Method of producing zeolite encapsulated nanoparticles

Patent metadata

Field	Value
Publication number	US-2016129429-A1
Application number	US-201414899460-A
Country	US
Kind code	A1
Filing date	Jul 7, 2014
Priority date	Jul 5, 2013
Publication date	May 12, 2016
Grant date	—

Abstract

The invention therefore relates to a method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles, the method comprises the steps of: 1) Adding one or more metal precursors to a silica or alumina source; 2) Reducing the one or more metal precursors to form metal nanoparticles on the surface of the silica or alumina source; 3) Passing a gaseous hydrocarbon, alkyl alcohol or alkyl ether over the silica or alumina supported metal nanoparticles to form a carbon template coated zeolite, zeolite-like or zeotype precursor composition; 4a) Adding a structure directing agent to the carbon template coated zeolite, zeolite-like or zeotype precursor composition thereby creating a zeolite, zeolite-like or zeotype gel composition; 4b) Crystallising the zeolite, zeolite-like or zeotype gel composition by subjecting said composition to a hydrothermal treatment; 5) Removing the carbon template and structure directing agent and isolating the resulting zeolite, zeolite-like or zeotype encapsulated metal nanoparticles.

First claim

1 . A method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles, comprising:
1) Adding one or more metal precursors to a silica or alumina source; 2) Reducing the one or more metal precursors to form metal nanoparticles on the surface of the silica or alumina source; 3) Passing a gaseous hydrocarbon, alkyl alcohol or alkyl ether over the silica or alumina supported metal nanoparticles to form a carbon template coated zeolite, zeolite-like or zeotype precursor composition; 4a) Adding a structure directing agent to the carbon template coated zeolite, zeolite-like or zeotype precursor composition thereby creating a zeolite, zeolite-like or zeotype gel composition; 4b) Crystallising the zeolite, zeolite-like or zeotype gel composition by subjecting said composition to a hydrothermal treatment; and 5) Removing the carbon template and structure directing agent and isolating the resulting zeolite, zeolite-like or zeotype encapsulated metal nanoparticles; wherein the carbon template coated zeolite, zeolite-like or zeotype precursor composition of step 3 is used directly in step 4a without removing the silica or alumina source.

2 - 16 . (canceled)

17 . The method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 1 , wherein the one or more metal(s) is selected from the group consisting of group 4 elements, group 6 elements, group 7 elements, group 8 elements, group 9 elements, group 10 elements, group 11 elements and group 12 elements or mixtures thereof.

18 . The method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 1 , wherein the one or more metal(s) is selected from the group consisting of titanium, osmium, iridium, platinum, ruthenium, palladium, rhodium, rhenium, copper, nickel, iron, cobalt, silver, gold, cadmium, and molybdenium or mixtures thereof.

19 . The method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 1 , wherein the hydrocarbon is selected from the group consisting of aliphatic hydrocarbons having 1 to 8 carbon atoms, having 1 to 3 carbon atoms, alkenes having 2 to 6 carbon atoms, aromatic hydrocarbons having 6 to 10 carbon atoms and cyclic hydrocarbons having 3 to 8 carbon atoms.

20 . The method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 1 , wherein the one or more metal precursor is loaded to the silica or alumina in an amount of from 0.5 to 20 wt %, from 0.5 to 5 wt %, from 0.5 to 2 wt %, or 1 wt % during step 1.

21 . The method for producing zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 1 , comprising adding an Al, Sn Ti, Zr or Ge source during step 4a.

22 . The method for producing zeolite, zeolite-like or zeotype particles according to claim 1 , wherein the hydrothermal treatment comprises heating the zeolite, zeolite-like or zeotype gel composition to a temperature between 70 and 300° C., or 180° C., under an autogeneous pressure in an autoclave or open flask for 24 hours or more.

23 . A zeolite, zeolite-like or zeotype encapsulated metal nanoparticles manufactured by the method according to claim 1 .

24 . A zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 , wherein said metal nanoparticles are located predominantly in the secondary porosity of the zeolite structure, or more than 70%, more than 80%, more than 90% or more than 95% of the total amount of the encapsulated metal nanoparticles.

25 . The zeolite zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 , wherein the particle is a hierarchical mesoporous zeolite, zeolite-like or zeotype particle.

26 . The zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 , wherein the amount of metal nanoparticles are in the range from 0.1 to 25 wt %, 0.5 to 20 wt %, 0.5 to 10 wt %, 0.5 to 5%, 1.0 to 5 wt %, 1 to 2 wt %, or 1 wt %.

27 . The zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 , wherein the one or more metal(s) is selected from the group consisting of group 4 elements, group 6 elements, group 7 elements, group 8 elements, group 9 elements, group 10 elements, group 11 elements and group 12 elements or mixtures thereof.

28 . The zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 , wherein the one or more metal(s) is selected from the group consisting of titanium, osmium, iridium, platinum, ruthenium, palladium, rhodium, rhenium, copper, nickel, iron, cobalt, silver, gold, cadmium, and molybdenum or mixtures thereof.

29 . The zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 , comprising an Al, Sn, Ti, Zr or Ge source in the framework of the crystal structure.

30 . A method of using the zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 in shape-selective catalysis comprising:
Providing the zeolite, zeolite-like or zeotype encapsulated metal nanoparticles according to claim 23 ; and
Conducting shape-selective catalysis using said nanoparticles.

Assignees

• Univ Danmarks Tekniske

Inventors

• Kegnæs Søren
• Abildstrøm Jacob Oskar
• Mielby Jerrik Jørgen
• Gallas-Hulin Agata

Classifications

• B01J29/89 Primary

  Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium {(B01J29/005 takes precedence)} · CPC title

• C07C2529/072

  Iron group metals or copper · CPC title

• C07C2529/068

  Noble metals · CPC title

• B01J37/16

  Reducing · CPC title

• C07C5/2737

  with crystalline alumino-silicates, e.g. molecular sieves · CPC title