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KR-102961217-B1 - PRECURSOR FOR PRODUCING AMMONIA SYNTHESIS CATALYST, AMMONIA SYNTHESIS CATALYST PREPARED THEREFROM, AND AMMONIA SYNTHESIS METHOD USING THE SAME

KR102961217B1KR 102961217 B1KR102961217 B1KR 102961217B1KR-102961217-B1

Abstract

The precursor for manufacturing an ammonia synthesis catalyst according to the present invention is manufactured according to a specific method, so that the ratio of a specific peak in X-ray diffraction (XRD) analysis satisfies 0.4 or higher, and thereby a quaternary catalyst exhibiting high efficiency can be manufactured. The ammonia synthesis catalyst manufactured from the above precursor can have a fast ammonia synthesis rate, and thus ammonia can be manufactured with high efficiency even with a small amount of catalyst.

Inventors

  • 박선영
  • 강기혁
  • 윤다님
  • 서필원

Assignees

  • 한국화학연구원

Dates

Publication Date
20260507
Application Date
20231213

Claims (20)

  1. It contains molybdenum (Mo), cobalt (Co), and iron (Fe), A precursor for preparing an ammonia synthesis catalyst, wherein, based on X-ray diffraction (XRD) analysis results, the ratio of the third peak intensity (I 26.5° ) at 2θ=26.5±0.2° to the fourth peak intensity (I 28.5° ) at 2θ=28.5±0.2° (I 26.5° /I 28.5° ) is 0.4 or greater.
  2. In Article 1, The above precursor is a precursor for preparing an ammonia synthesis catalyst represented as (Co 1-x Fe x )Mo 1 O 4 (0<x<1).
  3. In Paragraph 2, The above x is a precursor for manufacturing an ammonia synthesis catalyst, wherein x is 0.05 to 0.1.
  4. In Article 1, The above precursor is a precursor for preparing an ammonia synthesis catalyst, further comprising cesium (Cs) and represented as (Co 1-x Fe x Cs z )Mo 1 O 4 (0<x<1, 0.01≤z≤0.1).
  5. In Paragraph 4, A precursor for preparing an ammonia synthesis catalyst in which z/x is 0.3 to 0.6.
  6. In Article 1, A precursor for preparing an ammonia synthesis catalyst, which, as a result of X-ray diffraction (XRD) analysis, shows a first peak at 2θ=14.5±0.2°, a second peak at 2θ=25.5±0.2°, a fifth peak at 2θ=32.7±0.2°, and a sixth peak at 2θ=44.0±0.2°.
  7. An ammonia synthesis catalyst prepared from a precursor for the preparation of an ammonia synthesis catalyst selected from any one of claims 1 to 6.
  8. In Article 7, The above catalyst is an ammonia synthesis catalyst represented as (Co 1-x Fe x )Mo 1 N y (0<x<1, 0.2<y<0.4).
  9. In Article 7, The above catalyst is an ammonia synthesis catalyst represented by (Co 1-x Fe x Cs z )Mo 1 N y (0<x<1, 0.2<y<0.4, 0.01≤z≤0.1).
  10. In Article 7, An ammonia synthesis catalyst that, as a result of X-ray diffraction (XRD) analysis, exhibits a first peak at 2θ=32.5±0.2°, a second peak at 2θ=35.5±0.2°, a third peak at 2θ=40.0±0.2°, a fourth peak at 2θ=42.5±0.2°, and a fifth peak at 2θ=47.0±0.2°.
  11. (A) A step of preparing a precursor for the production of an ammonia synthesis catalyst; and (B) an ammonolysis step of heat-treating the precursor for the ammonia synthesis catalyst in an ammonia atmosphere; comprising, The above step (A) is (S1) A step of introducing a molybdenum precursor and a cobalt precursor; (S2) Step of adding an organic acid of C3-10; and (S3) A step of introducing an iron precursor; a method for preparing an ammonia synthesis catalyst.
  12. delete
  13. In Paragraph 11, A method for preparing an ammonia synthesis catalyst in which the molar ratio of the iron precursor to the total molar amount of the iron precursor and the cobalt precursor is 0.05 to 0.1.
  14. In Paragraph 11, A method for manufacturing an ammonia synthesis catalyst, further comprising the step (S4) of introducing a polyalcohol after the above step (S3).
  15. In Paragraph 14, A method for preparing an ammonia synthesis catalyst in which the molar ratio of polyhydric alcohol to the organic acid is 0.1 to 2.0.
  16. In Paragraph 11, The above (S3) step is a method for preparing an ammonia synthesis catalyst by a co-precipitation method.
  17. In Paragraph 11, A method for preparing an ammonia synthesis catalyst comprising, after the above step (S3), the step (S3-1) of introducing a cesium (Cs) precursor.
  18. In Paragraph 17, A method for preparing an ammonia synthesis catalyst in which the molar ratio of the cesium precursor to the total molar amount of the iron precursor and the cesium precursor is 0.05 to 0.1.
  19. In Paragraph 17, The above (S3-1) step is a method for preparing an ammonia synthesis catalyst by a co-precipitation method.
  20. In Paragraph 11, A method for manufacturing an ammonia synthesis catalyst, wherein the above step (A) further performs the drying and calcination step (S5) to produce a precursor for manufacturing an ammonia synthesis catalyst.

