Zeolitic materials having encapsulated bimetallic clusters

Patent metadata

Field	Value
Publication number	US-10512904-B2
Application number	US-201715602797-A
Country	US
Kind code	B2
Filing date	May 23, 2017
Priority date	May 25, 2016
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

Zeolites having highly dispersed bimetallic clusters, uniformly distributed in size and composition, encapsulated therein are disclosed. Metal encapsulation and alloying is conferred by introducing ligated metal cation precursors into zeolite synthesis gels, which are subsequently crystallized hydrothermally to form zeolites with metal cations occluded in the pores. The ligated cations are anchored to the zeolite framework via siloxane bridges which enforces their uniform dispersion throughout the zeolite crystals. Treatment of the crystallized zeolites in O2 and then H2 forms bimetallic clusters, which remain narrowly distributed in size and composition.

First claim

What is claimed is:

1. An aluminosilicate zeolite having an alloyed bimetallic cluster encapsulated in the pores of the aluminosilicate zeolite, with the zeolite being a small pore zeolite or a medium pore zeolite.

2. The aluminosilicate zeolite of claim 1 , wherein the aluminosilicate zeolite is a small pore zeolite having a CHA, ERI, GIS, KFI, LEV, LTA, RTH, or SOD framework type.

3. The aluminosilicate zeolite of claim 2 , wherein the small pore zeolite has the framework type LTA.

4. The aluminosilicate zeolite of claim 1 , wherein the aluminosilicate zeolite is a medium pore zeolite having an EUO, FER, HEU, MEL, MFI, MFS, MTT, MTW, or TON framework type.

5. The aluminosilicate zeolite of claim 1 , wherein the alloyed bimetallic cluster has a dispersity index of 1 to 1.5.

6. The aluminosilicate zeolite of claim 1 , wherein metals in the alloyed bimetallic cluster are selected from Groups 8 to 12 of the Periodic Table.

7. The aluminosilicate zeolite of claim 6 , wherein a collective amount of metals of Groups 8 to 12 is from 0.1 to 5.0 wt. % of the total weight of composite.

8. The composition of claim 1 , wherein the alloyed bimetallic cluster comprises gold and palladium, gold and platinum, or palladium and platinum.

9. A method of synthesizing the aluminosilicate zeolite of claim 1 , the method comprising the steps of:
(a) preparing a reaction mixture capable of forming the zeolite, the reaction mixture comprising: a source of silicon oxide; a source of aluminum oxide; a source of a Group 1 or 2 metal (X); hydroxide ions; sources of a first metal precursor (M 1 ) and a second metal precursor (M 2 ) of Groups 8 to 12 of the Periodic Table of the Elements; a ligating agent (L) having a thiol group and an alkoxysilyl group; and water;
(b) heating the reaction mixture under crystallization conditions including a temperature of 85° C. to 180° C. and a time from 5 to 250 hours until crystals of the aluminosilicate zeolite are formed;
(c) recovering the aluminosilicate zeolite from step (b):
(d) contacting the aluminosilicate zeolite of step (c) with oxygen under oxidative conditions including a temperature of 250° C. to 500° C. and a time of 0.5 to 5 h; and
(e) contacting the oxidized aluminosilicate zeolite of step (d) with hydrogen under reductive conditions including a temperature of 250° C. to 500° C. and a time of 0.5 to 5 h.

10. The method of claim 9 , wherein the aluminosilicate zeolite is zeolite is prepared from a reaction comprising, in terms of mole ratios, the following:

SiO 2 /Al 2 O 3
≥1

X/SiO 2
0.25 to 1.00

OH/SiO 2
0.25 to 1.00

(M 1 + M 2 )/SiO 2
0.005 to 0.025

L/SiO 2
0.02 to 0.25

H 2 O/SiO 2
≥50. 

11. The method of 9 , wherein the reaction mixture is substantially free of organotemplate materials.

12. The method of claim 9 , wherein the ligating agent is selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (mercaptomethyl)dimethylethoxysilane, mercaptomethyltrimethoxysilane, and combinations thereof.

13. A process for converting a feedstock comprising an organic compound to a conversion product which comprises the step of contacting the feedstock with a catalyst, at organic compound conversion conditions, the catalyst comprising the aluminosilicate zeolite of claim 1 .

14. A process for selectively reducing nitrogen oxides (NO x ), the method comprising contacting a gaseous stream containing NO x with a catalyst comprising the aluminosilicate zeolite of claim 1 .

Assignees

• Univ California
• Chevron Usa Inc

Inventors

• OTTO Trenton
• Iglesia Enrique
• Zones Stacey Ian

Classifications

• B01J23/44

  Palladium · CPC title

• B01J23/52

  Gold · CPC title

• C07C1/20

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• B01J29/74 Primary

  Noble metals · CPC title

• B01J37/009

  Preparation by separation, e.g. by filtration, decantation, screening · CPC title