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Preparation method of sulfurized gasoline hydro-upgrading catalyst

A gasoline hydrogenation and catalyst technology, which is applied in catalyst activation/preparation, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve the problems of increasing catalyst preparation and operating costs, increasing equipment investment costs, and cumbersome vulcanization process, etc., to achieve It is beneficial to personal and environmental safety, saves investment costs, and shortens the start-up period

Active Publication Date: 2019-11-19
CHINA UNIV OF PETROLEUM (EAST CHINA)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This kind of internal vulcanization method has been widely used in industry for a long time, but this method usually has the following disadvantages: (1) special pre-sulfurization equipment needs to be set up on the hydrogenation unit, thereby increasing the investment cost of the unit; (2) The vulcanizing agent added during the vulcanization process and the water and high-concentration hydrogen sulfide generated by the reaction can easily cause corrosion of the high-pressure reactor and related equipment and pipelines, resulting in equipment damage and potential safety hazards; (3) The vulcanization process is long, making the start-up period Longer; (4) The vulcanizing agent used is flammable and toxic, and it is easy to pollute the environment during the vulcanization process; (5) The cost of pre-vulcanization in the device is relatively high
In addition, the existing external presulfurization technologies at home and abroad inevitably have disadvantages such as cumbersome vulcanization process, sulfur loss, and heat release concentration, which increase the preparation and operation costs of the catalyst.

Method used

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  • Preparation method of sulfurized gasoline hydro-upgrading catalyst
  • Preparation method of sulfurized gasoline hydro-upgrading catalyst
  • Preparation method of sulfurized gasoline hydro-upgrading catalyst

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preparation example Construction

[0032] In addition, the present invention provides a method for preparing a sulfurized gasoline hydro-upgrading catalyst, comprising the following steps:

[0033] S101: Immerse the gasoline hydrogenation catalyst in the modifier to obtain a passivated and presulfided catalyst; wherein, the molar ratio of the metal content in the gasoline hydrogenation catalyst to the nitrogen content in the passivator is: metal / N=1 : (0.1~0.5), the molar ratio of the metal content in the gasoline hydrogenation catalyst and the sulfur content in the polysulfide is: metal / S=1: (1~4); wherein, the condition of impregnating is: reaction temperature is 25 ℃ ~100°C, the reaction time is 0.5~3 hours.

[0034] S102: heat-treat the catalyst obtained in S101 under a nitrogen atmosphere, and then obtain a sulfurized gasoline hydroreforming catalyst; wherein, the conditions of the heat treatment are: the temperature is 100-400° C., and the time is 1-4 hours.

[0035] Preferably, the gasoline hydrogenatio...

Embodiment 1

[0043] The present invention provides a kind of preparation method of sulfurized gasoline hydrogenation upgrading catalyst, comprises the following steps:

[0044] S101: Measure a certain amount of ammonium sulfide and ethanolamine, and mix them uniformly to obtain a polysulfide ion vulcanizing agent (that is, a modifier for gasoline hydrogenation catalyst); wherein, the sulfur content of ammonium sulfide is the same as that of the metal in gasoline hydrogenation catalyst MC1 The ratio is: the molar ratio of S / metal (Mo, Ni, Ce) = 3 / 1, the molar ratio of the nitrogen content of the passivating agent ethanolamine to the metal (Mo, Ni, Ce) in the gasoline hydrogenation catalyst = 0.2 / 1. Afterwards, the catalyst MC1 was impregnated with the polysulfide ion vulcanizing agent by an equal-volume impregnation method, and the temperature during the impregnation process was controlled at 90° C. for 2 hours to obtain a vulcanized catalyst.

[0045] S102: heat-treat the sulfided cataly...

Embodiment 2

[0047] The present invention provides a kind of preparation method of sulfurized gasoline hydrogenation upgrading catalyst, comprises the following steps:

[0048] S101: Measure a certain amount of potassium sulfide, ammonium sulfide, and ethanolamine, and mix them uniformly to obtain a polysulfide ion vulcanizing agent (that is, a modifier for gasoline hydrogenation catalyst); wherein, the sulfur content in the sulfide is the same as that of the gasoline hydrogenation catalyst The ratio of metals in MC1 is: the molar ratio of S / metal (Mo, Ni, Ce) = 3 / 1, the nitrogen content of passivating agent ethanolamine and the mole of metal (Mo, Ni, Ce) in gasoline hydrogenation catalyst Ratio=0.2 / 1, potassium sulfide is 1% by weight (in K 2 O weight basis content in the catalyst). Afterwards, the catalyst MC1 was impregnated with the polysulfide ion vulcanizing agent by an equal-volume impregnation method, and the temperature during the impregnation process was controlled at 90° C. for...

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Abstract

The invention relates to a method for preparing a gasoline hydrogenation modification catalyst, which uses a polysulfide ion sulfurizing agent containing an organic nitrogen compound as a passivating agent to treat the gasoline hydrogenation catalyst at low temperature, wherein the active component in the gasoline hydrogenation catalyst is the third One or more of Group VIB Mo, W or Group VIIIB Co, Ni, the stabilizer is one or more of Group IIB Zn, Cd or Group IA Na, K or rare earth metal La, Ce, This achieves stepwise complete sulfidation of metal oxides or their precursors and selective passivation of strongly acidic sites in the ZSM-5 molecular sieve composite carrier. The sulfurized gasoline hydrogenation modification catalyst prepared by the invention has the advantages of short start-up time, high hydrogenation olefin modification activity and selectivity, strong carbon deposition resistance, small octane number loss and high liquid yield, and It is especially suitable for low-cost hydrogenation and olefin reduction modification of inferior catalytic cracking gasoline to produce clean gasoline components.

Description

technical field [0001] The invention relates to the technical field of petrochemical industry, in particular to a preparation method of a sulfurized gasoline hydrogenation upgrading catalyst. Background technique [0002] At present, the smog is becoming more and more serious, and the environmental pollution caused by vehicle exhaust emissions has become a major problem that must be solved for the sustainable development of the national economy and society. For this reason, the standards for vehicle fuel in various countries in the world are becoming increasingly stringent. In recent years, my country's gasoline quality upgrade has progressed rapidly. On January 1, 2017, the national implementation of the sulfur content less than 10μg·g -1 National V standard. Recently, my country has introduced more stringent National VI standards, which are scheduled to be implemented on January 1, 2019. The National VI standard stipulates that the olefin content of gasoline will be redu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J37/20B01J29/48C10G45/12
CPCC10G45/12B01J29/48B01J37/20B01J2229/18C10G2400/02B01J35/633B01J35/615
Inventor 刘宾刘晨光柴永明黄汇江李奕川柳云骐殷长龙邢金仙
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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