., 2014, ACS Catal., 4:4189-4195).
  • XRD patterns in Figure 12 show the crystallinity of the Ni-CIT-6 and the Ni-MOF-74 synthesized and used in the study with ETS-10 particles made by Method 2.
  • the TEM images of the synthesized ETS-10 catalysts provide further evidence of their crystallinity (see Figure 13A for ETS-10 particles made by Method 1).
  • Microporous ETS- 10 particles made by both Method 1 and Method 2 have a square bi-pyramidal morphology and a size of less than 500 nm (see Figure 13B for ETS-10 particles made by Method 1 and Figure 3 A for those made by Method 2).
  • High-resolution TEM image of the ETS-10 nanoparticle synthesized via Method 2 provides further evidence of its crystallinity (Figure 14A), where the typical stacking faults of ETS-10 and the resulting 18-member rings are visible. Elemental analysis shows that a Si/Ti ratio of 5.03 was obtained from the ETS-10 synthesized via Method 2 (Table 1).
  • Ni 2+ ions in Ni 2+ -ETS-lO as is evident from TEM-EDS of Ni 2+ -ETS-lO made using Method 1 ( Figure 15) and STEM-EDS of Ni 2+ -ETS-lO made using Method 2 (Ni loading 6.85 wt%, Figures 14B-E).
  • Ni/Ti molar ratio of 0.97 was obtained for Ni 2+ -ETS-lO obtained by Method 1 by performing elemental analysis. This obtained ratio is almost equal to the maximum amount of divalent Ni 2+ which can be theoretically exchanged in ETS-10 based on charge balance (i.e.
  • Elemental analysis of Ni 2+ -ETS-lO obtained by Method 2 shows a Ni/Ti molar ratio of 0.35-0.56 (Table 1).
  • Ni 2+ -ETS-lO has not been studied for ethylene oligomerization before.
  • the results (Table 2) show that Ni 2+ -ETS-lO is a promising catalyst for ethylene oligomerization with the obtained maximum activity of 6.45 goiigomers/(gcataiyst h). This activity is greater than that obtained from traditional microporous zeolites like Ni 2+ -CIT-6 and Ni 2+ -H + -ZSM-5 (Table 2).
  • C 4 (selectivity >88%) and C6 (selectivity >10%) oligomers were the main reaction products (Table 2, Figure 16) with no observed cracking by-products (representing the absence of catalytically active BA sites in Ni 2+ -ETS-lO).
  • Ni-ETS-lO The catalytic performance of Ni-ETS-lO was compared with two other ethylene oligomerization catalysts with comparable particle sizes, Ni-CIT-6 and Ni-MOF-74.
  • Figure 17A and Table 3 show that Ni-ETS-lO is a promising catalyst for ethylene oligomerization with the obtained maximum turnover frequency of 688.96 molc2/(molNi h), when the Ni loading was 3.9 wt%. This rate is greater than those obtained from previously-reported microporous catalysts such as Ni-CIT-6 (with a comparable Ni loading of 3.3 wt%) and Ni-MOF-74 (Figure 17A).
  • Ni-ETS 10 nanoparticles exhibited higher ethylene conversion rates than Ni-CIT-6 and Ni-MOF- 74 over the entire time-on-stream range investigated. Since the catalyst particles have comparable particle sizes ( Figures 3 A, C, and D), the higher rate on Ni-ETS- 10 may not be due to diffusion limitation, but due to the property of the active sites. Ni-ETS-lO with lower loading (Ni(3.90 wt%)-ETS-lO) showed higher initial TOF than Ni-ETS-lO with higher Ni loading
  • heterogeneous catalysts Reaction conditions: 180 °C, 5 atm ethylene absolute pressure, 90 gethyiene/(gcataiyst h). *Oligomeric wt% calculations done for the maximum obtained activity injection in GC. Others: Cs, Ci alkanes + alkenes.
  • Ni(6.85 wt%)-ETS-l0 also showed the lowest C6 selectivity over the entire period of 6 hours ( Figure 19). Overall, these observations indicate that Ni(6.85 wt%)-ETS-l0 is a stable catalyst for ethylene oligomerization to C 4 and that Ni-ETS-lO is a promising catalyst for ethylene oligomerization.
  • Ni-ETS-lO catalyst was active for ethylene oligomerization, which shows higher rate (based on total Ni) than other microporous catalysts. Ni-ETS-lO also showed highest selectivity to C 4 and higher stability than other microporous catalysts investigated in this work.

Abstract

The present invention relates in part to method of fabricating a porous composite by mixing a solution comprising a metal silicate with a solution comprising a titanium source to form a combined solution, heating the combined solution of metal silicate and titanium source to form a gel, and contacting the gel with a solution comprising a nickel salt. The invention also relates in part to porous composites produced using said method and to a method of using said porous composites as catalysts in reactions involving olefins.

Description

TITLE
Porous Composites and Methods of Making and Using the Same
CROSS-REFERENCE TO RELATED APPLICATIONS The present application claims priority to U.S. Provisional Application Serial No. 62/638,366, filed on March 5, 2018, which is incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
With limited oil reserves and the projected increase in demand in the near future, there is a need to find alternative, environmentally greener ways for generation of olefins (C4- Cio, especially C4-C6) which can be used as or to manufacture commodity chemicals (e.g. liquid transportation fuels) (NOAA National Centers for Environmental Information, Climate at a Glance: Global Time Series, published June 2017; 2015 World Oil Outlook, Organization of the Petroleum Exporting Countries (OPEC), Ban et ak, October 2015, retrieved on July 16, 2017; Muraza, O., 2015, Ind. Eng. Chem. Res., 54:781-789). One promising possibility is via oligomerization of smaller alkenes (especially ethylene, C2) because a) oligomerization of ethylene carried over heterogeneous catalysts provides an environmentally friendly route for the direct generation of as desired oligomers (e.g. C4-C6) and b) ethylene as a raw material can be derived readily in abundance from various sources (e.g. bio-ethanol or by cracking of ethane obtained in abundance during natural gas extraction) (Finiels et ak, 2014, Catal. Sci. Technok, 4:2412-2426). Additionally, the oligomerization of smaller alkenes can be used to generate liquid fuels or their additives, free of aromatics and sulfur, in an environmentally friendly manner (based on process temperature and pressure) (Corma et ak, 2013, Journal of Catalysis, 300: 183-196).
The oligomerization of ethylene has been studied on various heterogenous catalysts such as metal oxides and sulfates (Sanati, et ak, 1999, Catalysis, 14:236-287; Xu et ak, 2018, ACS Catal., 8:2488-2497; Sohn et ak, 2007, J. Ind. Eng. Chem., 13:47-56; Lavrenov et ak, 2010, Kinet. Catal., 51 :404-409; Sohn et ak, 2002, Catal. Lett., 81 :259-264), micro- and mesoporous aluminosilicates such as zeolites (Sanati, et ak, 1999, Catalysis, 14:236-287; Corma et ak, Chapter 6, Catalysts for Fine Chemical Synthesis, Vol. 4, Microporous and Mesoporous Solid Catalysts, 2006 John Wiley & Sons, Ltd; Muraza, O., 2015, Ind. Eng. Chem. Res., 54:781-789; Finiels et al., 2014, Catal. Sci. Technol., 4:2412-2426; Heveling et al., 1988, Appl. Catal., 42:325-336; Bonneviot et al., 1983, J. Mol. Catal., 21 :415-430; Martinez et al., 2013, Appl. Catal. A, 467:509-518; Lallemand et al., 2006, Appl. Catal. A, 301 : 196-201, Brogaard et al., 2016, ACS Catal., 6: 1205- 1214; Tanaka et al, 2012, J. Phys. Chem. C, 116:5664-5672; Hwang et al., 2017, Catal. Lett., 147: 1303- 1314; Lallemand et al., 2008, Appl. Catal. A, 338:37- 43; Moussa et al., 2018, ACS Catal., 8:3903 -3912), and metal organic frameworks (MOFs) (Madrahimov et al., 2015, ACS Catal., 5:6713-6718; Liu et al., 2014, RSC Adv., 4:62343- 62346; Klet et al., 2015, J. Am. Chem. Soc., 137: 15680- 15683; Metzger et al., 2016, ACS Cent. Sci., 2:148-153; Canivet et al., 2013, J. Am. Chem. Soc., 135:4195-4198; Kyogoku et al., 2010, J. Jpn. Pet. Inst., 53:308-312).
Zeolites are often used as catalysts in olefin oligomerization reactions despite problems associated with the oligomerization of smaller alkenes in the presence of conventional zeolites. Zeolites are 3-D framework materials comprising comer sharing [Si04] and/or [AlCL] units which generate networks of microporous dimensions (Corma, A., 1995, Chem. Rev., 95:559-414). The presence of trivalent Al3+ in a tetrahedral geometry generates a -1 charge usually balanced by a cation or a proton (H+); leading to the generation of a Bransted acid (BA) site (i.e. Ό— H+ site) in zeolites.
Oligomerization of ethylene on pure BA zeolites may occur via the formation of unstable 1° carbenium ions on BA sites and therefore requires higher reaction temperatures (T>250 °C) compared to C3+ oligomerizations (Sanati, et al., 1999, Catalysis, 14:236-287;
Corma et al., Chapter 6, Catalysts for Fine Chemical Synthesis, Vol. 4, Microporous and Mesoporous Solid Catalysts, 2006 John Wiley & Sons, Ltd; O'Connor et al., 1990, Catal. Today, 6:329-349). The requirement of such high temperatures increases the catalytic activity of BA sites and leads to the formation of a broad spectrum of side-products (due to the side reactions like isomerization, cracking, and aromatization), severe catalyst deactivation by pore blocking, and low oligomeric product selectivity (Muraza, O., 2015, Ind. Eng. Chem. Res., 54:781-789; Finiels et al., 2014, Catal. Sci. Technol., 4:2412-2426). The activity of BA sites is also correlated to site concentration wherein a higher local concentration of BA sites leads to a lower activity (due to the formation of long chain oligomeric products (waxes) strongly adsorbed on active sites which cause pore blocking and catalyst deactivation) (Finiels et al., 2014, Catal. Sci. Technol., 4:2412-2426; Martinez et al., 2013, App. Cata. A: General, 467:509-518; Lallemand et al., 2008, App. Cata. A: General, 338:37-43; Lallemand et al., 2006, App. Cata. A: General, 301 : 196-201; Lallemand et al., 2007, Stud. Surf. Sci. Cata., 170: 1863-1869; Hulea et al., 2004,
J. Cata., 225:213-222; Andrei et al., 2015, J. Cata., 323:76-84; Lallemand et al., 2011, Chem. Eng. J., 172: 1078-1082; Andrei et al., 2015, Eur. Phys. J. Spec. Top., 224: 1831-1841; Zhang et al., 2014, Energy Environment Focus, 3 :246-256). Reducing the concentration of BA sites decreases deactivation but also reduces product branching and chain length and, in turn, fuel quality (Klerk, A., Fischer-Tropsch Refining, First Edition, Chapter 25. 2011, Wiley-VCH Verlag GmbH & Co. KGaA; Klerk, A., Fischer-Tropsch Refining, First Edition, Chapter 27. 2011, Wiley-VCH Verlag GmbH & Co. KGaA; Klerk, A., Fischer-Tropsch Refining, First Edition, Chapter 19. 2011 Wiley-VCH Verlag GmbH & Co. KGaA; Martinez et al., 2013, App. Cata. A: General, 467:509-518).
There is a need in the art for zeolite catalysts with improved properties that will allow for the synthesis of desired hydrocarbon oligomers and for methods to make such catalysts. The present invention satisfies this unmet need.
SUMMARY OF THE INVENTION
In one aspect, the present invention relates to a porous composite comprising nickel cations and a covalent framework of silicon, oxygen, and titanium atoms. In one embodiment, the framework of the porous composite comprises other metal or metalloid atoms selected from the group consisting of boron, aluminum, gallium, indium, thallium, calcium, copper, barium, zinc, iron, cobalt, nickel, lead, and combinations thereof. In one embodiment, the porous composite has a diameter of 450 to 550 nm. In one embodiment, the porous composite has a diameter of 0.5 to 10 nm. In one embodiment, the porous composite comprises mesoporous having a diameter of 2 to 10 nm.
The present invention also relates in part to an olefin reaction catalyst comprising the porous composite.
