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CN-119909691-B - Methane dry reforming catalyst, preparation method and application thereof, and methane dry reforming method

CN119909691BCN 119909691 BCN119909691 BCN 119909691BCN-119909691-B

Abstract

The invention relates to the field of catalyst preparation, and discloses a methane dry reforming catalyst, a preparation method and application thereof, and a methane dry reforming method, wherein the methane dry reforming catalyst comprises a catalyst carrier and active metal, the active metal is at least one selected from Ni, ru, rh, ir and Pt, the mass percent of the catalyst carrier is 80-99wt% based on the total mass of the catalyst, the mass percent of the active metal is 1-20wt% based on oxide, the average mechanical strength of the catalyst carrier is 20-60N/mm, and the particle mechanical strength discrete coefficient of the catalyst carrier is in the range of 0-0.52. The catalyst is used in the reaction of preparing synthetic gas by methane dry reforming, and has high methane conversion rate and hydrogen selectivity.

Inventors

  • SUN XIA
  • ZHANG RONGJUN
  • LI HONGWEI
  • Wang tianye
  • WU YU
  • XIA GUOFU

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260505
Application Date
20231031

Claims (20)

  1. 1. A dry methane reforming catalyst, characterized in that the dry methane reforming catalyst comprises a catalyst support and an active metal; the active metal is selected from at least one of Ni, ru, rh, ir and Pt; The mass percentage of the catalyst carrier is 80-99wt% based on the total mass of the catalyst, and the mass percentage of the active metal calculated by oxide is 1-20wt%; the average mechanical strength of the catalyst carrier is 20-60N/mm; The catalyst support has a particle mechanical strength dispersion coefficient in the range of 0 to 0.5; the particle diameter of the catalyst carrier is 3-20mm, and the catalyst carrier is selected from alumina; The preparation method of the catalyst comprises the following steps: (1) Mixing the carrier precursor with a peptizing agent, and then forming and roasting to obtain a catalyst; (2) Impregnating a catalyst carrier in a solution containing active metals, and calcining to obtain a methane dry reforming catalyst; wherein the temperature change of the material before and after molding is less than 12 ℃; the mixing comprises dry mixing, kneading and/or milling; the mixing and/or milling conditions comprise mixing and/or milling time of 8-160min; The molding conditions comprise molding temperature of 5-50 ℃ and molding pressure of 4-15MPa.
  2. 2. The catalyst according to claim 1, wherein the mass percentage of the catalyst carrier is 82-98wt% based on the total mass of the catalyst, and the mass percentage of the active metal in terms of oxide is 2-18wt%.
  3. 3. The catalyst of claim 1, wherein the catalyst support has an average mechanical strength of 22-56N/mm.
  4. 4. The catalyst according to claim 1, wherein the specific surface area of the catalyst carrier is 40-120m 2 /g; And/or the pore volume of the catalyst carrier is 0.25-0.45mL/g.
  5. 5. The catalyst according to claim 4, wherein the specific surface area of the catalyst carrier is 55-118m 2 /g; And/or the pore volume of the catalyst carrier is 0.28-0.42mL/g.
  6. 6. A method of preparing a methane dry reforming catalyst according to any one of claims 1 to 5, comprising: (1) Mixing the carrier precursor with a peptizing agent, and then forming and roasting to obtain a catalyst; (2) Impregnating a catalyst carrier in a solution containing active metals, and calcining to obtain a methane dry reforming catalyst; wherein the temperature change of the material before and after molding is less than 12 ℃; the active metal is selected from at least one of Ni, ru, rh, ir and Pt; the mixing comprises dry mixing, kneading and/or milling; the mixing and/or milling conditions comprise mixing and/or milling time of 8-160min; The molding conditions comprise molding temperature of 5-50 ℃ and molding pressure of 4-15MPa.
  7. 7. The method of claim 6, wherein the temperature of the material before and after molding varies by less than 10 ℃.
  8. 8. The method of claim 6, wherein the active metal is introduced from an active metal compound.
  9. 9. The production method according to claim 8, wherein the active metal compound is selected from at least one of a nitrate, a carbonate, a basic carbonate, a phosphate, a sulfate, and a chloride containing an active metal.
  10. 10. The preparation method according to claim 6, wherein the impregnation conditions comprise an impregnation temperature of 20-80 ℃ and an impregnation time of 0.2-6 hours; And/or the calcining conditions comprise a calcining temperature of 400-800 ℃ and a calcining time of 1-8 hours.
  11. 11. The preparation method according to claim 10, wherein the impregnation conditions include an impregnation temperature of 25-70 ℃ and an impregnation time of 0.5-4 hours; And/or the calcining conditions comprise a calcining temperature of 450-750 ℃ and a calcining time of 2-6 hours.
  12. 12. The preparation method according to claim 6, wherein the mass percentage of the catalyst carrier is 80 to 99wt% based on the total mass of the methane dry reforming catalyst, and the mass percentage of the active metal in terms of oxide is 1 to 20wt%.
  13. 13. The production method according to claim 12, wherein the mass percentage of the catalyst carrier is 82 to 98wt% based on the total mass of the methane dry reforming catalyst, and the mass percentage of the active metal in terms of oxide is 2 to 18wt%.
  14. 14. The process according to claim 6, wherein in the step (1), the mixing further comprises adding water and a modifying assistant.
  15. 15. The method according to claim 14, wherein the volume of water added is 0.6 to 1mL based on 1g of the carrier precursor.
  16. 16. The process according to claim 15, wherein the volume of water added is 0.65 to 0.95mL based on 1g of the carrier precursor.
  17. 17. The production method according to claim 14, wherein the modifying aid is selected from at least one of alkali metal element-containing, alkaline earth metal element-containing and rare earth metal element-containing compounds.
  18. 18. The production method according to claim 17, wherein the modifying aid is at least one selected from the group consisting of oxides, carbonates, basic carbonates, organic salts, nitrates and hydroxides of alkaline earth metal elements and rare earth metal elements.
  19. 19. The preparation method according to claim 18, wherein the modifying additive is at least one selected from lanthanum nitrate, magnesium nitrate, cerium nitrate, magnesium oxide, calcium oxide, barium oxide, strontium oxide, cerium oxide, lanthanum oxide, and yttrium oxide.
  20. 20. The production method according to claim 14, wherein the modifying assistant is added in an amount of 0.6 to 15 parts by weight relative to 100 parts by weight of the carrier precursor.

