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A Ni-based dual-metal nanocapsule catalyst, and preparation and application thereof

A technology of nanocapsules and catalysts, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, nanotechnology, etc. Interaction and other issues, to reduce the reduction electrode potential, promote rapid formation, and avoid mutual interference.

Active Publication Date: 2018-12-07
SHANXI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the limited active metal exposed surface (Ni particles are usually larger than 10nm, the larger the particle, the less exposed active surface) and the dense shell thickness of core-shell catalysts, the active Ni sites are not enough for the rapid diffusion of reactants and convert
In addition, the metal particles encapsulated in the shell cavity can move freely, resulting in poor metal-support interaction, which is not suitable for the reforming reaction process with high methane concentration

Method used

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  • A Ni-based dual-metal nanocapsule catalyst, and preparation and application thereof
  • A Ni-based dual-metal nanocapsule catalyst, and preparation and application thereof
  • A Ni-based dual-metal nanocapsule catalyst, and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1: Weigh 10 g of polyoxyethylene (10) cetyl ether into a conical flask, add cyclohexane to 100 mL, heat and stir at 40° C. When it is observed that the solution becomes clear, add 5 mL of 2.0 mol / L nickel nitrate and copper nitrate mixed solution (Ni:Cu molar ratio is 1:1), stir until well mixed, then add 2 mL of hydrazine hydrate. After aging for 0.5h, increase the rotation speed and add a mixed solution of 2ml of concentrated ammonia water (25wt.%) and 13mL of deionized water, then slowly add 10mL of TEOS, after hydrolysis for 1h, add isopropanol to break the emulsion, and centrifuge. Finally, the obtained sample was dried at 110° C. for 12 h, and then calcined at 500° C. at a rate of 1° C. / min in an air atmosphere to obtain bimetallic nanocapsule catalyst 1 .

[0036] The calcined catalyst 1 was pressed into tablets and sieved, and 0.1g of the 20-40 mesh catalyst was taken, mixed evenly with quartz sand and then put into a reaction tube, and then reduced for ...

Embodiment 2

[0037] Example 2: Weigh 20 g of polyoxyethylene (10) cetyl ether into a conical flask, add cyclohexane to 100 mL, heat and stir at 45° C. When it is observed that the solution becomes clear, add 7 mL of 1.8 mol / L nickel nitrate and cobalt nitrate mixed solution (Ni:Co molar ratio is 2:1), stir until well mixed, then add 3 mL of hydrazine hydrate. After aging for 1.5 hours, increase the speed and add a mixed solution of 1.5ml of concentrated ammonia water and 13.5mL of deionized water, then slowly add 12.5mL of TEOS, after hydrolysis for 6 hours, add isopropanol to break the emulsion, and centrifuge. Finally, the obtained sample was dried at 80° C. for 24 h, and then calcined at 600° C. at a rate of 1.5° C. / min in an air atmosphere to obtain bimetallic nanocapsule catalyst 2 .

[0038] The calcined catalyst 2 was pressed into tablets and sieved, and 0.1g of 40-60-mesh catalyst was taken, mixed evenly with quartz sand, and then put into a reaction tube, and then reduced for 1 ho...

Embodiment 3

[0039] Example 3: Weigh 34g of polyoxyethylene (10) cetyl ether into a conical flask, add cyclohexane to 100mL, heat and stir at 50°C. When it is observed that the solution becomes clear, add 5 mL of 1.5 mol / L nickel nitrate and copper nitrate mixed solution (Ni:Cu molar ratio is 4:1), stir until well mixed, then add 4 mL of hydrazine hydrate. After aging for 3 hours, increase the rotation speed and add a mixed solution of 1ml of concentrated ammonia water and 14mL of deionized water, then slowly add 10mL of TEOS, after hydrolysis for 12h, add isopropanol to break the emulsion, and centrifuge. Finally, the obtained sample was dried at 100° C. for 12 h, and then calcined at 700° C. at a rate of 2° C. / min in an air atmosphere to obtain bimetallic nanocapsule catalyst 3 .

[0040] The calcined catalyst 3 was pressed into tablets and sieved, and 0.1g of 20-40 mesh catalyst was taken, mixed evenly with quartz sand and then put into a reaction tube, and then reduced for 1 hour at 70...

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Abstract

A Ni-based dual-metal nanocapsule catalyst, and preparation and application thereof are disclosed. The catalyst includes a capsule shell layer that is silicon oxide and a metal core that is dual-metalnickel-copper or nickel-cobalt particles. In the catalyst, the total content of nickel and copper or the total content of nickel and cobalt is 10-20 wt%, the particle size of the nickel-copper or nickel-cobalt particles is 1-4 nm, the size of a capsule cavity is (6.5-7.5) nm *(15-60) nm, and the thickness of the capsule shell layer is 5.5 + / - 3 nm. The catalyst has a two-stage channel structure,wherein pores having a size of 3-4 nm are derived from penetrating channels of the shell layer and pores having a size of 12-15 nm are derived from the hollow cavity of the capsule. A unique space-confined structure (including highly nanocrystallized metal particles, metal particle anchoring in the shell layer, a proper shell cavity space, and steric hindrance of the capsule structure) of the catalyst and synergistic effects of dual metals can effectively suppress sintering of active components and carbon deposition in high-temperature reactions, and the catalyst has good activity and stability in a biomass gas reforming reaction.

Description

technical field [0001] The invention relates to a catalyst with a nanocapsule structure, in particular to a Ni-based bimetallic nanocapsule catalyst and a preparation method thereof, as well as the application of the catalyst in biomass gas reforming reactions. Background technique [0002] Biomass gas mainly comes from the anaerobic degradation of biomass in crop straw, forest waste and industrial wastewater. Its main components are methane (50%-70%) and carbon dioxide (30%-50%). It can be used as a natural raw material for methane carbon dioxide reforming to produce synthesis gas, and then applied to hydrogen production, fuel cells or synthetic oil products and other fields. However, methane is usually slightly more than carbon dioxide in the composition of biomass gas. Excessive methane will easily promote the sintering of catalyst active metals and cause serious carbon deposition, which requires higher catalysts. [0003] Nickel-based catalysts are considered to be pref...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/755B01J35/10B01J35/02B82Y30/00B82Y40/00C01B3/40B01J35/00
CPCB82Y30/00B82Y40/00C01B3/40B01J23/755C01B2203/0238C01B2203/1058C01B2203/1241B01J35/396B01J35/50B01J35/40B01J35/647Y02P20/52
Inventor 王长真赵永祥李海涛仇媛周玮
Owner SHANXI UNIV
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