Method for desulfurization of fuel oil by oxidation process with modified titanium silicalite molecular sieve as catalyst

A titanium-silicon molecular sieve and catalyst technology, which is applied in the petroleum industry, refining hydrocarbon oil, etc., to achieve the effect of improving reusability, mild reaction conditions, and simple equipment

Inactive Publication Date: 2006-10-11
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] So far, there have been no reports on the use of silanized modified titanium-silicon molecular sieves for catalytic oxidation to remove the macromolecular sulfide 4,6-dimethyldibenzothiophene (DMDBT) in diesel oil and to improve the catalyst’s reusable performance

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] This example illustrates the preparation method of a silanization-modified titanium-silicon molecular sieve provided by the present invention. Titanium-silicon molecular sieve Ti-HMS is prepared by using dodecylamine as a template and ethyl orthosilicate as a silicon source according to the literature [Chin J Catal, 2004, 25(2):89]. Modified titanium silicate molecular sieves were prepared by impregnation method using tetraethyl orthosilicate as silylating agent. Stir 1g of titanium-silicon molecular sieve Ti-HMS and 8mL of 4.33g / L ethyl orthosilicate cyclohexane solution evenly, and the loading of orthosilicate on the titanium-silicon molecular sieve is 3.47wt%, then impregnate at room temperature for 10h, and let it dry After drying, the temperature was programmed to dry at 363K for 6h, and then roasted at 810K for 5h to obtain SiO 2 1.0wt% SiO loading 2 / Ti-HMS catalyst.

Embodiment 2

[0022] This example illustrates the preparation method of a silanization-modified titanium-silicon molecular sieve provided by the present invention. Titanium-silicon molecular sieve Ti-HMS is prepared by using dodecylamine as a template and ethyl orthosilicate as a silicon source according to the literature [Chin J Catal, 2004, 25(2):89]. Modified titanium silicate molecular sieves were prepared by impregnation method using tetraethyl orthosilicate as silylating agent. Stir 1g of titanium-silicon molecular sieve Ti-HMS and 8mL 5.63g / L cyclohexane solution of ethyl orthosilicate evenly, the loading of orthosilicate on the titanium-silicon molecular sieve is 4.51wt%, then impregnate at room temperature for 10h, and let it dry After drying, the temperature was programmed to dry at 363K for 6h, and then roasted at 810K for 5h to obtain SiO 2 SiO with a loading of 1.3 wt% 2 / Ti-HMS catalyst.

Embodiment 3

[0024] This example illustrates the preparation method of a silanization-modified titanium-silicon molecular sieve provided by the present invention. Titanium-silicon molecular sieve Ti-HMS is prepared by using dodecylamine as a template and ethyl orthosilicate as a silicon source according to the literature [Chin J Catal, 2004, 25(2):89]. Modified titanium silicate molecular sieves were prepared by impregnation method using tetraethyl orthosilicate as silylating agent. Stir 1g of titanium-silicon molecular sieve Ti-HMS and 8mL 8.66g / L cyclohexane solution of ethyl orthosilicate evenly, the loading of orthosilicate on the titanium-silicon molecular sieve is 6.94wt%, then impregnate at room temperature for 10h, and let it dry After drying, the temperature was programmed to dry at 363K for 6h, and then roasted at 810K for 5h to obtain SiO 2 2.0wt% SiO loading 2 / Ti-HMS catalyst.

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Abstract

An oxidation sweetening method for fuel oil selecting modified titanium-silicon molecular screen as accelerating agent belongs to technical sphere of petroleum process. The invention provides an accelerating agent of modified titanium-silicon molecular screen which can be used in oxidation sweetening of fuel oil. The charge number of earth silicon in this invention adopting immersion method is 1.0wt%-3.0wt%. The obtained modified titanium-silicon molecular screen is used for catalytic and oxidation desulfurization of fuel oil. The significance effect of this invention is that it improves the repetitive use of accelerating agent in oxidation sweetening reaction. The method includes selecting modified titanium-silicon molecular screen as accelerating agent and removing sulfidization of fuel oil by hydrocarbonylation, which can reduce the sulfur content of fuel oil to 29.7 mu/g from 226.1 mu/g and reach deep desulfuration, and the accelerating agent can be recovered and the catalytic oxidation susceptibility of the recovered accelerating agent is good. The invention is of mild reaction condition, simple equipment and no consumption of hydrogen gas.

Description

technical field [0001] The invention belongs to the technical field of petroleum processing. The invention relates to a method for desulfurization by a fuel oil oxidation method using a silanized modified titanium-silicon molecular sieve catalyst. Background technique [0002] Combustion of sulfur compounds in liquid fuels can cause environmental pollution. In the clean fuel standards formulated by countries around the world, the restrictions on sulfur content are becoming more and more stringent. It is very difficult to remove macromolecular sulfides by traditional hydrodesulfurization methods. The catalytic oxidation method is effective in removing organic sulfides from liquid fuels, especially macromolecular sulfides. It is a new technology with low investment and mild reaction conditions. It can also be used as a subsequent deep desulfurization process for hydrodesulfurization. Catalysts used in catalytic oxidation desulfurization include liquid acids, heteropolyacids...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G27/00
Inventor 李钢王云王祥生金长子
Owner DALIAN UNIV OF TECH
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