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Hydrothermal deposition preparation of load type single metal hydrogenation catalyst

A hydrogenation catalyst and hydrothermal deposition technology, applied in metal/metal oxide/metal hydroxide catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems affecting the catalytic activity and active phase structure of catalysts Control, low type I sulfide activity and other issues, to achieve the effect of weakened interaction, strong penetration ability, high reactivity and

Active Publication Date: 2008-11-05
BC P INC CHINA NAT PETROLEUM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003]In the supported catalyst prepared by the traditional impregnation method, the active components are formed during the drying and roasting of the catalyst, and the structure of the active phase is difficult to control. The active ingredient has large particles and low dispersion
In the prior art, the method for improving the dispersion of active components in hydrorefining catalysts is mainly to reduce the particle size of active components by enhancing the interaction between active components and supports, such as the equilibrium adsorption method using active component precursors The reaction with the hydroxyl group on the surface of the alumina carrier makes the active component loaded on the carrier, which can make the active component form a small crystal grain and have a good contact with the carrier surface, and distribute evenly, thus bringing high dispersion ( See N.Spanos et al., Journal of Catalysis, 1990, 124:301; L. Karakonstantis et al., Journal of Catalysis, 1996, 162:306; J.Vakros et al., J.Phys.Chem.B , 2003, 107: 804, C; Kordulis et al., Applied Catalysis A: General, 2001, 209: 85), but the enhancement of the interaction between the active ingredient and the carrier will make it difficult for the active ingredient to vulcanize completely, and it is easy to form low Active type I sulfide active phase, which affects the catalytic activity of the catalyst
On the other hand, although the interaction between the active component and the carrier can be weakened by adding F, P and a complexing agent, it will form larger active component particles, resulting in a decrease in dispersion. Restricted reactions are unfavorable (see M. Sun et al., Catalysis Today, 2003, 86:173; European patents EP0601722, EP 1418002, EP0870003)

Method used

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  • Hydrothermal deposition preparation of load type single metal hydrogenation catalyst
  • Hydrothermal deposition preparation of load type single metal hydrogenation catalyst
  • Hydrothermal deposition preparation of load type single metal hydrogenation catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Weigh 20-40 mesh γ-Al 2 o 3 Put 3g of carrier into a 100ml autoclave, add 27.81ml of 0.1mol / l sodium tungstate solution, then add 2.32ml of 2.4mol / l hydrochloric acid, stir evenly, add 3.48ml of 0.8mol / l oxalic acid solution, oxalic acid The molar ratio to sodium tungstate is 1:1. Maintain the temperature up to 150°C, stir and react for 24 hours, cool to room temperature, filter the suspension, wash with water, dry the obtained solid product at 110°C for 2 hours, and roast at 550°C for 4 hours to obtain W / γ-Al 2 o 3 Catalyst S1, the content of tungsten oxide was determined to be 17.7wt% by X-ray fluorescence spectrometry.

Embodiment 2

[0025] Weigh 20-40 mesh γ-Al 2 o 3 Put 3g of carrier into a 100ml autoclave, add 27.81ml of 0.1mol / l sodium tungstate solution, then add 2.32ml of 2.4mol / l hydrochloric acid, stir evenly, add 6.96ml of 0.8mol / l oxalic acid solution, oxalic acid The molar ratio to sodium tungstate is 2:1. Maintain the temperature up to 150°C, stir and react for 24 hours, cool to room temperature, filter the suspension, wash with water, dry the obtained solid product at 110°C for 2 hours, and roast at 550°C for 4 hours to obtain W / γ-Al 2 o 3 For catalyst S2, the content of tungsten oxide was determined to be 17.7wt% by X-ray fluorescence spectrometry.

Embodiment 3

[0027] Weigh 20-40 mesh γ-Al 2 o 3Put 3g of carrier into a 100ml autoclave, add 27.81ml of 0.1mol / l sodium tungstate solution, then add 2.32ml of 2.4mol / l hydrochloric acid, stir well, add 27.81ml of 0.2mol / l oxalic acid solution, oxalic acid The molar ratio to sodium tungstate is 2:1. Maintain the temperature up to 150°C, stir and react for 12 hours, cool to room temperature, filter the suspension, wash with water, dry the obtained solid product at 110°C for 2 hours, and roast at 550°C for 4 hours to obtain W / γ-Al 2 o 3 For catalyst S3, the content of tungsten oxide was determined to be 17.7wt% by X-ray fluorescence spectrometry.

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Abstract

The invention provides a preparation method for a load type hydrogenation catalyst with high activation by hot water deposition. The saline solution of the reactive metal of VIB family is taken as a precursor, an inorganic acid solution as a precipitator and an organic acid as a dispersant; the metallic oxide particles are generated by a liquid deposition reaction in a hydrothermal condition; the organic acid is used for avoiding the conglobation of the oxide particles as well as reducing mutual effects between the oxide and a carrier; the high reaction activation and strong penetrability of subcritical water is utilized to evenly disperse active components on the carrier. The method is particularly suitable for preparing a W / gamma-Al2O3 catalyst, the prepared W / gamma-Al2O3 catalyst has high dispersion degree, relatively weak mutual effects between the active components and the carrier and higher desulfurization activation compared with a catalyst which has same content of active components and is prepared by a conventional pore volume saturation soaking method.

Description

technical field [0001] The invention belongs to the technical field of preparation of hydrorefining catalysts, and in particular relates to a preparation method of a loaded hydrogenation catalyst capable of realizing higher hydrodesulfurization activity. Background technique [0002] The increasingly stringent quality standards for oil products place higher demands on the desulfurization activity of the hydrofining catalysts used. The supported catalyst with transition metal W or Mo as the main agent, Ni or Co as the auxiliary agent, and alumina as the carrier is currently the most widely used hydrorefining catalyst. In addition to continuous research and exploration on the selection of active components and supports, trying to improve the dispersion of active components in the catalyst is also one of the effective means to improve the activity of supported catalysts, because the preparation method and preparation conditions have great influence on the dispersion and Cataly...

Claims

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Application Information

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IPC IPC(8): B01J23/30B01J21/04C10G45/04
Inventor 鲍晓军范煜王豪石冈刘海燕白跃华兰玲
Owner BC P INC CHINA NAT PETROLEUM CORP
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