The present invention also relates in part to a method of making a porous composite, the method comprising the steps of mixing a solution comprising a metal silicate with a solution comprising a titanium source to form a combined solution; heating the combined solution at a temperature between about 150 °C and 250 °C to form a gel; and contacting the gel with a solution comprising a nickel salt. In one embodiment, the titanium source is selected from the group consisting of: titanium di chloride, titanium trichloride, titanium tetrachloride, titanium dibromide, titanium tribromide, titanium tetrabromide, titanium difluoride, titanium trifluoride, titanium tetrafluoride, titanium dioxide, titanium (II) oxide, titanium (III) oxide, titanium oxychloride, titanium oxybromide, titanium oxyfluoride, (NH4)2F6Ti, (NH^BmTi, and
(NH4)2Cl6Ti.
In one embodiment, the step of mixing the solution comprising the metal silicate and the solution comprising the titanium source further comprises the step of adding at least one metal or metalloid compound wherein the metal or metalloid compound is added to the solution comprising the metal silicate, the solution comprising the titanium source, or the combined solution of metal silicate and titanium source. In one embodiment, the metal or metalloid compound is selected from the group consisting of cobalt nitrate, nickel nitrate, gallium nitrate, boron nitrate, gallium (III) chloride, gallium (III) bromide, gallium (III) fluoride, boron (III) chloride, boron (III) bromide, boron (III) fluoride, nickel (II) bromide, nickel (II) chloride, nickel (II) fluoride, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) fluoride, sodium aluminate, aluminum chloride, aluminum bromide, aluminum fluoride, alumina, metakaolin, gallium oxides, and boron oxides.
In one embodiment, the step of mixing the metal silicate solution and the titanium source further comprises the step of adding a surfactant selected from the group consisting of N,N-dimethyl-N-octadecyl-N-(3 -tri ethoxy silylpropyl) ammonium halides; N,N-di ethyl -N- octadecyl-N-(3-tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-butyl-N-(3- tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-hexyl-N-(3 -tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-octyl-N-(3-triethoxysilylpropyl) ammonium halides; N,N- dimethyl-N-decyl-N-(3-triethoxysilylpropyl) ammonium halides; N,N-dimethyl-N-dodecyl-N- (3 -tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-tetradecyl-N-(3
trimethoxysilylpropyl) ammonium halides; N,N-dimethyl-N-hexadecyl-N-(3- triethoxysilylpropyl) ammonium halides; N,N-dimethyl-N-octadecyl-N-(3
trimethoxysilylpropyl) ammonium halides; C22H45-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3 halides; C20H4i-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3 halides; Ci8H37-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3 halides; Ci6H33-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3 halides; Ci4H29-N+(CH3)2-C6Hi2-N+(CH3)2- CeHi3 halides; Ci2H25-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3 halides; and CioH2i-N+(CH3)2-C6Hi2- N+(CH3)2-C6Hi3 halides. In one embodiment, the step of contacting the gel with a solution of a nickel salt further comprises the steps of drying the gel at a temperature of 100 °C and 800 °C.
In some embodiments, the gel is contacted with a solution comprising an ammonium salt before it is dried. In some embodiments, the gel is contacted with a solution comprising a base before it is dried. In some embodiments, the gel is contacted with a solution comprising an ammonium salt and a solution comprising a base before it is dried.
The present invention further relates in part to a method for producing a hydrocarbon by oligomerizing an olefin at elevated temperature and pressure which comprises contacting an olefin with a porous composite catalyst comprising nickel cations and a covalent framework of silicon, oxygen, and titanium atoms. In one embodiment, said contacting of an olefin is carried out at a temperature less than 210 °C. In one embodiment, said contacting of an olefin is carried out at a pressure of at least 3 atm. In one embodiment, the catalyst is mixed with a support selected from the group consisting of activated carbon, alumina, silica, and ceramic. In one embodiment, the olefin oligomerization occurs in the gas phase. In one embodiment, the olefin is a C2 to C4 olefin.
BRIEF DESCRIPTION OF THE DRAWINGS
The following detailed description of various embodiments of the invention will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings illustrative embodiments. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities of the embodiments shown in the drawings.
Figure l is a flowchart of an exemplary method for the fabrication of a porous composite material.
Figure 2 depicts powder X-ray diffraction (XRD) patterns of ETS-10 with compositions of 3.4Na20 : I.5K2O : IT1O2 : 5.5Si02 : xHCl : (116.7 + 3.45x)H20 (with x = 6.6- 8.1), where x = 6.95 showed the least impurities. Peaks from impurities are marked with triangles (▼) and diamonds (¨).
Figure 3, comprising Figures 3A-D, depicts SEM micrographs. Figure 3A depicts a micrograph of ETS-10 nanoparticles. Figure 3B depicts a micrograph of micron-sized ETS particles. Figure 3C depicts a micrograph of Ni-CIT-6. Figure 3D depicts a micrograph of Ni- MOF-74.
Figure 4 depicts the percent conversion of several Ni2+-containing catalysts (Ni- ETS-10, Ni-CIT-6, and Ni-MOF-74 with time on stream for ethylene oligomerization reaction at 180 °C, 5 atm pressure, and 90gc2/(gcataiyst h) space velocity.
Figure 5, comprising Figures 5A-E, depicts different views of ETS-10. Figure 5A represents the overall structure of ETS-10. Figure 5B depicts another view of the overall structure of ETS-10, wherein cylinders represent micropores containing -Ti-O-Ti- chains. Figure 5C depicts framework units in ETS-10. Figure 5D depicts Ni2+ ETS-10. Figure 5E depicts another view of Ni2+-ETS-lO.
Figure 6 depicts a M2+ exchanged zeolite.
Figure 7 depicts the role of Ni2+ and H+ sites during ethylene oligomerization.
Figure 8, comprising Figures 8A-B, depicts the incorporation of different metals into ETS-10. Figure 8 A depicts exchanging K+ ions with Ni2+ ions to form Ni2+ ETS-10. Figure 8B depicts the substitution of tetrahedral Si in the ETS-10 framework with Co2+ ions, forming M2+-Co ETS-10.
Figure 9, comprising Figures 9A-B, depicts the incorporation of trivalent elements into the ETS-10 framework. Figure 9A depicts ETS-10 containing Al, B, and/or Ga. Figure 9B depicts Ni2+-H+-Ga ETS-10.
Figure 10, comprising Figures 10A-C, depicts a cartoon of mesopores several templates used to create mesopores. Figure 10A depicts the incorporation of mesopores into ETS-10. Figure 10B depicts quaternary ammonium surfactants that have been traditionally used as templates in zeolites. Figure 10C depicts a di quaternary ammonium surfactant that has been used as a template to make MFI zeolite nano-plates.
Figure 11 depicts powder XRD patterns of Ni2+ containing catalysts used for exemplary ethylene oligomerization reactions.
Figure 12 depicts powder XRD patterns of as-synthesized Ni-MOF-74 and calcined Ni-CIT-6 and Ni-ETS-lO catalysts compared in this study.
Figure 13, comprising Figures 13A-B, consists of micrographs of crystalline ETS- 10. Figure 13 A depicts a TEM of crystalline ETS-10 synthesized using a method described herein. Figure 13B depicts an SEM of crystalline ETS-10 synthesized using a method described herein.
Figure 14, comprising Figures 14A-E, depicts a TEM image of ETS-10 particles and element maps of Ni-ETS-lO particles. Figure 14A depicts a TEM image of ETS-10 particles synthesized using 3.4Na20 : 1.5 K2O : IT1O2 : 5.5SiC>2 : 6.95 HC1 : 140.7 H2O, where both 12- member rings and 18-member rings (from stacking faults) are visible in the TEM image. Figure 14B depicts an HAADF element map ofNi(6.85 wt%)-ETS-l0 showing a uniform distribution of elements. Figure 14C depicts an Si element map of Ni(6.85 wt%)-ETS-l0 showing a uniform distribution of elements. Figure 14D depicts a Ti element map of Ni(6.85 wt%)-ETS-l0 showing a uniform distribution of elements. Figure 14E depicts an Ni element map of Ni(6.85 wt%)-ETS-l0 showing a uniform distribution of elements.
Figure 15 depicts a TEM-EDS image of Ni2+-ETS-lO.
Figure 16 depicts the catalytic activity of different Ni2+ containing heterogeneous catalysts as a function of time.
Figure 17, comprising Figures 17A-C, depicts the catalytic behavior of four Ni2+- containing catalysts (Ni-ETS-lO, Ni-CIT-6, and Ni-MOF-74) with time on stream (TOS). Figure 17A depicts turnover frequency (TOF) based on total C2 consumed and total Ni loading. Figure 17B depicts C4 selectivity. Figure 17C depicts C4 oligomer product distribution (all C4 alkenes normalized to 100%, averaged over the entire TOS range).
Figure 18, comprising Figures 18A-D, depicts the oligomeric isomer selectivities of four Ni2+-containing catalysts with time on stream for ethylene oligomerization reaction at 180 °C, 5 atm pressure, and 90 gc2/(gcataiyst h) space velocity. Figure 18A depicts Ni(6.85 wt%)- ETS-10. Figure 18B depicts Ni(3.90 wt%)-ETS-l0. Figure 18C depicts Ni-CIT-6. Figure 18D depicts Ni-MOF-74.
Figure 19 depicts the C6 selectivity of several Ni2+-containing catalysts (Ni-ETS- lO, Ni-CIT-6, and Ni-MOF-74) with time on stream.
DETAILED DESCRIPTION
It is to be understood that the Figures and descriptions of the present invention have been simplified to illustrate elements that are relevant for a clear understanding of the present invention, while eliminating, for the purpose of clarity, many other elements found in porous composites as well as methods of making and using such materials. Those of ordinary skill in the art may recognize that other elements and/or steps are desirable and/or required in implementing the present invention. However, because such elements and steps are well known in the art, and because they do not facilitate a better understanding of the present invention, a discussion of such elements and steps is not provided herein. The disclosure herein is directed to all such variations and modifications to such elements and methods known to those skilled in the art.
As used herein, each of the following terms has the meaning associated with it in this section. Unless defined otherwise, all technical and scientific terms used herein generally have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The articles“a” and“an” are used herein to refer to one or to more than one (i.e. to at least one) of the grammatical object of the article. By way of example,“an element” means one element or more than one element.
As used herein, the term“about” will be understood by persons of ordinary skill in the art and will vary to some extent depending on the context in which it is used. As used herein when referring to a measurable value such as an amount, a temporal duration, and the like, the term“about” is meant to encompass variations of ±20% or ±10%, more preferably ±5%, even more preferably ±1 %, and still more preferably ±0.1 % from the specified value, as such variations are appropriate to perform the disclosed methods.
Throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range.
For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range.
Description Porous Composite Composition
In one embodiment, the porous composite comprises a covalent framework of silicon, oxygen, and titanium atoms with associated nickel cations. In one embodiment, the covalent framework comprises additional metal or metalloid atoms. Exemplary metal or metalloid atoms include, but are not limited to, boron, aluminum, gallium, indium, thallium, calcium, copper, barium, zinc, iron, cobalt, nickel, lead, and combinations thereof. In one embodiment, the porous composite comprises Bruns ted Acid (BA) sites. In one embodiment, the BA sites comprise a metal or metalloid atom that generates a -1 charge which is balanced with a proton (H+).
In one embodiment, the ratio of total framework metal and metalloid atoms to silicon of the porous composite is 1 : 10. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :9. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :8. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :7. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :6. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :5. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :4. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :3. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 :2. In one embodiment, the ratio of total framework metal or metalloid atoms to silicon is 1 : 1.
In some embodiments, the porous composite comprises additional elemental cations associated with the framework. Exemplary cations include, but are not limited to, cations of ammonium, sodium, lithium, potassium, calcium, barium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, boron, lead, aluminum, gallium, indium, thallium, and combinations thereof. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 1 : 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.9: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.8: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.7: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.6: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.5: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.4: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.3: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.2: 1. In one embodiment, the ratio of total elemental cations to total framework metal or metalloid elements is 0.1 : 1.
In some embodiments, the porous composite comprises a zeolite. Exemplary zeolites include, but are not limited to, faujasites, such as zeolites X and Y, mordenite, zeolite beta, ZSM-3, ZSM-5, ZSM-l l, ZSM-12, ZSM-18, ZSM-20, ZSM-34, ZSM-38, ZSM-48, ferrierite, gmelinite, zeolite L, zeolite omega, offretite, NU-87, MCM-22, MCM-41, MCM-48, MCM-36, MCM-56, SSZ-24, Ni-Y, Ni-X, Ni-Beta, SBA-15, ETS-4, AM-6, SSZ-31, ETS-10, ETAS-10, ETBS-10, ETGS-10, TS-l, TS-2, MFI, MEL, MTW, EUO, MTT, HEU, FER, TON, CHA, ERI, KFI, LEV, and LTA, ZK-4, ZK-5, zeolite A, zeolite T, clinoptilolite, chabazite and erionite.
