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Organosulfur oxidation process

A sulfide and organic technology, applied in the field of organic sulfide oxidation, can solve problems such as difficult to remove and harsh reaction conditions

Inactive Publication Date: 2007-09-26
LYONDELL CHEM TECH LP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

While hydrodesulfurization readily converts mercaptans, thioethers, and disulfides, other organosulfur compounds such as substituted and unsubstituted thiophenes, benzothiophenes, and dibenzothiophenes are difficult to remove and require harsher reaction conditions

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Example 1: Preparation of the catalyst of the present invention

[0042] Catalyst 1A: The silica carrier (Grace Davison DAVICAT P-732, particle size 0.6-1.4 mm, surface area 300 meters 2 / G) Dry in air at 400°C for 4 hours. The dried silica (47 grams) was placed in a 1 liter round bottom flask. Then, titanium (IV) containing diisopropoxide di(acetylacetonate) (15.1 g, 75% isopropanol solution) and isopropanol (89 g) were added to the silica and mixed thoroughly. The solvent was removed by rotary evaporation at 90°C. The impregnated material was fired in air at 800°C for 2 hours. The unsilylated catalyst 1A was measured to contain 3.2% (weight) Ti and <0.1% (weight) C.

[0043] Catalyst 1B: The silylated catalyst 1B was prepared using the steps of unsilylated catalyst 1A. The difference was that the silica was dried at 450°C and used titanium (IV) containing diisopropoxide (acetylacetonate) ) (16.3 g, 75% isopropanol solution) and isopropanol (82 g) solution impregnated with...

Embodiment 2

[0054] Example 2. Oxidation of thiophene with TBHP oxide

[0055] Catalysts 1A-F were tested in the oxidation of various organic sulfur compounds. The test results are listed in Table 1. The feed is prepared by mixing toluene or ethylbenzene with dibenzothiophene (DBT) and Lyondell TBHP oxide (containing approximately 43% by weight of TBHP and 56% by weight of tert-butanol). The feed contains 0.175% by weight of dibenzothiophene (DBT), 0.32% by weight of tert-butanol (TBA), and 0.24% by weight of tert-butyl hydroperoxide (TBHP). The molar ratio of DBT to TBHP is 2.8.

Embodiment 2A-F

[0056] Examples 2A-F: Toluene-containing feed (28 grams) was heated and stirred in a round bottom flask under a nitrogen atmosphere at 50°C. Then Ti / silica catalyst (0.2 g, powdered) was added and reacted at 50° C. in a nitrogen atmosphere for 0.5 hours. The reaction mixture was analyzed by GC and HPLC. As determined by GC and GC-MS, the oxidation products of thiophene were found to be the corresponding sulfoxides and sulfones.

[0057] Example 2G was carried out under the same steps as Examples 2A-F, except that 0.04 g of particulate catalyst 1D was used, and the reaction temperature was 80°C.

[0058] Example 2H was carried out under the same steps as Example 2G, except that 4,6-dimethyldibenzothiophene (DMDBT) was used instead of DBT. The molar ratio of DMDBT to TBHP is 2.4.

[0059] Examples 2I-J were carried out under the same steps as Examples 2A-F, except that a solution containing ethylbenzene was used, 0.02 g of particulate catalyst 1D was used, the reaction temperature w...

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Abstract

This invention is a method of oxidizing organosulfur impurites found in fuel streams. The method comprises reacting the organosulfur impurities with an organic hydroperoxide in the presence of a titanium-containing catalyst. The titanium-containing catalyst is obtained by impregnating a siliceous solid with a titanium halide in a hydrocarbon solvent, or a vapor stream of titanium tetrachloride, followed by calcination. The resulting sulfones are more readily removed from the fuel stream than the non-oxidized organosulfur impurities.

Description

Technical field [0001] The invention relates to a method for the oxidation of organic sulfide impurities contained in a fuel stream. The method includes reacting organic sulfide impurities with organic hydroperoxide in the presence of a titanium-containing catalyst. The titanium-containing catalyst is prepared by the following steps: impregnating the silicon-containing solid with titanium halide in a hydrocarbon solvent or with a vapor stream of titanium tetrachloride, and then roasting. The catalyst is particularly effective when the sulfur-containing impurities contained in the fuel are oxidized. Background technique [0002] The hydrocarbon fractions produced in the petroleum industry are usually contaminated with various sulfur-containing impurities. These hydrocarbon fractions include diesel fuel and gasoline, including natural gasoline, straight-run gasoline, and cracked gasoline. Other sulfur-containing hydrocarbon fractions include ordinary gas petroleum fractions, as wel...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G27/12C10G29/20
CPCC10G27/12
Inventor D·W·莱申L·J·卡拉斯韩元璋K·M·卡罗尔
Owner LYONDELL CHEM TECH LP