Description

Precursor for producing an ammonia synthesis catalyst, an ammonia synthesis catalyst prepared therefrom, and a method for synthesizing ammonia using the same The present invention relates to a precursor for manufacturing an ammonia synthesis catalyst, a method for manufacturing the same, an ammonia synthesis catalyst manufactured therefrom, and a method for synthesizing ammonia using the same. Ammonia is recognized as an important medium for providing a stable food supply to humanity and is regarded as a promising source of future energy. Currently, as renewable energy derived from electricity is difficult to ship and store, research is underway to convert hydrogen generated from solar and wind energy into ammonia. This method is expected to provide a renewable energy solution by enabling easy shipping and storage similar to petroleum products. In particular, ammonia has a density 1.5 times that of liquid hydrogen, making it possible to establish infrastructure at a relatively high density and low cost. Consequently, ammonia is designed to have relatively low manufacturing costs. Furthermore, hydrogen can be supplied by utilizing existing ammonia supply chains, and it offers the advantage of being directly used as energy in the power generation sector without the need for dehydrogenation reactions for hydrogen extraction. Therefore, efficiently controlling the synthesis and decomposition reactions of ammonia can accelerate the arrival of a carbon-free energy era. However, conventional ammonia synthesis is a process with very high energy consumption because it uses the Haber-Bosch process, which requires high temperature and pressure. To address this, new processes such as electrochemistry are being proposed for lower cost and energy efficiency, but research is needed to improve energy efficiency by effectively utilizing existing process equipment. One such method is to synthesize ammonia at low temperatures (below 500°C) and pressures (1 to 100 bar) using a new catalyst-based method, and for this, the development of catalysts with high production efficiency is essential. Although iron (Fe) and ruthenium (Ru) are known as representative active metals for ammonia synthesis or decomposition, they have not yet yielded satisfactory results. Furthermore, since ruthenium faces the problem of low commercial viability due to its high cost, there is an urgent need to develop catalysts that are more economical and highly efficient than conventional ones. Figure 1 shows the X-ray diffraction (XRD) analysis results of precursors prepared according to Preparation Examples 1 and 3 to 7. Figure 2 shows the X-ray diffraction (XRD) analysis results of ammonia synthesis catalysts prepared according to Examples 1 and 8 to 10. Figure 3 is a schematic diagram illustrating the esterification reaction between an organic acid and a polyalcohol. The present invention will be described in more detail below through specific examples or embodiments, including the attached drawings. However, the following specific examples or embodiments are merely references for the detailed description of the present invention and the present invention is not limited thereto and may be implemented in various forms. Furthermore, unless otherwise defined, all technical and scientific terms have the same meaning as generally understood by one of the art to which the present invention pertains. The terms used in the description of the present invention are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention. Additionally, the singular form used in the specification and the appended claims may be intended to include the plural form unless specifically indicated otherwise in the context. Additionally, units used herein without special mention are based on weight, for example, units of % or ratio mean weight % or weight ratio, and weight % means the weight percentage of any one component of the total composition that occupies the composition, unless otherwise defined. Furthermore, when a part in this specification is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Additionally, the numerical ranges used in this specification may include lower and upper limits and all values within the range, increments logically derived from the form and width of the defined range, all of which are limited values, and all possible combinations of upper and lower limits of numerical ranges defined in different forms. Unless otherwise specifically defined in the specification of this invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range. Hereinafter, a precursor for manufacturing an ammonia synthesis catalyst and a method for manufacturing the same according to one embodiment of