In one embodiment, the porous composite comprises pores having diameters between 0.001 nm and 100 nm. In one embodiment, the porous composite comprises micropores having average diameters < 2 nm. In one embodiment, the micropores are between 0 and 1.25 nm. In one embodiment, the micropores are between 0 and 1 nm. In one embodiment, the micropores are between 0.25 and 1 nm. In one embodiment, the micropores are between 0.3 and 0.85 nm. In one embodiment, the porous composite comprises mesopores having average diameters of 2 - 50 nm. In one embodiment, the mesopores are between 40 and 50 nm. In one embodiment, the mesopores are between 30 and 40 nm. In one embodiment, the mesopores are between 20 and 30 nm. In one embodiment, the mesopores are between 10 and 20 nm. In one embodiment, the mesopores are between 2 and 10 nm. In one embodiment, the porous composite comprises macropores having average diameters greater than 50 nm. In one embodiment, the diameter of the macropores is between 50 and 60 nm. In one embodiment, the diameter of the macropores is between 60 and 70 nm. In one embodiment, the diameter of the macropores is between 70 and 80 nm. In one embodiment, the diameter of the macropores is between 80 and 90 nm. In one embodiment, the diameter of the macropores is between 90 and 100 nm. In one embodiment, the diameter of the macropores is greater than 100 nm. In some embodiments, the porous composite comprises pores having various diameters disclosed herein.
The porous composite can be formed into any shape known in the art. In one embodiment, the porous composite is formed into pellets. Exemplary pellet shapes include, but are not limited to, oblong, tapered, square, rectangular, cylindrical, triangular, and spherical. In another embodiment, the porous composite is formed into sheets or plates. Exemplary sheets include, but are not limited to, nanosheets, nanoplates, microsheets, and microplates. In another embodiment, the porous composite has an amorphous shape.
In one embodiment, the porous composite has a diameter between 0.5 and 600 nm. In one embodiment, the porous composite has a diameter between 50 and 600 nm. In one embodiment, the porous composite has a diameter between 100 and 600 nm. In one
embodiment, the porous composite has a diameter between 150 and 600 nm. In one
embodiment, the porous composite has a diameter between 200 and 600 nm. In one
embodiment, the porous composite has a diameter between 250 and 600 nm. In one
embodiment, the porous composite has a diameter between 300 and 600 nm. In one
embodiment, the porous composite has a diameter between 350 and 600 nm. In one
embodiment, the porous composite has a diameter between 400 and 600 nm. In one
embodiment, the porous composite has a diameter between 450 and 600 nm. In one
embodiment, the porous composite has a diameter between 450 and 550 nm.
In one embodiment, the porous composite has a diameter between 0.5 and 10 nm. In one embodiment, the porous composite has a diameter between 0.5 and 9 nm. In one embodiment, the porous composite has a diameter between 0.5 and 8 nm. In one embodiment, the porous composite has a diameter between 0.5 and 7 nm. In one embodiment, the porous composite has a diameter between 0.5 and 6 nm. In one embodiment, the porous composite has a diameter between 0.5 and 5 nm. In one embodiment, the porous composite has a diameter between 0.5 and 4 nm. In one embodiment, the porous composite has a diameter between 0.5 and 3 nm. In one embodiment, the porous composite has a diameter between 1 and 3 nm. In one embodiment, the porous composite has a diameter between 1.5 and 2.5 nm.
Method of Making a Porous Composite In one aspect, the invention relates to a method of producing a porous composite material. Exemplary process 100 is shown in Figure 1. In step 110, a solution comprising a metal silicate and a solution comprising a transition metal source is provided. In step 120, the metal silicate solution and the solution of the transition metal source are mixed. In step 130, the combined solution is heated to form a gel. In step 140, the gel is contacted with a solution of a nickel salt.
In step 110, the silicate may comprise any metal silicate known to those of skill in the art. Exemplary metal silicates include, but are not limited to silicates with the following formulas: (Na2Si02)n0, Al2C>3*Si02, Al2C>3*2Si02*2H20, Al203*2Si02, 3Al202*2Si02,
2Al203*Si02, LriSiCh, K2Si03, and MgOnSi02 »H20. In one embodiment, the solution of metal silicate comprises an aqueous solution. In one embodiment, the metal silicate solution has an acidic pH. Exemplary chemicals used to make a metal silicate solution having an acidic pH include, but are not limited to, hydrochloric acid, sulfuric acid, acetic acid, citric acid, nitric acid, perchloric acid, hydrobromic acid, and phosphoric acid. In one embodiment, the metal silicate solution has a basic pH. Exemplary chemicals used to make a metal silicate solution having a basic pH include, but are not limited to, sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, ammonium hydroxide, and aluminum hydroxide. In one embodiment, the metal silicate solution has a neutral pH.
The transition metal source may comprise any inorganic source of transition metal. Exemplary transition metal sources include, but are not limited to, transition metal halides (such as metal dichlorides, trichlorides, tetrachlorides, dibromides, tribromides, tetrabromides, difluorides, trifluorides, and tetrafluorides), transition metal sulfates (such metal sulfates, metal (II) sulfates, and metal (III) sulfates), transition metal oxides (such metal dioxides, metal (II) oxides, and metal (III) oxides), transition metal oxyhalides (such as metal oxychlorides, oxybromides, and oxyfluorides), diammonium hexahalide transition metal salts (such as (NH4)2F6Pt, (NH BGdTΐ, (NH OEMh), and the like. In one embodiment, the transition metal source is a titanium source.
In step 120, the solution comprising the metal silicate is mixed with the solution comprising the transition metal source. In one embodiment, the solution comprising the transition metal source is added to the solution comprising the metal silicate. In one
embodiment, the solution comprising the transition metal source is added dropwise to the solution comprising the metal silicate. In one embodiment, the solution comprising the transition metal source is added all at once to the solution comprising the metal silicate. In one
embodiment, the solution comprising the metal silicate solution is added to the solution comprising the transition metal source. In one embodiment, the solution comprising the metal silicate is added dropwise to the solution comprising the transition metal source. In one embodiment, the solution comprising the metal silicate is added all at once to the solution comprising the transition metal source. In one embodiment, the addition occurs at room temperature. In one embodiment, the solution comprising the metal silicate is heated to a temperature between 30 °C and 100 °C. In one embodiment, the solution comprising the transition metal source is heated to a temperature between 30 °C and 100 °C. In one
embodiment, the solution comprising the metal silicate is cooled to a temperature between 13 °C and -78 °C. In one embodiment, the solution comprising the transition metal source is cooled to a temperature between 13 °C and -78 °C. In one embodiment, the solution comprising the metal silicate is stirred during the addition. In one embodiment, the solution comprising the transition metal source is stirred during the addition. In one embodiment, the mixture is stirred after the solutions of metal silicate and transition metal source are combined. In one embodiment, the solution comprising the metal silicate is shaken during the addition. In one embodiment, the solution comprising the transition metal source is shaken during the addition. In one
embodiment, the mixture is shaken after the solutions of metal silicate and transition metal source are combined. In one embodiment, the shaking is provided using an orbital shaker.
In some embodiments, the step of mixing the silicate solution with the transition metal source further comprises step 122, wherein at least one metal or metalloid compound is added to the mixture. Exemplary metal or metalloid compounds include, but are not limited to, cobalt nitrate, nickel nitrate, chromium (III) nitrate, gallium nitrate, boron nitrate, manganese (II) nitrate, iron (III) chloride, iron (III) bromide, iron (III) fluoride, gallium (III) chloride, gallium (III) bromide, gallium (III) fluoride, boron (III) chloride, boron (III) bromide, boron (III) fluoride, nickel (II) bromide, nickel (II) chloride, nickel (II) fluoride, copper (II) chloride, copper (II) bromide, copper (II) fluoride, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) fluoride, silver nitrate, sodium aluminate, aluminum chloride, aluminum bromide, aluminum fluoride, alumina, metakaolin, gallium oxides, boron oxides, and combinations thereof. In one embodiment, the metal or metalloid compound is added to the solution comprising the transition metal source. In one embodiment, the metal or metalloid compound is added to the solution comprising the metal silicate. In one embodiment, the metal or metalloid compound is added after the solution comprising the metal silicate and the solution comprising the transition metal source are combined.
In some embodiments, the step of mixing the silicate solution with the transition metal source further comprises step 124, wherein a surfactant is added to the combined solution. There is no limitation to the surfactant used. The surfactant may comprise a cationic, anionic, or neutral surfactant, as would be understood by one of skill in the art. In one embodiment, the surfactant is neutral. Exemplary neutral surfactants include, but are not limited to, alkyl- polyethylene oxides (such as those related to the TERGITOL® l5-S-m products or the BRIJ® series of surfactants), alkyl-phenyl polyethylene oxides (such as IGEPAL® RC surfactants or the TRITON® X series of surfactants), polyethylene oxide (PEO) polypropylene oxide (PPO) block co-polymers (such as the PLEIRONIC® series of surfactants), primary amines (such as propylamine or iso-propylamine, diamines (such as diaminopentane, diaminohexane and diaminododecane), and organosilanes (such as 3- (N-allylamino)propyltrimethoxysilane; O- allyloxy(polyethyleneoxy)-trimethylsilane; N-(2-aminoethyl)-3-aminopropylmethyl- dimethoxy silane; N-(2-aminoethyl)-3-aminopropyltri-methoxy silane N-[3- (trimethoxysilyl)propyl]ethylenediamine;N-(6-aminohexyl)aminopropyl-trimethoxysilane; 2- [Methoxy(polyethyleneoxy)propyl]trimethoxysilane;
(3-Trimethoxysilylpropyl)diethylene-triamine 95%; Trivinylmethoxysilane; 3- Cyanopropyldimethylmethoxy silane; 3 -Cyanopropyltri ethoxy silane; (3- Cyclopentadienylpropyl)triethoxysilane; Diphenyldiethoxysilane; Diphenyldimethoxysilane; Diphenylsilanediol; Diphenylvinylethoxysilane;
(Mercaptomethyl)dimethylethoxy silane; (Mercaptomethyl)methyldi ethoxy silane; 3- Mercaptopropylmethyldimethoxy silane; 3 -Mercaptopropyltrimethoxy silane; 3- Mercaptopropyltri ethoxy silane; 3-Methacryloxypropyldimethylethoxy-silane; 3- Methacryloxypropyldimethylmethoxy silane; 3 -Methacryloxypropylmethyldi ethoxy-silane; 3- Methacryloxypropylmethyldimethoxysilane; 3-methacryloxypropyltrimethoxysilane;
Methylphenyldimethoxysilane; Methyl [2-(3-trimethoxysilylpropylamino)-ethylamino]-3- propionate (65% in methanol); 7-Oct-l-enyltrimethoxysilane; Phenethyltrimethoxysilane; N- Phenylaminopropyltrimethoxysilane; Phenyldimethylethoxysilane; Phenyltriethoxysilane;
Phenyltrimethoxysilane; Phenylvinyldiethoxysilane; N-[3-(triethoxysilyl)propyl]-4, 5-dihydro- imidazole; 2-(Trimethoxysilyl)ethyl-2 -Pyridine;
Trimethoxysilylpropyldiethylenetriamine (95%); N[(3-trimethoxysilyl)propyl]ethylene-diamine triacetic acid, trisodium salt (50% in water); N-(3-trimethoxysilylpropyl)pyrrole;
Triphenylsilanol; Vinyldimethylethoxysilane; Vinylmethyldiethoxysilane; Vinyltriethoxysilane; Vinyltrimethoxysilane; 3-Cyanopropyldimethylmethoxysilane; 3 -Cyanopropyltri ethoxy silane; (3-Cyclopentadienylpropyl)triethoxysilane; Diphenyldimethoxysilane; Diphenylsilanediol; Diphenylvinylethoxysilane; (Mercaptomethyl)dimethylethoxysilane;
(Mercaptomethyl)methyldi ethoxy silane; 3 -Mercaptopropylmethyldimethoxy silane; 3- Mercaptopropyltrimethoxy silane; 3 -Mercaptopropyltri ethoxy silane; 3- Methacryloxypropyldimethylethoxy-silane; 3 -methacryloxypropyldimethylmethoxy silane; 3- Methacryloxyproopylmethyldi ethoxy-silane; 3 -Methacryloxypropylmethyldimethoxy silane; 3- Methacryloxypropyltrimethyoxy silane; Methylphenyldimethoxy silane; Methyl [2-(3- trimethoxysilylpropylamino)-ethylamine]-3-propionate (65% in methano); 7-Oct-l- 3nyltrimethoxysilane; Phenethyltrimethoxysilane; N-phenylaminopropyltrimethoxysilane;
Phenyl dimethyl ethoxy sil ane ; Pheny ltri ethoxy sil ane ;
Phenyltrimethoxysilane; Phenylvinyldiethoxysilane; N-[3-(triethoxysilyl)propyl]-4, 5-dihydro- imidazole; 2-(Trimethoxysilyl)ethyl-2-pyridine; Trimethoxysilylpropyldiethylenetriamine (95%); N-[(3-trimethoxysilyl)propyl]ethylene-diamine triacetic acid, trisodium salt (50% in water); N-(3-trimethoxysilylpropyl)pyrrole;
Triphenylsilanol; Vinyldimethylethoxysilane; Vinylmethyldiethoxysilane; Vinyltriethoxysilane; Vinyltrimethoxysilane. N-(trimethoxysilylpropyl)ethylene-diamine, triacetic acid, trisodium salt; 4- Aminobutyldimethylmethoxy silane; 4- Aminobutyltri ethoxy silane (95%); N-(2-aminoethyl)-3- aminopropylmethyldi-methoxysilane; EhNCEhCEhCEhSiOEt 3- aminopropyldimethylethoxy silane; 3 -Aminopropylmethyldi ethoxy silane; 3- Aminopropyldiisopropylethoxysilane; 3 -Aminopropyltri ethoxy silane; 3- Aminopropyltrimethoxysilane; N-(triethoxysilylpropyl)urea (50% in methanol). N-[3- (triethoxysilyl)propyl]phthalamic acid (95%).
