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KR-20260063541-A - CATALYST FOR DEHYDROGEN REACTION AND MANUFACTURING METHOD OF THEREOF

KR20260063541AKR 20260063541 AKR20260063541 AKR 20260063541AKR-20260063541-A

Abstract

The present invention provides a hydrogen extraction reaction catalyst comprising a support including ceria ( CeO2 ) and alumina ( Al2O3 ); and platinum and sulfur supported on the support, satisfying Formula 1 below. [Equation 1] 0 < q×r ≤ 11 (In Equation 1 above, q is the absolute value of the rate of change of DoDH (Degree of dehydrogenation) at a specific time t, r is the absolute value of the magnitude of the change in DoDH before and after the regeneration process at a specific time t, and the specific time t refers to the time during which the hydrogen extraction reaction catalyst is used in the reaction.)

Inventors

  • 정향수
  • 김용민
  • 손현태
  • 온의림
  • 남석우

Assignees

  • 한국전력공사
  • 한국과학기술연구원

Dates

Publication Date
20260507
Application Date
20241030

Claims (15)

  1. A support comprising ceria ( CeO2 ) and alumina ( Al2O3 ); and It comprises platinum and sulfur supported on the above support, and Satisfying Equation 1 below, Hydrogen extraction reaction catalyst. [Equation 1] 0 < q×r ≤ 11 (In Equation 1 above, q is the absolute value of the rate of change of DoDH (Degree of dehydrogenation) at a specific time t before the regeneration process, r is the absolute value of the magnitude of change of DoDH at a specific time t before and after the regeneration process, and the specific time t refers to an arbitrary time during the hydrogen extraction reaction.)
  2. In paragraph 1, Satisfying Equation 2 below, Hydrogen extraction reaction catalyst. [Equation 2] 97 ≤ p/q ≤ 150 (In Equation 2 above, p is the absolute value of DoDH at a specific time t before the regeneration process, q is the absolute value of the rate of change of DoDH at a specific time t before the regeneration process, and the specific time t refers to an arbitrary time during the hydrogen extraction reaction.)
  3. In paragraph 1, Satisfying Equation 3 below, Hydrogen extraction reaction catalyst. [Equation 3] 5 ≤ p/r ≤ 12 (In Equation 3 above, p is the absolute value of DoDH at a specific time t before the regeneration process, r is the absolute value of the magnitude of the change in DoDH at a specific time t before and after the regeneration process, and the specific time t refers to an arbitrary time during the hydrogen extraction reaction.)
  4. In paragraph 1, Satisfying the following Equation 4, Hydrogen extraction reaction catalyst. [Equation 4] 7 ≤ p/(q×r) ≤ 30 (In Equation 4 above, p is the absolute value of DoDH at a specific time t before the regeneration process, q is the absolute value of the rate of change of DoDH at a specific time t before the regeneration process, r is the absolute value of the magnitude of the change in DoDH at a specific time t before and after the regeneration process, and the specific time t refers to an arbitrary time during the hydrogen extraction reaction.)
  5. In any one of paragraphs 2 through 4, In the above equations 2 to 4, 50 ≤ p < 100, Hydrogen extraction reaction catalyst.
  6. In any one of paragraphs 1 through 4, In the above Equation 1, 0 < q ≤ 0.8, Hydrogen extraction reaction catalyst.
  7. In any one of paragraphs 1 through 4, In the above Equation 1, 0 ≤ r ≤ 9, Hydrogen extraction reaction catalyst.
  8. In paragraph 1, The ratio of the wt% of sulfur to the wt% of platinum with respect to a total of 100 wt% is in the range of 0.15 to 0.5, Hydrogen extraction reaction catalyst.
  9. In paragraph 8, The above wt% of sulfur is in the range of greater than 0 and less than or equal to 0.3, Hydrogen extraction reaction catalyst.
  10. In paragraph 1, With respect to 100 wt% of the entire support, the wt% of the ceria is in the range of greater than 0 and less than or equal to 10, Hydrogen extraction reaction catalyst.
  11. (S1) A step of stabilizing the crystal structure of an alumina ( Al₂O₃ ) support by heat treatment in an air atmosphere; (S2) A step of preparing a support comprising ceria ( CeO2 ) and alumina by stirring, evaporating, and heat-treating the stabilized alumina support with a cerium precursor; (S3) A step of supporting the above-mentioned support containing ceria and alumina on a platinum precursor, followed by drying and heat treatment; and (S4) A step comprising immersing the platinum-supported support in a sulfur precursor and then drying and heat-treating, Method for preparing a hydrogen extraction reaction catalyst.
  12. In Paragraph 11, The above step (S1) involves heat treatment in a temperature range of 700 to 1000℃, Method for preparing a hydrogen extraction reaction catalyst.
  13. In Paragraph 11, In the above (S2) step, the heat treatment further includes a reduction process, and The above reducing gas comprises 5 to 20% of at least one of H₂ , N₂ , NH₃ , CH₄ , and mixtures thereof, Method for preparing a hydrogen extraction reaction catalyst.
  14. In Paragraph 13, The above reduction process is carried out for 4 to 8 hours at a temperature range of 600 to 800℃, Method for preparing a hydrogen extraction reaction catalyst.
  15. In Paragraph 11, At least one of the above steps (S3) and (S4) is the heat treatment carried out in an air atmosphere at a temperature range of 350 to 600°C for 2 to 4 hours. Method for preparing a hydrogen extraction reaction catalyst.

