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Core-shell catalyst, preparation method thereof and application of core-shell catalyst in hydrogen production by reforming

A catalyst and core-shell technology, which is applied in the field of core-shell catalysts and their preparation, can solve problems such as deactivation, limited catalyst reactivity, and difficulty in industrialization

Inactive Publication Date: 2019-04-12
SHANDONG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Among them, the use of bio-oil steam reforming to produce hydrogen is the core step of this process. This reaction process has always been limited by the reactivity of the catalyst and the deactivation phenomenon caused by carbon deposition and sintering, making it difficult to promote industrialization.
The patent (CN 103272604 B) discloses a fly ash catalyst for hydrogen production by catalytic reforming of bio-oil and its preparation method. This technology uses fly ash from a coal-fired power plant as a carrier to prepare a catalyst, which can improve catalytic activity. However, the catalyst described in this technology is prone to carbon deposition, which makes the service life of the catalyst relatively low.

Method used

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  • Core-shell catalyst, preparation method thereof and application of core-shell catalyst in hydrogen production by reforming
  • Core-shell catalyst, preparation method thereof and application of core-shell catalyst in hydrogen production by reforming
  • Core-shell catalyst, preparation method thereof and application of core-shell catalyst in hydrogen production by reforming

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preparation example Construction

[0031] The invention provides a method for preparing a core-shell catalyst, comprising the following steps:

[0032] (1) immersing the biomass pyrolysis ash in the inner core active metal salt solution, followed by drying and calcination treatment to obtain the catalyst inner core;

[0033] (2) mixing cetyltrimethylammonium bromide, ammoniacal liquor, ethanol, deionized water and catalyst core to obtain catalyst core dispersion;

[0034] (3) Ethyl tetrasilicate is slowly dropped into the catalyst core dispersion liquid for mixing, and then the mixed liquid is transferred to a polytetrafluoroethylene-lined stainless steel reactor for crystallization, and the crystallized products are sequentially dried and calcination treatment to obtain a core-shell catalyst precursor;

[0035] (4) impregnating the core-shell catalyst precursor in the shell active metal salt solution, followed by drying, calcining and hydrogen reduction treatment in sequence to obtain the core-shell catalyst....

Embodiment 1

[0052] (1) 30.00 g of pyrolytic carbon from corn stalks was placed in a muffle furnace, and ashed at 500° C. for 1 hour to obtain 10.23 g of biomass pyrolytic ash;

[0053] (2) Prepare a 0.2mol / L nickel nitrate solution, then put 10.00g of biomass pyrolysis ash into the nickel nitrate solution, stir and impregnate at a constant temperature of 60°C for 2h, then dry at 105°C for 24h, and calcined at 800°C 2h, 10.18g of the catalyst inner core was obtained;

[0054] (3) Ultrasonic dispersion and dissolution of CTAB, deionized water, ethanol, and ammonia water was mixed to form a transparent solution. During the process, the molar ratio of CTAB:ammonia water:ethanol:water was 1:10:150:275. Then get 3.00 g of the catalyst inner core prepared in step 1 and disperse it in the solution, stir evenly to obtain the catalyst inner core dispersion, wherein the quality of CTAB is 3.64 g;

[0055] (4) Add 3.12 g of tetraethyl orthosilicate dropwise to the catalyst core dispersion in step (3...

Embodiment 2

[0065] (1) Pyrolytic carbon from rice husks was placed in a muffle furnace, and ashed at 450°C for 1.5 hours to obtain biomass pyrolysis ash;

[0066] (2) Immerse the obtained biomass pyrolysis ash in 0.5mol / L nickel acetate solution for 0.5h, control the mass ratio of nickel acetate to biomass pyrolysis ash to be 1:10, then dry at 80°C for 12h, 650 Calcined at ℃ for 4h to obtain the catalyst core;

[0067](3) Ultrasonic dispersion and dissolution of CTAB, deionized water, ethanol, and ammonia water was used to form a transparent solution. During the process, the molar ratio of CTAB:ammonia water:ethanol:water was 1:15:100:300. Then take the catalyst core prepared in step 1 and disperse it in the solution, wherein the mass ratio of CTAB to the catalyst core is 1:5, stir evenly to obtain the catalyst core dispersion;

[0068] (4) Add orthosilicate ethyl ester dropwise to the catalyst core dispersion liquid described in step (3), wherein the mass ratio of orthosilicate to the c...

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Abstract

The invention provides a core-shell catalyst, a preparation method thereof and an application of the core-shell catalyst in hydrogen production by reforming, and belongs to the technical field of catalysts. The catalyst provided by the invention has a core-shell structure, catalytic activity of an active metal of an inner core can be protected, and carbon deposit coverage caused by a reforming reaction is avoided; biomass pyrolysis ash in the inner core of the catalyst has a porous structure, and the active metal of the inner core can be effectively supported, so that catalytic activity centers are uniformly distributed; and a catalyst outer shell supports a shell-layer active metal, and the shell-layer active metal can catalyze a carbon deposition reaction, inhibit generation of depositedcarbon, and promote consumption of the deposited carbon, so that the service life of the catalyst is prolonged. The invention provides the preparation method of the core-shell catalyst, and the method is simple and is easy to operate. The invention further provides the application of the core-shell catalyst in a reforming hydrogen production reaction.

Description

technical field [0001] The invention relates to the technical field of supported catalysts, in particular to a core-shell catalyst, a preparation method thereof and an application in reforming hydrogen production. Background technique [0002] my country is a large agricultural country with a vast territory and huge reserves of biomass resources. Since the beginning of the 21st century, the world is facing different degrees of energy crisis and environmental pollution. Biomass energy, as a renewable and clean energy, has attracted more and more attention from all countries. The use of agricultural and forestry wastes for pyrolysis and liquefaction to prepare bio-oil is one of the more effective means of indirect utilization of biomass energy resources, which can improve energy density and comprehensive utilization efficiency of resources. [0003] The bio-oil produced by biomass pyrolysis has problems such as high oxygen content, low calorific value, high water content, aci...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/889C01B3/40
CPCC01B3/40B01J23/8892C01B2203/1211B01J35/397Y02P20/52
Inventor 张安东李志合易维明付鹏王丽红王绍庆祁志强罗珊
Owner SHANDONG UNIV OF TECH
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