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Hydrodesulfurization catalyst and system, preparation method thereof, and method for hydrodesulfurization of diesel

A hydrodesulfurization and catalyst technology, which is applied in the direction of catalyst activation/preparation, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of unfavorable catalyst regeneration, complexity, and catalyst preparation technology that cannot meet the requirements, and achieve high desulfurization activity, increase the degree of sulfidation, and improve the effect of desulfurization activity

Active Publication Date: 2018-01-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The above-mentioned filling method is relatively complicated in actual use, which is not conducive to the regeneration of the catalyst
However, with the stricter environmental protection standards and the decline in the quality of diesel raw materials, the existing catalyst preparation technology is gradually unable to meet the requirements

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0040] According to the preparation method of the catalyst of the present invention, preferably, the method further comprises increasing the temperature by 20-150°C from the temperature corresponding to the highest exothermic peak of the carboxylic acid compound at a rate of 1-20°C / h. °C is preferably 1-10 °C, more preferably 5-10 °C and is kept constant for 1-15 h, preferably 1-10 hours.

[0041] By adopting a multi-stage sulfuration method, the degree of sulfuration of the metal in the catalyst is increased, so the catalyst has a high number of active centers.

[0042] In order to improve the activity of the catalyst, a special sulfidation step is taken in the present invention. The method can convert more active metals in the oxidized catalyst into a sulfurized state, increase the number of active components, and increase the proportion of active phases stacked with four or more layers, so that the catalyst exhibits higher hydrodesulfurization activity.

[0043] When the o...

Embodiment 1

[0087] The carboxylic acid compound contained in the catalyst A1 is citric acid, the content of cobalt oxide is 5%, the content of molybdenum oxide is 17%, P 2 o 5 The content is 6%, and the molar ratio of citric acid to cobalt is 1.5:1.

[0088] Catalyst B1 contains nickel oxide 5%, molybdenum oxide content is 22%, P 2 o 5 The content is 6%, and the molar ratio of citric acid to nickel is 1.5:1.

[0089] The catalyst is determined by temperature-programmed oxidation experiments, and it can decompose and release CO between 230°C-300°C and 300°C-400°C. 2 , and the release temperatures were 290°C and 370°C, respectively.

[0090] Catalyst A1 is packed in the upper bed, catalyst B1 is packed in the lower bed, and the volume ratio of catalyst A1 to catalyst B1 is 1:1.

[0091] The hydrodesulfurization activity evaluation of the catalyst was carried out on a 20mL high-pressure hydrodesulfurization evaluation device, and the catalyst system was vulcanized by the sulfidation met...

Embodiment 2

[0103] The carboxylic acid compound contained in catalyst A2 is tartaric acid, the content of cobalt oxide is 6%, the content of molybdenum oxide is 20%, the content of MgO is 5.4%, and the molar ratio of tartaric acid to cobalt is 1:1.

[0104] Catalyst B2 contains 6% nickel oxide, 20% molybdenum oxide, 5.4% MgO, and the molar ratio of tartaric acid to nickel is 1:1.

[0105] Catalyst A2 is packed in the upper bed, catalyst B2 is packed in the lower bed, and the volume ratio of catalyst A2 to catalyst B2 is 2:1. According to the temperature-programmed oxidation test, the catalysts decompose and release CO at 280°C and 350°C respectively. 2 .

[0106] Carry out the vulcanization and vulcanization performance test of the catalyst system according to the method of Example 1, the difference is that the vulcanization program is changed to: be heated to 280 ° C at a heating rate of 5 ° C / h and then keep the temperature for 2 h, and then at a temperature of 5 ° C / h The heating...

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Abstract

The invention relates to a hydrodesulfurization catalyst, a preparation method thereof, a hydrodesulfurization catalyst system, and a diesel hydrodesulfurization method. The hydrodesulfurization catalyst comprises a carrier and sulfide-state metal active components and trace elements loaded on the carrier. The trace elements are one or more selected from P, F, Si, B and Mg. The metal active components comprise Group VIII and Group VIB metal elements. The catalyst is characterized in that, tested with XPS, the vulcanization degree of the Group VIII metal elements in the catalyst is no lower than 70%, and the vulcanization degree of the Group VIB metal elements in the catalyst is no lower than 70%; and counted with TEM, an active phase ratio of a three-layer stack of the catalyst is no lower than 18%, and an active phase ratio of a four-layer-and-above stack of the catalyst is no lower than 8%. With the hydrodesulfurization catalyst provided by the invention, good desulfurization effect is provided.

Description

technical field [0001] The invention relates to a hydrodesulfurization catalyst, a preparation method thereof, a hydrodesulfurization catalyst system and a method for using the catalyst system to carry out hydrodesulfurization of diesel oil. Background technique [0002] With the increasingly stringent environmental protection regulations, the quality requirements of diesel oil are becoming more and more stringent, and gradually develop towards ultra-low sulfur content (sulfur content is not higher than 10ppm). On the other hand, the proportion of low-quality crude oil is getting higher and higher, resulting in low-quality and diversified sources of diesel oil, which has caused enormous pressure on today's diesel hydrogenation units. The properties of different diesel hydrogenation raw materials are very different, such as sulfur content, sulfide type, nitrogen content, aromatics content, etc. may be significantly different. Moreover, these sulfur-containing compounds, nitr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/051B01J37/20C10G45/08
Inventor 陈文斌龙湘云王轶凡李明丰聂红李大东鞠雪艳
Owner CHINA PETROLEUM & CHEM CORP