General method to incorporate metal nanoparticles in zeolites and zeotypes
US-2017036197-A1 · Feb 9, 2017 · US
US11654422B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-11654422-B2 |
| Application number | US-201916698558-A |
| Country | US |
| Kind code | B2 |
| Filing date | Nov 27, 2019 |
| Priority date | May 31, 2017 |
| Publication date | May 23, 2023 |
| Grant date | May 23, 2023 |
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To provide a structured catalyst for catalytic cracking or hydrodesulfurization that suppresses decline in catalytic activity, achieves efficient catalytic cracking, and allows simple and stable obtaining of a substance to be modified. The structured catalyst for catalytic cracking or hydrodesulfurization ( 1 ) includes a support ( 10 ) of a porous structure composed of a zeolite-type compound and at least one type of metal oxide nanoparticles ( 20 ) present in the support ( 10 ), in which the support ( 10 ) has channels ( 11 ) that connect with each other, the metal oxide nanoparticles ( 20 ) are present at least in the channels ( 11 ) of the support ( 10 ), and the metal oxide nanoparticles ( 20 ) are composed of a material containing any one or two more of the oxides of Fe, Al, Zn, Zr, Cu, Co, Ni, Ce, Nb, Ti, Mo, V, Cr, Pd, and Ru.
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What is claimed is: 1. A structured catalyst for catalytic cracking or hydrodesulfurization comprising: a support of a porous structure comprising a zeolite compound having a framework; and at least one type of metal oxide nanoparticles present in the support, wherein the support has a plurality of channels connecting with each other, the metal oxide nanoparticles are present at least in the channels of the support, and the metal oxide nanoparticles are composed of a material containing any one or two or more of the oxides of Fe, Al, Zn, Zr, Cu, Co, Ni, Ce, Nb, Ti, Mo, V, Cr, Pd, and Ru, wherein the channels have any one of a one-dimensional pore, a two-dimensional pore, and a three-dimensional pore defined by the framework of the zeolite compound and an enlarged pore portion that has an inner diameter greater than that of any of the one-dimensional pore, the two-dimensional pore, and the three-dimensional pore, is not defined by the framework of the zeolite-type compound, and is greater than or equal to an average particle size of the metal oxide nanoparticles, wherein the metal oxide nanoparticles are present at least in the enlarged pore portion to prevent contact between the metal oxide nanoparticles in the enlarged pore portions, and the average particle size of the metal oxide nanoparticles is greater than any one of the one-dimensional pore, the two-dimensional pore, and the three-dimensional pore defined by the framework of the zeolite-type compound, and wherein a skeletal structure of the zeolite compound is selected from a FAU type, a MTW type, a MFI type, a FER type, a LTA type, a MWW type, a MOR type, a LTL type, and a BEA type. 2. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein the metal oxide nanoparticles are complex metal oxide nanoparticles composed of a material including two or more of metal oxides, and the complex metal oxide nanoparticles have a first metal oxide including any one or two or more of the oxides of Fe, Al, Zn, Cu, Co, Ni, Nb, Mo, V, Cr and Pd, and a second metal oxide including any one or two or more of the oxides of Zr, Ce, Ti, and Ru. 3. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein the enlarged pore portion connects a plurality of pores constituting any one of the one-dimensional pore, the two-dimensional pore, and the three-dimensional pore to another plurality of pores constituting another one of the one-dimensional pore, the two-dimensional pore, and the three-dimensional pore. 4. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein the average particle size of the metal oxide nanoparticles is less than or equal to the inner diameter of the enlarged pore portion. 5. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein a metal element of the metal oxide nanoparticles is contained in an amount from 0.5 mass % to 2.5 mass % based on the structured catalyst. 6. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein the average particle size of the metal oxide nanoparticles is from 0.1 nm to 50 nm. 7. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein a ratio of the average particle size of the metal oxide nanoparticles to an average inner diameter of the channels is from 1.1 to b 36 . 8. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 7 , wherein the ratio of the average particle size of the metal oxide nanoparticles to the average inner diameter of the channels is from 1.7 to 4.5. 9. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein the average inner diameter of the channels is from 0.1 nm to 1.5 nm, and the inner diameter of the enlarged pore portion is from 0.5 nm to 50 nm. 10. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , further comprising at least one other type of the metal oxide nanoparticles held on an outer surface of the support. 11. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 10 , wherein a content of the at least one type of metal oxide nanoparticles present in the support is greater than a content of the at least one other type of metal oxide nanoparticles held on the outer surface of the support. 12. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein the structured catalyst has a cylindrical, foliate, dumbbell column, or ring-shaped pellet shape, and an average particle size of the structured catalyst is from 100 μm to 15 cm. 13. The structured catalyst for catalytic cracking or hydrodesulfurization according to claim 1 , wherein the enlarged pore portion connects a plurality of pores constituting any one of the one-dimensional pore, the two-dimensional pore, and the three-dimensional pore to another plurality of pores constituting one of the one-dimensional pore, the two-dimensional pore, and the three-dimensional pore.
Nanoparticles · CPC title
Scanning electron microscopy; Transmission electron microscopy · CPC title
Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title
Metal or metal oxide crystallite size · CPC title
Crystalline silica-polymorphs, e.g. silicalites {dealuminated aluminosilicate zeolites} · CPC title
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