Description

Methane dry reforming catalyst, preparation method and application thereof, and methane dry reforming method Technical Field The invention relates to the field of catalyst preparation, in particular to a methane dry reforming catalyst, a preparation method and application thereof, and a methane dry reforming method. Background The active development of high-value utilization technology of CO 2 is an effective way for reducing emission of CO 2 at present. Wherein, the volume ratio of H 2/CO in the synthesis gas (methane dry reforming) prepared by the reaction of methane and CO 2 is less than or equal to 1, and the method is particularly suitable for being used as a raw material for oxo synthesis and Fischer-Tropsch synthesis, and further is used for preparing clean oil products or high-added-value chemicals by Fischer-Tropsch synthesis or methanol synthesis, thereby being a methane and CO 2 utilization path with great potential application prospect. The dry reforming of methane not only can realize the waste utilization of CO 2 and change waste into valuable, but also provides an effective way for the efficient utilization of methane. Simultaneously, greenhouse gases CH 4 and CO 2 are utilized to relieve the greenhouse effect caused by the two gases. Although methane dry reforming reaction has been studied for nearly a hundred years, the process has not been applied industrially so far, and the sintering and carbon deposition of the catalyst under high-temperature reaction conditions are the most major obstacles restricting the industrialization of the process, and especially the carbon deposition of the catalyst under pressurized conditions is outstanding. CN101112692A, CN1011122693a discloses a Ni/Mg xTi1-x O methane-steam-carbon dioxide-oxygen three reforming catalyst with Ni as active component and Mg xTi1-x O as carrier, wherein x is adjustable between 0.05-0.95. However, these two patent applications mainly focus on the preparation of raw catalyst powder and the addition of various surfactants during the preparation process increases the preparation cost, and do not relate to the preparation process of the industrial molded catalyst. CN103949265A discloses a methane-steam-carbon dioxide-oxygen tri-reforming catalyst comprising 11-13wt% Ni, 1-3wt% CeO 2, 1-3wt% La 2O3 and a support having an average particle size of 425-700 microns. This patent application is also concerned with the preparation of catalyst powders and does not relate to the preparation of industrially shaped catalysts. Currently, methane dry reforming catalysts are mainly classified into two types, noble metal catalysts and non-noble metal catalysts. Noble metal catalysts have the advantages of high activity, strong carbon deposit resistance and the like, but are difficult to apply in large-scale industry due to high price. Therefore, there is a need to develop a methane dry reforming catalyst with high activity, high selectivity and high stability. Disclosure of Invention The invention aims to solve the problems of poor catalytic activity and catalytic selectivity, insufficient mechanical strength, easy crushing and poor thermal stability of a methane dry reforming catalyst in the prior art, provides a methane dry reforming catalyst, a preparation method and application thereof, and a methane dry reforming method, the methane dry reforming catalyst has larger specific surface area and pore volume, and the catalyst has higher average mechanical strength when being combined with the supported active metal, so that the catalyst has high methane conversion rate and hydrogen selectivity when being used in the reaction of preparing synthetic gas by methane dry reforming. In order to achieve the above object, a first aspect of the present invention provides a dry methane reforming catalyst comprising a catalyst support and an active metal; the active metal is selected from at least one of Ni, ru, rh, ir and Pt; The mass percentage of the catalyst carrier is 80-99wt% based on the total mass of the catalyst, and the mass percentage of the active metal calculated by oxide is 1-20wt%; the average mechanical strength of the catalyst carrier is 20-60N/mm; the catalyst support has a particle mechanical strength dispersion coefficient in the range of 0 to 0.52. The second aspect of the invention provides a method for preparing a methane dry reforming catalyst, wherein the method comprises the following steps: (1) Mixing the carrier precursor with a peptizing agent, and then forming and roasting to obtain a catalyst; (2) Impregnating a catalyst carrier in a solution containing active metals, and calcining to obtain a methane dry reforming catalyst; wherein the temperature change of the material before and after molding is less than 12 ℃; The active metal is selected from at least one of Ni, ru, rh, ir and Pt. In a third aspect, the present invention provides a methane dry reforming catalyst prepared by the preparation method described in the second as