In one embodiment, the surfactant comprises a cationic surfactant. In one embodiment, the cationic surfactant comprises a quaternary ammonium salt. Exemplary quaternary ammonium cations include, but are not limited to, tetra n-propyl ammonium, tetra n- butyl ammonium, tetraethyl ammonium, tetramethyl ammonium, methyl tri-n-butyl ammonium, triethyl methyl ammonium, n-hexyl trimethyl ammonium, trimethyl ammonium, benzyl triethyl ammonium, n-dodecyl trimethyl ammonium, benzyl tri-n-propyl ammonium, tetra n-pentyl ammonium, ethyl pyridinium, diethyl piperidinium, tetra-n-hexyl ammonium, tetra-n-octyl ammonium, tetra-n-dodecyl ammonium, trimethyl ethanol ammonium, hexamethylene bis (diethyl methylammonium), and hexamethonium. The counter ion of the quaternary ammonium salt may be any suitable species, but typically is hydroxide, halide, or the like.
In one embodiment, the cationic surfactant comprises a quaternary phosphonium salt. Exemplary quaternary phosphonium cations include, but are not limited to, tetra n-propyl phosphonium, tetra n-butyl phosphonium, tetraethyl phosphonium, tetramethyl phosphonium, methyl tri-n-butyl phosphonium, triethyl methyl phosphonium, n-hexyl trimethyl phosphonium, trimethyl phosphonium, benzyl triethyl phosphonium, n-dodecyl trimethyl phosphonium, benzyl tri-n-propyl phosphonium, tetra n-pentyl phosphonium, tetra-n-hexyl phosphonium, tetra-n-octyl phosphonium, tetra-n-dodecyl phosphonium, trimethyl ethanol phosphonium, and
hexamethylene bis (diethyl methylphosphonium). The counter ion of the quaternary ammonium salt may be any suitable species, but typically is hydroxide, halide, or the like.
In one embodiment, the cationic surfactant comprises a quaternary ammonium salt containing an organosilane. Exemplary quaternary ammonium cations containing an organosilane include, but are not limited to, N,N-dimethyl-N-tetradecyl-N-(3
trimethoxysilylpropyl) ammonium halides; N,N-dimethyl-N-octadecyl-N-(3- trimethoxysilylpropyl) ammonium; N,N-dimethyl-N-octadecyl-N-(3 -tri ethoxy silylpropyl) ammonium (Ni et ah, 2016, J. Porous Mater., 23 :423-429; Xiang et ah, 2015, ChemCatChem, 7:521 - 525); N,N-diethyl-N-octadecyl-N-(3 -tri ethoxy silylpropyl) ammonium; N,N-dimethyl-N- butyl-N-(3 -tri ethoxy silylpropyl) ammonium; N,N-dimethyl-N-hexyl-N-(3-triethoxysilylpropyl) ammonium; N,N-dimethyl-N-octyl-N-(3 -tri ethoxy silylpropyl) ammonium; N,N-dimethyl-N- decyl-N-(3 -tri ethoxy silylpropyl) ammonium; N,N-dimethyl-N-dodecyl-N-(3- triethoxysilylpropyl) ammonium; N,N-dimethyl-N-hexadecyl-N-(3-triethoxysilylpropyl) ammonium; [3 -(trimethyl silyl) propyl] hexadecyl dimethyl; [3 -(trimethyl silyl) propyl] butyl dimethyl ammonium; [3 -(trimethyl silyl) propyl] hexyl dimethyl ammonium; [3 -(trimethyl silyl) propyl] octyl dimethyl ammonium; [3 -(trimethyl silyl) propyl] decyl dimethyl ammonium; [3- (trimethyl silyl) propyl] dodecyl dimethyl ammonium; and [3-(trimethylsilyl) propyl] octadecyl dimethyl ammonium. The anion portion of the quaternary ammonium salt may be any suitable species, but typically is hydroxide, halide, or the like.
In some embodiments, the cationic surfactant is a diquatemary diammonium salt. Exemplary diquatemary diammonium cations include, but are not limited to, N, N, N, N', N', N',- hexamethyl-8,l l-[4.3.3.0]dodecane diammonium (U.S. Pat. No. 4,910,006); N, N, N, N', N', N',- hexamethyl-8,l l-[4.3.3.0]butyl diammonium; N, N, N, N', N', N',-hexamethyl-8, 11- [4.3.3.0]hexane diammonium; N, N, N, N', N', N',-hexamethyl-8,l l-[4.3.3.0]octane
diammonium; N, N, N, N', N', N',-hexamethyl-8,l l-[4.3.3.0]decane diammonium; N, N, N, N', N', N',-hexamethyl-8,l l-[4.3.3.0]hexadecane diammonium; N, N, N, N', N', N',-hexamethyl- 8, 1 l-[4.3.3.0]octadecane diammonium; C22H45-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3; C20H41- N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3; Ci8H37-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3 (Choi et ak, 2009, Nature, 461 :246-250; Rani et al., 2016, Cryst. Growth Des., 16:3323-3333); Ci6H33-N+(CH3)2- C6Hl2-N+(CH3)2-C6Hl3; Cl4H29-N+(CH3)2-C6Hl2-N+(CH3)2-C6Hl3; Cl2H25-N+(CH3)2-C6Hl2- N+(CH3)2-C6Hi3; and CioH2i-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3.
In one embodiment, the surfactant is an anionic surfactant. The anionic surfactant is not limited, and can be any surfactant having an anionic functional group, as would be understood by one of skill in the art. Exemplary anionic surfactants include, but are not limited to, sodium dodecyl sulfate, dodecyl-p-benzenesulfonic acid, alkylphosphoric acid salts and fatty acids.
In one embodiment, the surfactant is a templating or directing agent. In one embodiment, the surfactant controls the size of the pores formed in the porous composite. In one embodiment, the surfactant controls the diameter of the porous composite. In one embodiment, the length of the alkyl chains in the surfactant affect the pore sizes in the porous composite. In one embodiment, the length of the alkyl chains in the surfactant affect the diameter of the porous composite.
In some embodiments, the step of mixing the silicate solution with the transition metal source further comprises step 126 wherein a templating agent is added to the combined solution. Exemplary templating agents include, but are not limited to, porous carbon (such as activated charcoal and carbon nanotubes), organic polymers (such as poly(methyl methacrylate), starch, and latex), organic small molecules (such as tetraethylene glycol, triethanolamine, triisopropanolamine, triethylene glycol, sulfolane, and diethylglycoldibenzoate), and inorganic salts (such as Mg(OH)2 and CaCCb).
In one embodiment, the templating agent controls the size of the pores formed in the porous composite. In one embodiment, the templating agent controls the diameter of the porous composite.
In step 130, the combined solution is heated to form a gel. In one embodiment, the reaction mixture is heated to a temperature between 100 °C and 300 °C. In one embodiment, the reaction mixture is heated to a temperature between 120 °C and 290 °C. In one embodiment, the reaction mixture is heated to a temperature between 140 °C and 280 °C. In one embodiment, the reaction mixture is heated to a temperature between 160 °C and 270 °C. In one embodiment, the reaction mixture is heated to a temperature between 180 °C and 260 °C. In one embodiment, the reaction mixture is heated to a temperature between 200 °C and 240 °C. In one embodiment, the reaction mixture is heated to a temperature between 200 °C and 230 °C. In one embodiment, the reaction mixture is heated under atmospheric pressure. In one embodiment, the reaction mixture is heated under elevated pressure. In one embodiment, the reaction mixture is heated under pressures of 0.5 to 30.0 atm. In one embodiment, the reaction mixture is heated under reduced pressure.
In one embodiment, the gel formed upon heating is filtered to remove liquids. In one embodiment, the gel is washed with water. In one embodiment, the gel is washed with an organic solvent. Exemplary organic solvents include, but are not limited to, hexane, pentane, diethyl ether, dichloromethane, benzene, toluene, chloroform, acetone, and ethyl acetate. In one embodiment, the gel is dried to form a solid. In one embodiment, the gel is dried at room temperature. In one embodiment, the gel is dried at an elevated temperature. In one
embodiment, the gel is dried at a lower temperature.
In step 140, the gel or dried solid is contacted with a solution comprising a transition metal salt. The transition metal salt may comprise any source of transition metal. Exemplary transition metals include, but are not limited to, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and mercury. In one embodiment, the transition metal salt is a nickel salt. In one embodiment, the solution of nickel salt is an aqueous solution. Exemplary nickel salts include, but are not limited to, nickel (II) chloride, nickel (III) chloride, nickel (II) bromide, nickel (III) bromide, nickel (II) fluoride, nickel (III) fluoride, nickel
(II) nitrate, nickel (III) nitrate, nickel (II) sulfide, nickel (III) sulfide, nickel (II) sulfate, nickel
(III) sulfate, and nickel phosphate.
In some embodiments, contacting the gel or dried solid with a solution comprising a transition metal salt further comprises step 142, wherein the gel or dried solid is contacted with a solution of an inorganic ammonium salt to form an ammonium ion-exchanged porous composite. Exemplary inorganic ammonium salts include, but are not limited to, ammonium nitrate, ammonium chloride, ammonium bromide, and ammonium acetate. In one embodiment, the ammonium ion-exchanged porous composite is dehydrated to form a protonated porous composite. In one embodiment, the porous composite is dehydrated by heating to a temperature between 100 °C and 800 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 200 °C and 700 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 300 °C and 600 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 400 °C and 500 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 475 °C and 525 °C. In one embodiment, the porous composite is dehydrated by heating to a temperature between 490 °C and 510 °C.
In some embodiments the step of contacting the gel or dried solid with a solution comprising a transition metal salt further comprises step 144, wherein the gel or dried solid is contacted with a solution of base. In one embodiment, the solution is an aqueous solution. In another embodiment, the solution is an organic solution. Exemplary organic solvents used in the solution include, but are not limited to, hexane, pentane, diethyl ether, dichloromethane, benzene, toluene, chloroform, acetone, and ethyl acetate. In one embodiment, the solution of base comprises an inorganic base. Exemplary inorganic bases include, but are not limited to, potassium hydroxide, sodium hydroxide, calcium hydroxide, and ammonium hydroxide. In one embodiment, the solution of base comprises an organic base. Exemplary organic bases include, but are not limited to, arginine, lysine, histidine, and tetraalkylammonium hydroxides.
