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A sulfided hydrogenation catalyst and its preparation method and application

A technology of hydrogenation catalyst and sulfide state, which is applied in the field of preparation of sulfide state hydrogenation catalyst, and can solve the problem of low sulfide degree

Active Publication Date: 2017-11-03
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] The object of the present invention is to overcome the defect that the degree of sulfidation obtained by sulfurizing the hydrogenation catalyst by the existing method is low, and to provide a method for preparing a sulfided hydrogenation catalyst capable of increasing the degree of sulfidation, obtained by the method Sulfide state hydrogenation catalyst and application of said sulfide state hydrogenation catalyst in hydrodesulfurization reaction

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  • A sulfided hydrogenation catalyst and its preparation method and application

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preparation example Construction

[0024] The preparation method of the sulfurized state hydrogenation catalyst provided by the invention comprises the following steps:

[0025] (1) Prepare an oxidized state hydrogenation catalyst, the oxidized state hydrogenation catalyst includes a carrier and a carboxylic acid compound and an active metal oxide supported on the carrier, and the carboxylic acid compound has at least one exothermic peak;

[0026] (2) In the presence of a vulcanization medium, the temperature of the oxidized hydrogenation catalyst is sequentially raised from room temperature to each exothermic peak of the carboxylic acid compound at 200-400°C at a rate of 1-20°C / h Constant temperature vulcanization at the corresponding temperature for 1-5 hours, and then increase the temperature at a rate of 1-20°C / h from the temperature corresponding to the highest exothermic peak of the carboxylic acid compound between 200-400°C Raise 20-150°C and vulcanize at constant temperature for 1-5 hours.

[0027] In...

Embodiment 1

[0045] This example is used to illustrate the sulfided hydrogenation catalyst provided by the present invention and its preparation method.

[0046] Prepare oxidation state hydrogenation catalyst A1 according to a conventional method, which includes alumina carrier and NiO and MoO supported on alumina carrier 3 Active metal components and acetic acid, wherein the molar ratio of carbon atoms to Ni metal atoms in oxidation state hydrogenation catalyst A1 is 2:1, based on the total weight of oxidation state hydrogenation catalyst, NiO and MoO 3 The mass content is respectively 3% and 15%. Oxidized state hydrogenation catalyst A1 can decompose and release CO at 230°C-295°C and 300°C-400°C through the temperature-programmed oxidation method (heating rate is 10°C / min, the same below). 2 , CO 2The temperatures corresponding to the release peaks were 290°C and 370°C, respectively. The oxidized state hydrogenation catalyst A1 is vulcanized by a dry vulcanization method, and the vulc...

Embodiment 2

[0054] This example is used to illustrate the sulfided hydrogenation catalyst provided by the present invention and its preparation method.

[0055] Oxidation state hydrogenation catalyst B1 was prepared according to a conventional method, which included an alumina support and NiO and WO supported on the alumina support. 3 Active metal components and citric acid, wherein the molar ratio of carbon atoms to Ni metal atoms in oxidation state hydrogenation catalyst B1 is 6:1, based on the total weight of oxidation state hydrogenation catalyst, NiO and WO 3 The mass content is respectively 2.5% and 20.5%. Oxidation hydrogenation catalyst B1 can decompose and release CO at temperatures between 200°C-295°C and 300°C-400°C as measured by the temperature-programmed oxidation method 2 , CO 2 The temperatures corresponding to the release peaks were 250°C, 300°C and 385°C, respectively. The oxidized state hydrogenation catalyst B1 is vulcanized by a dry vulcanization method, and the vu...

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Abstract

The invention provides a sulfurized state hydrogenation catalyst, a preparation method and application thereof. The preparation method of the sulfide state hydrogenation catalyst comprises the following steps: (1) prepare the oxidized state hydrogenation catalyst, the oxidized state hydrogenation catalyst comprises a carrier and a carboxylic acid compound and an active metal oxide loaded on the carrier, the carboxylic acid The compound has at least one exothermic peak at 200-400°C; (2) In the presence of a vulcanization medium, the temperature of the oxidized hydrogenation catalyst is sequentially raised from room temperature to carboxylic acid compound at a rate of 1-20°C / h at 200°C Constant temperature vulcanization at the temperature corresponding to each exothermic peak of ‑400°C for 1‑5 hours, and then increase the temperature at a rate of 1‑20°C / h from the highest temperature of the carboxylic acid compound between 200‑400°C The temperature corresponding to the peak value of the exothermic peak is raised by 20-150°C and vulcanized at constant temperature for 1-5 hours. Adopting the method of the invention can increase the sulfidation degree of the metal in the catalyst and the proportion of stacking structures with more than four layers, thereby facilitating the improvement of the hydrogenation desulfurization activity of the catalyst.

Description

technical field [0001] The invention relates to a preparation method of a sulfide hydrogenation catalyst, a sulfide hydrogenation catalyst obtained by the method and an application of the sulfide hydrogenation catalyst in hydrodesulfurization reaction. Background technique [0002] Hydroprocessing is a pillar technology in the modern oil refining industry, which plays an important role in producing clean fuels, improving product quality, making full use of petroleum resources and raw material pretreatment. With the development of economy, environmental protection and society, oil refining enterprises have continuously put forward higher requirements for the activity and stability of hydrogenation catalysts, and the activity and selectivity of hydrogenation catalysts need to be continuously improved. Among them, hydrodesulfurization activity is an important index to measure the performance of hydrogenation catalysts. [0003] Generally speaking, the active metal component of...

Claims

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Application Information

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IPC IPC(8): B01J23/883B01J23/888B01J23/882C10G45/08
Inventor 陈文斌龙湘云李明丰刘学芬赵新强刘清河王奎聂红丁石
Owner CHINA PETROLEUM & CHEM CORP
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