A sulfur-resistant methanation catalyst and its preparation method and application

Abstract

The invention provides a sulfur-tolerant methanation catalyst and application thereof. The catalyst is obtained through hydrothermal synthesis, 100 parts by weight of the catalyst contains, by weight, 15-50 parts of active component (M1) AOB, 2-20 parts of carrier modifier (M2) COD and 40-80 parts of carrier, wherein M1 is group-VIB metal elements and / or group-VB metal elements, and M2 is rare earth metals and / or group-IIIB metal elements. The invention provides a preparation method of the sulfur-tolerant methanation catalyst. The method includes the steps that a carrier precursor, an active component precursor and a carrier modifier precursor are mixed with a precipitate slow-release agent in the presence of an aqueous solvent, and the obtained mixed solution is subjected to hydro-thermal treatment under the airtight condition. The catalyst is simple in preparation process and good in repeatability and has high methanation activity and high methane selectivity in a low-temperature and high-water-vapor-content atmosphere.

Description

technical field [0001] The invention relates to a sulfur-resistant methanation catalyst, a preparation method of the sulfur-resistant methanation catalyst, and an application of the sulfur-resistant methanation catalyst of the invention in methanation reactions. Background technique [0002] The methanation reaction is the core of the coal-to-natural gas technology, and the performance of the methanation catalyst directly determines the economy and competitiveness of the entire coal-to-natural gas technology. Ni-based catalysts are often used in existing methanation technologies, but it is well known that Ni-based catalysts are very sensitive to carbon deposition and sulfur species, and are prone to rapid deactivation due to carbon deposition and sulfur poisoning during the reaction. [0003] In order to delay the deactivation of the catalyst due to carbon deposition and sulfur poisoning in the process of industrial application, the synthesis gas obtained from coal gasificat...

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Problems solved by technology

[0005] CN102350375A discloses a magnesium-aluminum spinel-loaded sulfur-resistant Mo-Ni-based methanation catalyst. The results show that the addition of Mo can only moderately improve the sulfur resistance of the Ni-based catalyst. When 50ppm of hydrogen sulfide is added, the activity of the catalyst is immediately decreased significantly

[0008] CN101745401B discloses a method for preparing a loaded Mo-based sulfur-resistant methanation catalyst using a sol-gel method. The catalyst prepared by the method has high low-temperature activity and good stability. However, the sol-gel method for preparing the catalyst is complex and has a long period. Huge water consumption and energy consumption

[0011] After reading CN85109420A and CN103433026A, it can be seen that the catalyst activity disclosed by the two depends on the carrier ZrO to a large extent 2 The specific surface area, however the high specific surface area of ​​ZrO 2 The preparation method is relatively complicated, and there are few high specific surface area ZrO 2 application report

[0012] As mentioned above, although Mo-based catalysts have excellent characteristics of sulfur resistance and carbon deposition resistance, how to improve their methanation activity is still a major challenge for the application of the catalyst in the field of methanation, especially at low temperature and high water vapor partial pressure. Under the atmosphere, the catalyst mainly exhibits high water vapor shift side reaction activity, while the methanation activity is greatly suppressed

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