In one embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 0 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 10 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 20 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 30 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 40 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 50 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 60 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 70 °C and 100 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 70 °C and 90 °C. In another embodiment, the gel or dried solid is contacted with the solution of base at a temperature between 75 °C and 85 °C. In step 150, the porous composite is dried. In one embodiment, the porous composite is calcined. In some embodiments, the porous composite is both dried and calcined. In one embodiment, the porous composite is dried at an elevated temperature. In one embodiment, the porous composite is dried at a temperature between 20 °C and 200 °C. In one embodiment, the porous composite is dried at a temperature between 30 °C and 190 °C. In one embodiment, the porous composite is dried at a temperature between 40 °C and 180 °C. In one embodiment, the porous composite is dried at a temperature between 50 °C and 170 °C. In one embodiment, the porous composite is dried at a temperature between 60 °C and 160 °C. In one embodiment, the porous composite is dried at a temperature between 70 °C and 150 °C. In one embodiment, the porous composite is dried at a temperature between 80 °C and 140 °C. In one embodiment, the porous composite is dried at a temperature between 90 °C and 130 °C. In one embodiment, the porous composite is dried at a temperature between 90 °C and 120 °C. In one embodiment, the porous composite is dried at a temperature between 95 °C and 115 °C.
In one embodiment, the porous composite is calcined. In one embodiment, the porous composite is calcined at a temperature between 400 °C and 550 °C. In one embodiment, the porous composite is calcined at a temperature between 410 °C and 540 °C. In one embodiment, the porous composite is calcined at a temperature between 420 °C and 530 °C. In one embodiment, the porous composite is calcined at a temperature between 430 °C and 520 °C. In one embodiment, the porous composite is calcined at a temperature between 440 °C and 510 °C. In one embodiment, the porous composite is calcined at a temperature between 450 °C and 500 °C.
Method of Olefin Oligomerization
The present invention relates in part to a method of reacting an olefin starting material in the presence of a porous composite of the present invention. Exemplary reactions involving olefins include, but are not limited to, olefin isomerization, olefin alkylation, olefin addition, olefin dimerization, olefin oligomerization, olefin polymerization, olefin aromatization, olefin cracking, and olefin hydrocracking. In one embodiment, the porous composite is used as a catalyst in an olefin oligomerization reaction. In one embodiment, the olefin starting material is a C2-C6 olefin. In one embodiment, the olefin starting material is a C2-C6 olefin. In one embodiment, the olefin starting material is a C2-C5 olefin. In one embodiment, the olefin starting material is a C2-C4 olefin. In one embodiment, the olefin starting material is a C2-C3 olefin. Exemplary olefins include, but are not limited to, ethylene (C2), propylene (C3), 1 -butene (C4), trans-2-butene (C4), cis-2-butene (C4), isobutene (C4), l-pentene (C5), cis-2-pentene (C5), trans- 2-pentene (C5) and (2E)-4-methyl-2-pentene (C6).
In one embodiment, the porous composite is used as a catalyst in an olefin oligomerization reaction. In one embodiment, the olefin is oligomerized to form an unbranched product. In one embodiment, the olefin is oligomerized to form a branched product. In one embodiment, the olefin is oligomerized to form a mixture of branched and unbranched products. In one embodiment, the oligomerization reaction produces a higher molecular weight olefin. Exemplary higher molecular weight olefins include, but are not limited to, olefins containing four carbons, olefins containing six carbons, olefins containing eight carbons, olefins containing ten carbons, olefins containing twelve carbons, olefins containing fourteen carbons, olefins containing sixteen carbons, and combinations and/or mixtures thereof. In one embodiment, the higher molecular weight olefin is a liquid fuel. In one embodiment, higher molecular weight olefin is a liquid fuel additive.
In one embodiment, the olefin is contacted with the porous composite in a chemical reactor. In one embodiment, the reactor is a tank. In one embodiment, the reactor is a tubular or pipe reactor. In one embodiment, the reactor is a packed bed reactor. In one embodiment, the reactor is a fluidized bed reactor. In one embodiment, the olefin is contacted with the porous composite in a continuous process. In one embodiment, the olefin is contacted with the porous composite in a batch process. In one embodiment, the olefin is contacted with the porous composite in the gas phase. In one embodiment, the olefin is contacted with the porous composite in the liquid phase. In one embodiment, the olefin is contacted with the porous composite in the solid phase.
In one embodiment, the porous composite is mixed with a support. Exemplary supports include, but are not limited to, silica, alumina, ceramic, or activated carbon. In one embodiment the ratio of porous composite to support is 1 :500. In one embodiment, the ratio of the porous composite to support is 1 :450. In one embodiment, the ratio of porous composite to support is 1 :400. In one embodiment, the ratio of porous composite to support is 1 :350. In one embodiment, the ratio of porous composite to support is 1 :300. In one embodiment, the mass ratio of porous composite to support is 1 :250. In one embodiment, the mass ratio of porous composite to support is 1 :200. In one embodiment, the mass ratio of porous composite to support is 1 : 150. In one embodiment, the mass ratio of porous composite to support is 1 : 100.
In one embodiment, the oligomerization reaction takes place in air. In one embodiment, the oligomerization reaction takes place in the presence of an inert gas. Exemplary inert gases include, but are not limited to, helium, nitrogen, and argon. In one embodiment, the oligomerization reaction occurs under atmospheric pressure. In one embodiment, the
oligomerization reaction occurs under pressures higher than atmospheric pressure. In one embodiment, the oligomerization reaction occurs under pressures lower than atmospheric pressure. In one embodiment, the oligomerization reaction occurs between 1 atm and 40 atm. In one embodiment, the oligomerization reaction occurs between 1 atm and 35 atm. In one embodiment, the oligomerization reaction occurs between 1 atm and 30 atm. In one
embodiment, the oligomerization reaction occurs between 1 atm and 25 atm. In one
embodiment, the oligomerization reaction occurs between 1 atm and 20 atm. In one
embodiment, the oligomerization reaction occurs between 1 atm and 15 atm. In one
embodiment, the oligomerization reaction occurs between 1 atm and 10 atm. In one
embodiment, the oligomerization reaction occurs between 2 atm and 9 atm. In one embodiment, the oligomerization reaction occurs between 3 atm and 8 atm. In one embodiment, the oligomerization reaction occurs between 4 atm and 7 atm. In one embodiment, the oligomerization reaction occurs between 4 atm and 6 atm. In one embodiment, the oligomerization reaction occurs between 4.5 and 5.5 atm.
In one embodiment, the oligomerization reaction is performed at room temperature. In one embodiment, the oligomerization reaction is performed at an elevated temperature. In one embodiment, the oligomerization reaction occurs between 50 °C and 300 °C. In one embodiment, the oligomerization reaction occurs between 75 °C and 275 °C. In one embodiment, the oligomerization reaction occurs between 100 °C and 250 °C. In one embodiment, the oligomerization reaction occurs between 125 °C and 225 °C. In one embodiment, the oligomerization reaction occurs between 150 °C and 200 °C. In one embodiment, the oligomerization reaction occurs between 175 °C and 200 °C. In one embodiment, the oligomerization reaction occurs between 175 °C and 190 °C.
EXPERIMENTAL EXAMPLES
The invention is now described with reference to the following Examples. These Examples are provided for the purpose of illustration only, and the invention is not limited to these Examples, but rather encompasses all variations that are evident as a result of the teachings provided herein.
Materials and Methods
Synthesis Method 1:
Synthesis of Microporous ETS-10
Microporous ETS-10 was synthesized using an optimized synthesis system of 3.4Na20 : l.5K20 : IT1O2 : 5.5SiC>2 : 7.0 HC1 : 144H20, modified from Lv et al. to reduce oxide impurities generated as by-products (Lv et al., 2004, Micro. Meso. Mat., 76: 113-122).
Generally, a first mixture is prepared by dissolving sodium silicate solution (S1O2, Na20, and H2O), NaOH, and KOH in deionized water by stirring the combined components for 10 minutes. A second mixture is prepared by dissolving T1O2 in deionized water under stirring for 10 minutes. The two mixtures are combined under stirring for 30 minutes to produce a slurry gel. The gel is placed in a Teflon-lined autoclave and heated to 200 or 230 °C. After 72 hours, the solids are filtered off, washed with deionized water, and dried at 100 °C.
Cobalt incorporated microporous ETS-10 was synthesized by modifying the molar ratio of reactant chemicals (3.4Na20 : l.5K20 : lTi02 : 5.5Si02 : 0.3 Co(N03)2 : 7.0 HC1 : 144H20) and using similar synthesis procedure as above where the Co(NCb)2 is combined with Ti02 prior to mixing this solution with the sodium silicate solution.
Synthesis of Mesoporous ETS-10
Mesoporous ETS-10 was synthesized using a synthesis system of 3.7Na20 : l.3K20 : l.OTiCh : 6.7Si02 : 0.6TPOAB : 163H20 (Hu et al., 2017, RSC Adv., 7:41204-41209). In general, 10.0 mL of an aqueous NaOH solution (5.38 M) and 9.4 mL of an aqueous KOH solution (4.75 M) are added to 17.8 mL of water glass. The mixture is stirred until it is cooled to room temperature. A solution of 13.1 g TiCb (17 wt% in HC1) is slowly added to this mixture and the contents are stirred for 240 minutes. 3.5 mL of TPOAB (N,N-dimethyl-N-octadecyl-N- (3-triethoxysilylpropyl)ammonium bromide) is added to the mixture, followed by stirring for 120 minutes. The resulting gel is placed in a Teflon-lined autoclave and heated to 230 °C for 72 hours. The solids are filtered off, washed with deionized water, dried overnight at 100 °C, and calcined in the air for 5 hours at 450 °C.
Mesoporous ETS-10 was alternatively synthesized from microporous ETS-10. Mesopores were generated by contacting ETS-10 with a solution of 1.0 mol/L NaOH at 80 °C for two hours. The product was then washed with distilled water.
Cobalt incorporated mesoporous ETS-10 was synthesized with the addition of cobalt nitrate by a similar synthesis procedure described above. In general, the synthesis procedure is identical to that of mesoporous ETS-10 except that 3 mL of a cobalt nitrate aqueous solution (1.1 M) is added to the reaction mixture with the TPOAB (Hu et al., 2017, RSC Adv., 7:41204-41209). The synthesis system for mesoporous ETS-10 incorporating cobalt is 3.7Na20 : l.3K20 : l.0TiO2 : 6.7Si02 : 0.6TPOAB : O. I8C0O : 163H20
Incorporation of Trivalent Metals into the Framework
Incorporation of aluminum, boron, and/or gallium into both microporous and mesoporous ETS-10 follows an identical procedure (Lv et al., 2007, Micro. Meso. Mater., 101 :355-362). In general, NaAlCh, B2O3, or Ga(NCb)3, are combined with the solution of the titanium source. This mixture is then combined with the solution of metal silicate under vigorous stirring for two hours. The resulting gel is heated to crystallization at 230 °C for 72 hours. The resulting solids are collected by filtration, washed with deionized water, and dried at 100 °C overnight.
Incorporation of Ni2+ and H+ by Ion Exchange
Ion exchange in both microporous and mesoporous ETS-10 follow an identical procedure (Uma et al., 2004, Micro. Meso. Mat., 67: 181-187). In general, to replace alkali metal ions with nickel such that the ratio of nickel to titanium is about 1 : 1, the titanosilicate starting material is stirred in a solution of N1CI2 (4 M) in 100 mL of water at room temperature. The solids are filtered off, washed with deionized water, and dried at 110 °C. To prepare protonated ETS-10, the titanosilicate is treated with NH4NO3 and then dehydrated at 500 °C for 1 hour.
Formation of ETS-10 Nano-plates
The synthesis of microporous and mesoporous ETS-10 nano-plates follows the respective synthesis of microporous and mesoporous ETS-10 with normal diameters (i.e. about 500 nm). A diquaternary ammonium surfactant, Ci8H37-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3, is added the mixture of metal silicate and titanium source, leading to the formation of zeolite nano- plates having diameters of about 2 nm.
