Nickel-based oxygen vacancy carrier catalyst as well as preparation method and application thereof

An oxygen vacancy and catalyst technology, applied in the field of nickel-based oxygen vacancy carrier catalyst and its preparation, can solve the problems of difficulty in maintaining high active catalytic performance, poor catalytic stability, deactivation by sulfur poisoning, etc., achieve excellent reforming performance, improve catalytic performance, etc. The effect of improving activity and coking

Active Publication Date: 2020-09-01
TSINGHUA UNIV
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  • Abstract
  • Description
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Problems solved by technology

However, when applied to steam reforming of diesel oil, serious carbon deposition and sulfur poisoning deactivation occur, so it is difficult to maintain high activity and long-term catalytic performance
In order to ensure that the production cost of the catalyst meets the requirements of large-scale use and can withstand the diesel SR process, the carrier or additive of the catalyst should be adjusted. In order to ensure the mechanical strength and hydrothermal stability of the catalyst, Al 2 o 3 as the main carrier, rather than Al alone 2 o 3 As a carrier, such as using lanthanide metal oxides (La, Pr, Nd, Eu, Gd) as promoters, the activity and anti-coking performance of the catalyst have been improved to a certain extent, but there are still problems of low hydrogen yield and poor catalytic stability.

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  • Nickel-based oxygen vacancy carrier catalyst as well as preparation method and application thereof
  • Nickel-based oxygen vacancy carrier catalyst as well as preparation method and application thereof

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preparation example Construction

[0030] The present invention also provides a preparation method of the nickel-based oxygen vacancy supported catalyst described in the above technical solution, comprising the following steps:

[0031] Mixing soluble lanthanum salt, soluble cerium salt and water to obtain a mixed solution;

[0032] Mix the mixed solution with γ-Al 2 o 3 performing a first equal-volume impregnation to obtain a first impregnation;

[0033] performing first drying and first calcination on the first impregnated material in sequence to obtain an oxygen vacancy carrier;

[0034] performing a second equal-volume impregnation of the oxygen vacancy carrier and a soluble nickel salt solution to obtain a second impregnated product;

[0035] performing second drying and second calcination on the second impregnated material in sequence to obtain a catalyst precursor;

[0036] The catalyst precursor is activated to obtain the nickel-based oxygen vacancy supported catalyst.

[0037] The invention mixes ...

Embodiment 1

[0062] Ni / γ-Al 2 o 3 (10wt% Ni and 90wt% γ-Al 2 o 3 ) is prepared by the following method: Weigh 50g of activated alumina and calcinate it in an air atmosphere at 900°C for 6h to obtain γ-Al 2 o 3 . Add 22g of Ni(NO 3 ) 3 , Stir with a magnet for 6h at room temperature. Weigh 40g of γ-Al 2 o 3 Place in the solution for equal volume impregnation, put the beaker containing the solution and the carrier into a shaker at room temperature and shake for 2 hours. The catalyst precursor was dried in an oven at 100 °C for 12 h. The dried precursor was calcined in a tube furnace at 500 °C for 6 h in an air atmosphere. After the catalyst was cooled to room temperature, it was placed in the tube furnace again and heated at 550 °C in 5% H 2 / N 2 Restore in the atmosphere for 10h.

[0063] Ni / CeO 2 -γ-Al 2 o 3 (10wt% Ni, 13.5wt% CeO 2 and 76.5wt% γ-Al 2 o 3 ) is prepared by the following method: Weigh 50g of activated alumina and calcinate it in an air atmosphere at 900°C...

Embodiment 2

[0067] The national VI standard 0# diesel oil and deionized water are used as the reaction raw materials. Ni / γ-Al 2 o 3 , Ni / CeO 2 -γ-Al 2 o 3 and Ni / Ce 0.8 La 0.2 o 2-δ -γ-Al 2 o 3 Placed in a fixed bed reactor for comparison, T=550°C, S / C=4, WHSV=0.3h -1 , P=0.2MPa Take the dried product gas and measure H in gas chromatography 2 , N 2 , CO, CH 4 , CO 2 content.

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Abstract

The invention provides a nickel-based oxygen vacancy carrier catalyst as well as a preparation method and application thereof, and belongs to the field of catalytic reforming and diesel hydrogen production. With the catalyst provided by the invention adopted, the problems of low activity, easy coking and poor sulfur resistance of a diesel reforming catalyst can be solved. Cerium dioxide is used asan oxygen carrier; heterovalent metal La is doped in the CeO2 to reduce oxygen vacancy generation energy; the enhancement of the oxygen storage and release capacity of the carrier can inhibit side reactions so as to improve the activity of a main reaction. Diesel oil H/C is low, a large amount of carbon deposits are likely to occur during reforming; when coking occurs, the oxygen vacancy carriercan release more oxygen to oxidize the carbon deposits, so that coking inactivation of the catalyst is avoided. Ni particles are smaller in size and more uniform in distribution, so that the catalyticactivity of the catalyst is improved, and the catalyst can still keep excellent reforming performance after part of active metal sulfur is poisoned; the oxide of lanthanum is mainly distributed on asurface phase, so that high-temperature stability of the catalyst can be improved, and high-temperature sintering of the catalyst carrier is avoided.

Description

technical field [0001] The invention relates to the technical fields of catalytic reforming and hydrogen production from diesel oil, in particular to a nickel-based oxygen vacancy carrier catalyst and its preparation method and application. Background technique [0002] Environmental issues such as the greenhouse effect and air pollution are closely related to the sharp increase in fossil fuel consumption. Therefore, the transformation of energy structure and the sustainable use of energy have become urgent problems for human society. As a link between secondary energy and traditional energy, hydrogen energy has gradually entered people's field of vision and become a representative of clean energy. The continuous supply of hydrogen is a key link to promote the advent of the "hydrogen era". The raw materials for hydrogen production mainly include fuel, biomass and water. Hydrogen production from liquid fuel reforming, as a hydrogen production method with high energy efficie...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/10B01J23/83B01J35/00C01B3/40
CPCB01J23/005B01J23/10B01J23/83B01J35/006C01B3/40C01B2203/0233C01B2203/1058C01B2203/1082Y02P20/52
Inventor 王玉军薛强强颜彬航
Owner TSINGHUA UNIV
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