Description

Catalyst for Dehydrogen Reaction and Method for Manufacturing the Same The present invention relates to a catalyst, and more specifically, to a catalyst for extracting hydrogen and a method for manufacturing the same. Hydrogen storage methods utilizing Liquid Organic Hydrogen Carriers (LOHCs) are being developed to store and transport large quantities of hydrogen. In LOHCs, organic matter from which hydrogen has been extracted (LOHC-) is converted into organic matter containing stored hydrogen (LOHC+) through a hydrogen storage reaction. This material is then transported via oil tankers or tank trucks, and upon arrival at the point of demand, it is converted back into LOHC- through a dehydrogenation reaction that releases hydrogen. This LOHC- material is then transported to a hydrogen production site where it is converted back into LOHC+. Representative LOHC-/LOHC+ substances include toluene/methylcyclohexane, benzyltoluene/perhydro-benzyltoluene, and dibenzyltoluene/perhydro-dibenzyltoluene, and much research and development is being conducted on benzyltoluene and dibenzyltoluene, which are safe to use due to their relatively low vapor pressure. This is because, unlike toluene, which burns immediately when organic matter is exposed to fire at room temperature, benzyltoluene and dibenzyltoluene do not ignite. The hydrogen extraction reaction of LOHCs is generally accelerated by using a catalyst at high temperatures above 200°C, and catalysts supported with platinum on a support such as alumina ( Al₂O₃ ) are well known to date. Additionally, technologies are being developed to improve the activity and durability of the hydrogen extraction reaction by adding sulfur components to platinum-based catalysts. While it has been reported that these catalysts have an effect on improving catalyst activity and durability, it is unknown what effect they have when reused after a catalyst regeneration process. Figure 1 is a graph of the Degree of Dehydrogenation (DoDH) for reaction time before and after a regeneration process according to one embodiment. Figure 2 is a graph of DoDH for reaction time according to the hydrogen extraction reaction catalyst examples and comparative examples. Figure 3 is a graph of the reaction time before and after the regeneration process according to the hydrogen extraction reaction catalyst example and comparative example 2. The technical terms used herein are for the reference of specific embodiments only and are not intended to limit the invention. The singular forms used herein include plural forms unless phrases clearly indicate otherwise. As used in the specification, the meaning of "comprising" specifies certain characteristics, areas, integers, steps, actions, elements, and/or components, and does not exclude the presence or addition of other characteristics, areas, integers, steps, actions, elements, and/or components. When it is stated that one part is "above" or "on" another part, it may be directly above or on the other part, or other parts may be involved in between. In contrast, when it is stated that one part is "directly above" another part, no other parts are interposed in between. Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as generally understood by those skilled in the art to which this invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with relevant technical literature and the present disclosure, and are not interpreted in an ideal or highly formal sense unless otherwise defined. Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below. Hydrogen extraction reaction catalyst In one embodiment of the present invention, a hydrogen extraction reaction catalyst is provided that includes ceria ( CeO2 ) on a support and is simultaneously supported with sulfur, thereby having high catalytic activity and durability, and having the advantage of having little reduction in catalytic activity even when reused. In one embodiment, the hydrogen extraction reaction catalyst comprises a support comprising ceria ( CeO2 ) and alumina ( Al2O3 ); and platinum and sulfur supported on the support, and may satisfy Formula 1 below. For q and r in Formula 1 below , reference may be made to FIG. 1, which will be described later. [Equation 1] 0 < q×r ≤ 11 In Equation 1 above, q is the absolute value of the rate of change of DoDH (Degree of dehydrogenation) at a specific time t before the regeneration process, r is the absolute value of the range of change of DoDH at a specific time t before and after the regeneration process, and the specific time t refers to an arbitrary time during the hydrogen extraction reaction. DoDH represents a quantitatively measured value of t