Synthesis Method 2:
Synthesis of Microporous ETS-10
Previous reports have shown that the final OH concentration (or pH value) of the ETS-10 synthesis gel plays an important role in the final product purity (Lv et al., 2004, Microporous Mesoporous Mater., 76: 113 - 122). Therefore, a set of experiments were carried out to minimize the impurities and maximize the mass fraction of active catalyst. A molar composition of 3.4Na20 : 1.5 K2O : IT1O2 : 5.5Si02 : 6.95HC1 : 140.7¾0 was shown to produce the highest purity, where the impurities (quartz and other dense S1O2 phases) were undetectable from powder X-ray diffraction (Figure 2). Microporous nanoparticle ETS-10 was synthesized using the conventional hydrothermal method based on a previous report (Lv et al., 2004, Microporous Mesoporous Mater., 76: 113-122). NaOH (EMD Millipore), KOH (EMD Millipore), Ti02 (P25, Acros Organics), sodium silicate solution (25.5-28.5% Si02, 7.5-8.5% Na20; EMD Millipore), and 37 wt% HC1 aqueous solution (Sigma-Aldrich) were used without further purification. DI water (resistivity=l8.2 W m) was used in the synthesis and subsequent washing of the final products.
A solution of Ti02 and DI water was combined with a solution mixture of NaOH, KOH, and sodium silicate solution at ambient temperature in a dropwise manner while stirring at 500 rpm. The HC1 solution was then added dropwise while stirring at 500 rpm. A thick gel was formed at the end of the addition of HC1 solution and was further stirred for 30 minutes (Thakkar et al., 2018, ChemCatChem., 10:4234-4237). The following molar ratio of the components, 3.4Na20 : 1.5 K20 : lTi02 : 5.5Si02 : xHCl : (1 l6.7+3.45x)H20 (x = 6.6-8.1) was achieved in the end.
The gel was then heated in a convection oven at 230 °C for 72 hours. The solid precipitate was recovered, washed with DI water until the pH of the supernatant was 9-10, and dried at 100 °C.
Micron-sized ETS-10 particles were synthesized according to the synthesis method based on a previous report (SEM images in Figure 3B) (Rocha et al., 1998, Microporous Mesoporous Mater., 23:253 -263; Casado et al., 2009, Mater. Res. Bull., 44: 1225- 1231).
Synthesis of Mesoporous ETS-10
Mesoporous ETS-10 was synthesized using a synthesis system of 3.7Na20 : l.3K20 : l.0TiO2 : 6.7Si02 : 0.6TPOAC1 : 160H2O : 0.39 HAcAc, modified from Hu et al. and Xiang et al. (Hu et al., 2017, RSC Adv., 7:41204-41209; Xiang et al., 2015, ChemCatChem., 7:521-525). NaOH, KOH, TiCb solution (20% w/v in 2N HC1), sodium silicate solution (25.5- 28.5% Si02, 7.5-8.5% Na20), N,N-dimethyl-N-octadecyl-N-(3- trimethoxysilylpropyl)ammonium chloride solution (60% in MeOH, TPOAC1) and acetylacetone (HAcAc) were used without further purification.
Briefly, the TiCb and acetylacetone solution mixture (pre-stirred at room temperature) was combined with NaOH, KOH and sodium silicate solution mixture at ambient temperature in a dropwise manner while stirring at 500 rpm. The thick gel formed at the end was stirred for 60 minutes before addition of N,N-dimethyl-N-octadecyl-N-(3- trimethoxysilylpropyl)ammonium chloride solution. The final gel was further stirred for 120 minutes before heating in a convection oven at 230 °C for 72 hours. The solid precipitate was recovered, washed with DI water until the pH of the supernatant is 9-10, dried at 100 °C, and calcined in air at 500 °C for 5 hours.
Incorporation of Divalent and Trivalent Metals into the Framework
Incorporation of trivalent metals (e.g. aluminum, boron, or gallium) or divalent metals (e.g. cobalt) into microporous ETS-10 follows an identical procedure for the synthesis of microporous ETS-10 mentioned above (in Method 2) except with the addition of NaAlCE, B2O3, Ga(NCb)3, or Co(NC>3)2 salt and DI water solution mixture after adding the T1O2 solution. The final molar ratio of the reactant chemicals was 3.4Na20 : I.5K2O : IT1O2 : 5.288S1O2 :
O.IO6AI2O3 : 7.1HC1 : 141.25H20, 3.4Na20 : l.5K20 : IT1O2 : 5.266Si02 : O.P7B2O3 : 7HC1 : 140.77H2O, 3.4Na20 : l.5K20 : IT1O2 : 5.29Si02 : 0.l05Ga2C>3 : 6.95HC1 : 140.4H2O, or 3.4Na20 : l.5K20 : IT1O2 : 5.3Si02 : O. IC02O3 : 7HC1 : 139.64H20, respectively.
Incorporation of Ni2+ and H+ by Ion Exchange
Two different ion-exchange procedures were used to obtain different levels of Ni2+ loading. After ion-exchange with Ni2+, three samples with Ni/Ti molar ratios of 0.36, 0.35 and 0.56 were obtained, corresponding to Ni mass percentages of 3.90%, 4.12% and 6.85 %, respectively.
In order to exchange the Na+ and K+ ions present in the microporous ETS-10 with Ni2+ ions, the as-synthesized ETS-10 was stirred in a 0.25 mol/L Ni(N03)2 aqueous solution for 18 hours at ambient temperature (or for 3 hours at 80 °C twice for higher Ni2+ loading), washed with DI water, and calcined at 500 °C for 5 hours (Thakkar et ah, 2018, ChemCatChem., 10:4234-4237).
Formation of ETS-10 Particles with a Size > ~2 5 pm
ETS-10 particles with size greater than ~2.5 pm were also synthesized in order to study the effect of crystallite size on the activity of catalyst in ethylene oligomerization reaction (Ni(4. l2 wt%, 2.5 pm)-ETS-l0) (Rocha et al., 1998, Microporous Mesoporous
Mater., 23:253-263; Casado et al., 2009, Mater. Res. Bull., 44: 1225-1231). Synthesis of Comparative Microporous Catalysts
Comparative microporous catalysts Ni-CIT-6 and Ni-MOF-74 were also used in order to compare the catalytic outcomes from Ni-ETS-lO. Ni-CIT-6 (Deimund et al., 2014, ACS Catal., 4:4189-4195) and Ni-MOF-74 (Mlinar et al., 2014, ACS Catal. 4:717-721) were synthesized and pretreated using previous reported methods.
Titanosilicate Characterization
XRD patterns of Ni2+-ETS-lO made using Method 1 and its comparative zeolites (Ni2+-CIT-6, Ni2+-MCM-4l, and Ni2+-H+-MCM-4l) were obtained using PANalytical Empyrean diffractometer, Cu Ka radiation (l = 1.5406 A), step size (°20) = 0.026 and 40mA, 45kV generator settings. Powder XRD patterns of Ni2+-ETS-lO made using Method 2 and its comparative microporous catalysts (Ni-CIT-6 and Ni-MOF-74) were obtained using PANalytical Empyrean diffractometer (40mA, 45kV), Cu Ka radiation (l = 1.54 A). TEM, STEM, and STEM-EDS images of the synthesized ETS-10 catalysts were taken using FEI Talos F200X instrument at 200kV. SEM images of the ETS-10 catalyst synthesized via Method 1 were obtained on FEI Helios NanoLab 660 FESEM at 5kV. SEM images of the ETS-10 catalyst synthesized via Method 2 were taken using FEI Helios NanoLab 660 FESEM and Thermo Fisher Scios 2 at 2 kV. Bruker Esprit software was used to collect the element maps. Physical adsorption analysis on non-ion exchanged ETS-10 degassed at 180 °C for 4 hrs was performed using Nz gas at -196 °C. ICP-AES analysis was performed on a Ni2+-ETS-lO sample made via Method 1 using Perkin-Elmer Optima 5300 instrument. Elemental analysis (ICP) on catalysts made via Method 2 was performed by Galbraith Laboratories, Inc.
Reactor Setup for Catalyst Studies
Reactor setup for catalysts made via Method 1
A down flow, packed bed, high pressure, isothermal, stainless steel reaction unit was built for testing the catalysts for ethylene oligomerization reaction in continuous gas phase mode. Pre-calcined 50 mg catalysts were diluted with pre-calcined (1000 °C, 24 hours) 13.5 gm silica gel (125-149 pm) to obtain a total bed length of 15 cm and bed volume of 11 cm3.
Isothermal catalyst bed temperature was maintained and monitored throughout the reaction duration using temperature controllers. Heated flow lines were used to eliminate condensation of large oligomeric reaction products.
The catalysts were pretreated in helium flow at 5 seem, 180 °C overnight before performing the reactions at 180 °C and 5 atm ethylene absolute pressure. Reaction products were quantified continuously at regular intervals using an online gas chromatograph - FID
(temperature ramp: -60 °C to 180 °C) and using the relative sensitivity response factors for various oligomers equal to 1.
Reactor setup for catalysts made via Method 2
A packed-bed reactor was used for testing the catalysts for ethylene oligomerization reaction in an isothermal, continuous gas flow mode. Pre-calcined 50 mg catalyst (125-149 pm) was diluted with pre-calcined (1000 °C, 24 hours) 13.5 g silica gel (125- 149 pm) to obtain a total bed length of 15 cm and bed volume of 11 cm3 in order to eliminate local hot spots and temperature gradients. Isothermal catalyst bed temperature was maintained and monitored throughout the reaction duration using temperature controllers. Heated flow lines (170 °C) were used to eliminate condensation of large oligomeric reaction products.
The catalysts were treated in-situ in helium flow at 180 °C for 16 hours before performing the reactions. (ETS-10 catalysts were additionally pretreated in-situ under dynamic vacuum (2 mmHg absolute) for 12 hours at 450 °C before helium treatment.) The reactions were carried out at 180 °C, 5 atm ethylene pressure and 90 gc2/(gcataiysth) space velocity (conversion <1% for all catalysts, Figure 4). Reaction products, rates, and selectivities were quantified continuously using an online gas chromatograph.
Results and Discussion
The present invention relates in part to novel porous materials formed using the methods described herein and the use of these porous materials as olefin oligomerization catalysts. The instant invention is in part based on the formation of a titanosilicate zeolite (known as ETS-10) with controlled dimensions, pore size, and placement of Ni2+ and H+ sites. This novel zeolite composition results in a catalyst with improved stability activity and product selectivity. Zeolites, including nickel (Ni2+) containing zeolites, are promising heterogeneous catalysts for ethylene oligomerization because their large pore sizes, their tunable structure, and chemical environment of their active sites (i.e. coordinatively unsaturated Lewis Acidic [LA] Ni2+ cations), provide the exclusive opportunity to precisely design the active sites and to control and optimize reaction rate and selectivity of these reactions (Zhang et al., 2012, Science
336: 1684-1687; Yoo et al., 2012, Micro. Meso. Mat., 149: 147-157; Kim et al., 2012, ACS Nano, 6:9978-9988; Furukawa et al., 2013, Science, 341 : 1230444; Furukawa et al., 2010, Science, 329:424-428). Furthermore, these porous catalysts provide the much needed mechanical and thermal stability in the desired reaction temperature range (T<200 °C), are regenerable, and can be utilized in gas-phase continuous reaction conditions without the requirement of a pyrophoric co-catalyst (e.g. methylaluminoxane, MAO) (Finiels et al., 2014, ACS Catak, 4:717-721; Corma et al., Chapter 6, Catalysts for Fine Chemical Synthesis, Vol. 4, Microporous and Mesoporous Solid Catalysts, 2006 John Wiley & Sons, Ltd). These framework materials are therefore promising catalysts and provide a very good foundation for the development of gas-phase ethylene oligomerization catalysts.
ETS-10 (Engelhard Titanosilicate 10) is a thermally stable microporous crystalline titanosilicate (Si/Ti=5) comprising of comer sharing [TiOr,] and [Si04] units (Figure 5A-C) (Datta et al., Catalysis Today, 2013, 204: 60-65; Anderson et al., 1994, Nature, 367:347- 351; Anderson et al., 1995, Philos. Mag. B, 71 :813 -841; Brandao et al., 2001, Phys. Chem. Chem. Phys., 3 : 1773-1777). ETS-10 is notable in that it has properties that make it amenable to optimization in order to overcome the problems in the field of olefin oligomerization. The 3-D structure of ETS-10 a) consists of -O-Ti-O-Ti-O- chains distributed uniformly, b) has large 12 member (7.6Ά X 4.9Ά) and aperiodic 18 member (14.3 A X 7.6Ά) ring pores, c) is thermally stable up to 650 °C, d) is easily modifiable (e.g. fabrication of mesopores and nano-crystals) compared to conventional zeolites, and e) can be synthesized using a template free procedure (eliminating the need of harsh calcination temperatures that destroy the zeolite framework) (Lv et al., 2007, Micro. Meso. Mat., 101 :355-362; Yang et al., 2001, Micro. Meso. Mat., 46: 1-11; Lv et al., 2004, Micro. Meso. Mat., 76: 113-122; Eldewik et al., 2001, Micro. Meso. Mat., 48:65-71; Guo et al., 2012, J. Phys. Chem. C, 116: 17124-17133; Rocha et al., 1995, J. Chem. Soc., Chem. Commun., 13 :867-868). Each [Tΐqό] unit generates a -2 charge (due to Ti4+) that are open for cation exchange with divalent cations, such as Ni2+, for ion exchange and water treatment applications (Oleksiienko et ak, 2017, Chem. Eng. J., 317:570-585; Popa et al., 2012,
Desalination, 293 :78-86). This leads to a high concentration of Ni2+ sites (Figure 5D-E) and therefore enhanced catalytic activity. Furthermore, the tetrahedral Si in [Si04] units can be selectively replaced by trivalent elements like Al, Ga and B.
Incorporation of Ni2+ cations by ion exchange lowers the reaction temperatures (T<200 °C) for ethylene oligomerization reaction as the reaction initiation now occurs via Cossee-Arlman mechanism on the Ni2+ cation sites as opposed to the generation of unstable 1° carbenium ions on BA sites (Figures 6, 7) (Finiels et al., 2014, Catal. Sci. Technok, 4:2412- 2426; Brogaard et ak, 2016, ACS Catak, 6: 1205-1214). However, since Ni2+ is a divalent cation it requires a combination of two nearby Al atoms in conventional zeolites for charge balance and ion exchange (Figure 6) (Deimund et ak, 2014, ACS Catak, 4:4189-4195). While increasing Al content in zeolite increases the probability to obtain two nearby Al atoms (consecutively increasing Ni2+ exchange and catalytic activity), it also simultaneously generates an uncontrolled large amount of isolated Al atoms (BA sites responsible for side reactions, decreasing product selectivity) (Deimund et ak, 2014, ACS Catak, 4:4189-4195). These Ni2+ containing
conventional bi-functional zeolites (due to the presence of Ni2+ and H+, Figure 6) such as Ni-Y (Heveling et ak, 1988, Applied Catalysis, 42:325-336), Ni-X (Bonneviot et ak, 1983, J. Mole. Cata., 21 :415-430), and Ni-Beta (Martinez et ak, 2013, App. Cata. A: General, 467:509-518) have demonstrated catalytic activity in the temperature range of 25-150 °C. They however suffer from a very low loading of isolated Ni2+ active cationic sites, a product selectivity that is difficult to fine tune in order to obtain desired oligomers, and lower activities compared to homogeneous catalysts (Finiels et ak, 2014, Catak Sci. Technok, 4:2412-2426). Based on this above discussion, it’s necessary to maximize Ni2+ loading to improve catalyst activity, stability, and product selectivity.
Decreasing the crystallite size of catalyst particles (e.g. synthesizing 2-D nano crystals) and/or generating mesopores reduces diffusion length and increases accessibility of active sites (Finiels et ak, 2014, Catak Sci. Technok, 4:2412-2426; Martinez et ak, 2013, App. Cata. A: General, 467:509-518; Moussa et ak, 2016, Cata. Today, 277:78-88; Ismail et ak, 2009, Micro. Meso. Mat., 120:454-459; Ganjkhanlou, et ak, 2016, Micro. Meso. Mat., 229:76-82; Choi et ak, 2009, Nature, 461 :246-250). This increases activity and reduces deactivation during the ethylene oligomerization reaction (Finiels et ak, 2014, Catak Sci. Technok, 4:2412-2426). Ni2+ containing mesoporous silica-alumina amorphous catalysts such as MCM-41, MCM-48, MCM- 36, and SBA-15 have been shown to increase the catalytic activity many folds (Finiels et al., 2014, Catal. Sci. Technol., 4:2412-2426; Lallemand et al., 2008, App. Cata. A: General, 338:37- 43; Hulea et al., 2004, J. Cata., 225:213-222; Andrei et al., 2015, J. Cata., 323:76-84; Andrei et al., 2015, Eur. Phys. J. Spec. Top., 224: 1831-1841).
The present invention relates to the improvement of an ETS-10 catalyst in order to increase the selectivity to C4 formed during olefin oligomerization reactions. One
improvement is the replacement of alkali metal cations in the zeolite with Ni2+ions by ion exchange. The unique structure of ETS-10 allows Ni2+ ions to be exchanged with alkali metal cations into the zeolite framework with a high concentration (Figures 5D, 8A). Furthermore, because [TiOr,] units are uniformly distributed in the framework, Ni2+ cations are also uniformly distributed in the framework; leading to the possible generation of isolated, identical and well- distributed active Ni2+ sites for ethylene oligomerization. The incorporation of divalent Co and or trivalent Al, B or Ga in the ETS-10 framework may help increase and or change the active site (Ni2+ ions) environment (Figure 8B). Specifically, the incorporation of divalent Co in a tetrahedral geometry will generate a -2 charge by substituting tetrahedral silicon (3 Si, lTi) in [Si04] units of the ETS-10 framework. The generation of this -2 charge is perfectly suitable for exchange with Ni2+ ions. Therefore, Co2+ may be incorporated into the zeolite framework in order to increase the loading of Ni2+ ions (Figures 8B, 9A) (Lv et al., 2007, Micro. Meso. Mat., 101 :355-362).
Another improvement is the incorporation of mesopores into ETS-10, which decreases the diffusion length and increases accessibility of active sites in the catalyst, consecutively increasing catalyst activity and reducing deactivation (Corma, 1995, Chem. Rev., 95:559-414; Shi et al., 2015, Chem. Soc. Rev., 44: 8877-8903). Thus, after achieving the uniform distribution of active sites, mesopores are incorporated into the ETS-10 framework (Figure 10A) while still maintaining its crystallinity (Donk et al., 2003, Catalysis Reviews, 45:297-319). Mesopores can be built into the ETS-10 framework by utilizing a surfactant, N,N- dimethyl-N-octadecyl-N-(3-triethyoxysilylpropyl) ammonium bromide, as a mesopore template (Figure 10B) (Ni et al., 2016, J. Porous Mater., 23:423-429; Xiang et al, 2015, ChemCatChem, 7:521 - 525). Varying the carbon chain length in the above mesopore template generates mesopores of varying pore size. Therefore, templates of different chain lengths can be used to synthesize mesoporous crystalline ETS-10 of variable pore sizes. Mesopores can also be built into the ETS-10 framework by contacting ETS-10 with a solution of base, wherein the concentration of the base can be used to control the mesopore size. A basic buffer solution can also be used to maintain the pH value during the dissolution process.
Additionally, there are several modifications to the ETS-10 structure which may benefit its catalytic activity and can be studied. One modification that may improve the catalyst is the generation of BA sites. As synthesized and unmodified, ETS-10 does not have an isolated -1 charge suitable for generation of a BA site, therefore an isolated -1 charge would need to be generated. This can be done by incorporating trivalent elements like Al, Ga and B in the framework (Lv et al., 2007, Micro. Meso. Mat., 101 :355-362) (Figure 9A-B). It has been shown that all of these trivalent elements selectively substitute tetrahedral Si (4Si, OTi) in the [Si04] units of ETS-10 and are uniformly distributed in the framework, leading to the generation of an isolated -1 charge capable of being balanced by a cation or proton (H+), thus generating a BA site (Lv et al., 2007, Micro. Meso. Mat., 101 :355-362; Rocha et al., 1995, J. Chem. Soc., Chem. Commun., 867-868). The concentration of these trivalent metal atoms in the framework is varied to charge the concentration of BA sites. The presence of BA sites may lower the reaction temperatures (T<200 °C) for the ethylene oligomerization reaction (Figure 7) while tuning the active site (i.e. Ni2+ and H+) concentration can further improve the catalyst stability, activity, and product selectivity.
A second optional modification which can be studied is the formation of ETS-10 nano-plates, having a diameter of around 2 nm. Although the synthesis of ETS-10 does not require the use of structure directing agents or templates as normally is the case with synthesis of aluminosilicates (e.g. MFI) (Yang et al., 2001, Micro. Meso. Mat., 46: 1-11; Pavel et al., 2004, Micro. Meso. Mat., 71 :77-85; Turta et al., 2008, Micro. Meso. Mat., 112:425-431), 2 nm thick MFI nano-plate crystals have been synthesized by utilizing novel diquatemary ammonium surfactants as template molecules (Figure 10C) (Choi et al., 2009, Nature, 461 :246-250; Rani et al., 2016, Cryst. Growth Des., 16:3323-3333). This surfactant is bifunctional, wherein ammonium groups direct the basic framework structure in MFI while the long chain hydrophobic part (Ci8 chain) generates nano-plates (Choi et al., 2009, Nature, 461 :246-250). The utilization of such bifunctional templates in the synthesis of ETS-10 will reduce the diameter of ETS-10 crystals from 500 nm to around 2 nm, as is the case with MFI. These template molecules are used for the synthesis of ETS-10. In addition, the chain length of hydrophobic part in the template structure is varied to obtain nano-sized ETS-10 crystals of different diameters. Such nano-sized plate crystals of ETS-10 may aid diffusion and may lead to the development of a highly active, stable catalyst for oligomerization.
Although there have been numerous attempts at utilizing zeolites and MOFs for ethylene oligomerization, gas phase ethylene oligomerization reaction in continuous mode on Ni2+ exchanged ETS-10 (Ni-ETS-lO) has not been studied before. In order to investigate the catalytic outcomes of Ni-ETS-lO, two other similar microporous materials that can load a significant amount of divalent transition metal, CIT-6 (Deimund et al., 2014, ACS Catal., 4:4189-4195) and MOF-74 (Mlinar et al., 2014, ACS Catal., 4:717-721), were chosen as comparative microporous catalysts. Zeolite CIT-6 has *BEA topology, but contains Zn2+ heteroatoms, where the framework Zn atoms generate a -2 charge per Zn (Deimund et al., 2014, ACS Catal., 4:4189-4195) and MOF-74 (Mlinar et al., 2014, ACS Catal., 4:717-721). The -2 charge can be used for loading Ni2+ for oligomerization, similar to ETS-10 (Deimund et al.,
2014, ACS Catal., 4:4189-4195) and MOF-74 (Mlinar et al., 2014, ACS Catal., 4:717-721). Ni- MOF-74 contains a significant amount of coordinatively unsaturated Ni2+ which can potentially be utilized for the ethylene oligomerization reaction (Mlinar et al., 2014, ACS Catal., 4:717- 721).
The present invention relates to the synthesis and catalytic behaviors of Ni-ETS- lO. A template-free and fluoride-free synthetic method that produces ETS-10 without the impurities commonly seen in other systems is presented. Ni-ETS-lO was found to be more active for ethylene oligomerization and has shown higher stability and higher selectivity to C4 than the other microporous catalysts (Ni-CIT-6 and Ni-MOF-74) compared in this study.
Characterization of Titanosilicates
Powder XRD patterns of the synthesized Ni2+-ETS-lO titanosilicate and other conventional zeolites Ni2+-CIT-6, Ni2+-MCM-4l and Ni2+-H+-MCM-4l match those reported in literature (Figure 11) (Hulea et al., 2004, J. Cata., 225:213-222; Lv et al., 2004, Micro. Meso. Mater., 76: 113-122; Deimund et al., 2014, ACS Catal., 4:4189-4195). XRD patterns in Figure 12 show the crystallinity of the Ni-CIT-6 and the Ni-MOF-74 synthesized and used in the study with ETS-10 particles made by Method 2. The TEM images of the synthesized ETS-10 catalysts provide further evidence of their crystallinity (see Figure 13A for ETS-10 particles made by Method 1). Microporous ETS- 10 particles made by both Method 1 and Method 2 have a square bi-pyramidal morphology and a size of less than 500 nm (see Figure 13B for ETS-10 particles made by Method 1 and Figure 3 A for those made by Method 2). High-resolution TEM image of the ETS-10 nanoparticle synthesized via Method 2 provides further evidence of its crystallinity (Figure 14A), where the typical stacking faults of ETS-10 and the resulting 18-member rings are visible. Elemental analysis shows that a Si/Ti ratio of 5.03 was obtained from the ETS-10 synthesized via Method 2 (Table 1).
Figure imgf000037_0001
*M: Ti in case of ETS-10 and Zn in case of CIT-6
Table 1. Elemental (ICP) analysis of inventive ETS-10 catalysts and comparative microporous catalysts. There is a uniform distribution of framework elements (Si, Ti) and exchanged
Ni2+ ions in Ni2+-ETS-lO as is evident from TEM-EDS of Ni2+-ETS-lO made using Method 1 (Figure 15) and STEM-EDS of Ni2+-ETS-lO made using Method 2 (Ni loading 6.85 wt%, Figures 14B-E). Ni/Ti molar ratio of 0.97 was obtained for Ni2+-ETS-lO obtained by Method 1 by performing elemental analysis. This obtained ratio is almost equal to the maximum amount of divalent Ni2+ which can be theoretically exchanged in ETS-10 based on charge balance (i.e. maximum ratio for Ni/Ti=l) - signifying a high loading of isolated Ni2+ sites in Ni2+-ETS-lO catalyst for ethylene oligomerization reaction. A t-plot micropore volume of 0.11 cm3/g, consistent with literature data, was obtained for ETS-10 obtained by Method 1 (Ni et al., 2016, J. Porous Mater., 23:423-429). Elemental analysis of Ni2+-ETS-lO obtained by Method 2 shows a Ni/Ti molar ratio of 0.35-0.56 (Table 1).
Titanosilicate Catalyst Activity Studies Studies of catalysts made via Method 1
Ni2+-ETS-lO has not been studied for ethylene oligomerization before. The results (Table 2) show that Ni2+-ETS-lO is a promising catalyst for ethylene oligomerization with the obtained maximum activity of 6.45 goiigomers/(gcataiyst h). This activity is greater than that obtained from traditional microporous zeolites like Ni2+-CIT-6 and Ni2+-H+-ZSM-5 (Table 2). C4 (selectivity >88%) and C6 (selectivity >10%) oligomers were the main reaction products (Table 2, Figure 16) with no observed cracking by-products (representing the absence of catalytically active BA sites in Ni2+-ETS-lO). Ethylene oligomerization reaction performed on pure, as synthesized ETS-10 (i.e. without Ni2+ ions) as a control experiment exhibited no catalytic activity - revealing that the obtained activity for ethylene oligomerization on Ni2+-ETS- 10 is solely from exchanged Ni2+ cations and that there are no other active (BA) sites in Ni2+-
ETS-10.
Figure imgf000038_0001
Table 2. Ethylene oligomerization catalytic outcomes on different Ni2+ containing
heterogeneous catalysts. Reaction conditions: 180 °C, 5 atm ethylene absolute pressure, 90 gethyiene/(gcataiyst h). *Oligomeric wt% calculations done for the maximum obtained activity injection in GC. Others: Cs, Ci alkanes + alkenes
Studies of catalysts made via Method 2
The catalytic performance of Ni-ETS-lO was compared with two other ethylene oligomerization catalysts with comparable particle sizes, Ni-CIT-6 and Ni-MOF-74. Figure 17A and Table 3 show that Ni-ETS-lO is a promising catalyst for ethylene oligomerization with the obtained maximum turnover frequency of 688.96 molc2/(molNi h), when the Ni loading was 3.9 wt%. This rate is greater than those obtained from previously-reported microporous catalysts such as Ni-CIT-6 (with a comparable Ni loading of 3.3 wt%) and Ni-MOF-74 (Figure 17A). The Ni-ETS 10 nanoparticles exhibited higher ethylene conversion rates than Ni-CIT-6 and Ni-MOF- 74 over the entire time-on-stream range investigated. Since the catalyst particles have comparable particle sizes (Figures 3 A, C, and D), the higher rate on Ni-ETS- 10 may not be due to diffusion limitation, but due to the property of the active sites. Ni-ETS-lO with lower loading (Ni(3.90 wt%)-ETS-lO) showed higher initial TOF than Ni-ETS-lO with higher Ni loading
(Ni(6.85 wt%)-ETS-lO). However, the ethylene TOF on Ni (3.90 wt%)-ETS-lO reduced over time on stream, and the TOF stabilized at a lower value than that of Ni(6.85 wt%)-ETS-lO. On the other hand, the TOF on Ni(6.85 wt%)-ETS-lO did not significantly change as the reaction progressed, indicating that a higher Ni loading is desirable for catalyst stability. Ethylene oligomerization reaction performed on pure, as synthesized ETS-10 (i. e. without Ni2+ ions) as a control experiment exhibited no catalytic activity - indicating that the obtained activity for ethylene oligomerization on Ni-ETS-lO is solely from exchanged Ni2+ cations.
Figure imgf000039_0001
Table 3. Ethylene oligomerization catalytic outcomes on different Ni2+ containing
heterogeneous catalysts. Reaction conditions: 180 °C, 5 atm ethylene absolute pressure, 90 gethyiene/(gcataiyst h). *Oligomeric wt% calculations done for the maximum obtained activity injection in GC. Others: Cs, Ci alkanes + alkenes.
The effect of ETS-10 particle size on ethylene oligomerization reaction was also studied (Figure 17 A), which indicates that large particle size resulted in lower turnover frequency. The obtained C4 selectivities over a period of 6 hours for catalysts are also shown in Figures 17 (B and C) and Figures 18A-D. The Ni(6.85 wt%)-ETS-l0 sample showed the highest C4 selectivity, especially after the reaction stabilized. Conventional aluminosilicate zeolites (such as zeolite Beta normally have strong Bruns ted acid sites (Hegde et ak, 1989, Zeolites, 9:231-237; Kiricsi et ak, 1994, J. Phys. Chem., 98:4627-4634; Camblor et ak, Microporous Mesoporous Mater., 1998, 25:59-74), which lead to reduced C4 selectivity. Therefore, the high C4 selectivity on ETS-10 may be attributed to the lack of strong Bransted acid sites (Rudakova et ak, 2008, Opt. Spectrosc., 105: 739-744; Hegde et ak, 1989, Zeolites, 9:231-237; Kiricsi et ak, 1994, J. Phys. Chem., 98:4627-4634; Camblor et ak, Microporous Mesoporous Mater., 1998, 25:59-74; Liepold et ak, 1997, Microporous Mesoporous Mater., 10:211-224; Anderson et ak, 1996, Microporous Mesoporous Mater., 6: 195-204; Robert et ak, 1995, J. Catak, 155:345-352;
Nash et ak, 2009, Appl. Catak B., 88:232-239; Pavel et ak, 2008, J. Catak, 254:84-90). This catalyst sample (Ni(6.85 wt%)-ETS-l0) also showed higher l-butene selectivity over the entire period of 6 hours when compared to Ni(3.9 wt%)-ETS-l0 and Ni-MOF-74 (Figures 18A-D).
The higher l-butene selectivity however decayed continuously over time, while the selectivity of trans- and cis-2 -butene increased over time (Figure 18 A), indicating that the generated l-butene product oligomer might be undergoing isomerization. Ni(6.85 wt%)-ETS-l0 also showed the lowest C6 selectivity over the entire period of 6 hours (Figure 19). Overall, these observations indicate that Ni(6.85 wt%)-ETS-l0 is a stable catalyst for ethylene oligomerization to C4 and that Ni-ETS-lO is a promising catalyst for ethylene oligomerization.
In conclusion, the present invention has exploited the ion-exchange capability of
ETS-10 for catalytic reactions, where Ni2+ was exchanged into ETS-10 for ethylene
oligomerization. The Ni-ETS-lO catalyst was active for ethylene oligomerization, which shows higher rate (based on total Ni) than other microporous catalysts. Ni-ETS-lO also showed highest selectivity to C4 and higher stability than other microporous catalysts investigated in this work.
The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. The appended claims are intended to be construed to include all such embodiments and equivalent variations.

Claims

CLAIMS We claim:
1. A porous composite comprising nickel cations and a covalent framework of silicon, oxygen, and titanium atoms.
2. The porous composite of claim 1, wherein the covalent framework further comprises a metal or metalloid selected from the group consisting of: boron, aluminum, gallium, indium, thallium, calcium, copper, barium, zinc, iron, cobalt, nickel, lead, and combinations thereof.
3. The porous composite of claim 1, wherein the composite has a diameter between about 450 and 550 nm.
4. The porous composite of claim 1, wherein the composite has a diameter between about 0.5 and 10 nm.
5. The porous composite of claim 3, wherein the composite comprises mesopores having a diameter between about 2 and 10 nm.
6. An olefin reaction catalyst comprising the composite of claim 1.
7. A method of making a porous composite, the method comprising:
mixing a solution comprising a metal silicate with a solution comprising a titanium source to form a combined solution;
heating the combined solution of metal silicate and titanium source to a temperature between about 150 and about 250 °C to form a gel; and
contacting the gel with a solution comprising a nickel salt.
8. The method of claim 7, wherein the metal silicate is selected from the group consisting of: sodium silicate, aluminum silicate, lithium silicate, potassium silicate, and magnesium silicate.
9. The method of claim 7, wherein the titanium source is selected from the group consisting of: titanium di chloride, titanium trichloride, titanium tetrachloride, titanium dibromide, titanium tribromide, titanium tetrabromide, titanium difluoride, titanium trifluoride, titanium tetrafluoride, titanium dioxide, titanium (II) oxide, titanium (III) oxide, titanium oxychloride, titanium oxybromide, titanium oxyfluoride, (NH4)2F6Ti, (NHfhBmTi, and (NH ObTΐ.
10. The method of claim 7, wherein the step of mixing the solution comprising the metal silicate and the solution comprising the titanium source further comprises the step of adding at least one metal or metalloid compound, and wherein the metal or metalloid compound is added to the solution comprising the metal silicate, the solution comprising the titanium source, or the combined solution of metal silicate and titanium source.
11. The method of claim 7, wherein the metal or metalloid compound is selected from the group consisting of: cobalt nitrate, nickel nitrate, gallium nitrate, boron nitrate, gallium (III) chloride, gallium (III) bromide, gallium (III) fluoride, boron (III) chloride, boron (III) bromide, boron (III) fluoride, nickel (II) bromide, nickel (II) chloride, nickel (II) fluoride, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) fluoride, sodium aluminate, aluminum chloride, aluminum bromide, aluminum fluoride, alumina, metakaolin, gallium oxides, and boron oxides.
12. The method of claim 7, wherein the step of mixing the metal silicate solution and the titanium source further comprises the step of adding a surfactant.
13. The method of claim 12, wherein the surfactant is selected from the group consisting of: N,N-dimethyl-N-octadecyl-N-(3 trimethoxysilylpropyl) ammonium halides; N,N-dimethyl-N- octadecyl-N-(3-triethoxysilylpropyl) ammonium halides; N,N-dimethyl-N-tetradecyl-N-(3 trimethoxysilylpropyl) ammonium halides; N,N-diethyl-N-octadecyl-N-(3-triethoxysilylpropyl) ammonium halides; N,N-dimethyl-N-butyl-N-(3-triethoxysilylpropyl) ammonium halides; N,N- dimethyl-N-hexyl-N-(3-tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-octyl-N-(3- tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-decyl-N-(3-tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-dodecyl-N-(3-tri ethoxy silylpropyl) ammonium halides; N,N-dimethyl-N-hexadecyl-N-(3 -tri ethoxy silylpropyl) ammonium halides; halides of C22H45- N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3; halides of C2oH4i-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3; halides of Ci8H37-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3; halides of Ci6H33-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3; halides of Ci4H29-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3; halides of Ci2H25-N+(CH3)2-C6Hi2- N+(CH3)2-C6Hi3; and halides of CioH2i-N+(CH3)2-C6Hi2-N+(CH3)2-C6Hi3.
14. The method of claim 7, wherein the step of contacting the gel with the solution of a nickel salt further comprises the steps of:
contacting the gel with a solution comprising an ammonium salt or a solution of base; or contacting the gel with a solution comprising an ammonium salt and a solution of base; and
dehydrating the gel at a temperature of 100 °C to 800 °C.
15. A method for producing a hydrocarbon by oligomerizing an olefin, the method comprising:
contacting an olefin with a porous composite catalyst;
wherein the catalyst comprises nickel cations and a covalent framework of silicon, oxygen, and titanium atoms.
16. The method of claim 15, wherein said contacting of the olefin with the porous composite catalyst is carried out at a temperature less than 210 °C.
17. The method of claim 15, wherein said contacting of the olefin is carried out at a pressure of at least 3 atm.
18. The method of claim 15, wherein the catalyst is mixed with a support selected from the group consisting of: activated carbon, alumina, silica, and ceramic.
19. The method of claim 15, wherein the olefin oligomerization occurs in the gas phase.
20. The method of claim 15, wherein the olefin is a C2 to C4 olefin.
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