Method for eliminating sulfur compound contained in fuel oil by catalytic oxidation of phase transition

A technology of phase transfer catalysis and phase transfer catalyst, which can be used in the purification of oxygen-containing compounds, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc. The catalyst is difficult to reuse and recover, and the reaction rate is slow, which is beneficial to industrial application, eliminating the need for adsorption and extraction processes, and short reaction time.

Inactive Publication Date: 2007-10-10
HEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The purpose of the present invention is to solve the problems of low contact probability between oxidizing agent and sulfur-containing compound, slow reaction rate, poor desulfurization effect and difficulty in reusing and recycling catalysts existing in the current selective oxidation method for removing sulfur-containing compounds in fuel oil, and to provide a A method for removing sulfur compounds in fuel oil by phase transfer catalytic oxidation, so as to realize the clean production of oil products

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] The sulfur content of FCC gasoline is 690 μg / g, and the distillation range is 60-200°C.

[0014] Under ultrasonic conditions, 12mL of catalytic cracking gasoline and 36mL of peroxyformic acid prepared by hydrogen peroxide and formic acid in a mass ratio of 3.3:1 were added to the reactor, and 0.10g of heteropolyacid quaternary ammonium salt phase transfer catalyst M-1 was added simultaneously. The reaction temperature was controlled at 40°C. FCC gasoline and peroxyformic acid were separated after 1.5 hours of reaction to obtain 11.76 mL of FCC diesel oil with a sulfur content of 94.8 μg / g and a desulfurization rate of 88%.

Embodiment 2

[0016] The sulfur content of FCC gasoline is 690 μg / g, and the distillation range is 60-200°C.

[0017] Under ultrasonic conditions, 24mL of catalytic cracking gasoline and 24mL of peroxyformic acid formulated by hydrogen peroxide and formic acid in a mass ratio of 3.3: 1.5 were added to the reactor, and 0.10g of heteropolyacid quaternary ammonium salt phase transfer catalyst M-2 was added simultaneously. The reaction temperature was controlled at 30°C. After 1.5 hours of reaction, FCC gasoline and peroxyformic acid were separated to obtain 23.04 mL of FCC diesel with a sulfur content of 7.9 μg / g, and the desulfurization rate was 99%.

Embodiment 3

[0019] The sulfur content of FCC gasoline is 690 μg / g, and the distillation range is 60-200°C.

[0020] Under ultrasonic conditions, 36mL of catalytic cracking gasoline and 12mL of peroxyformic acid prepared by hydrogen peroxide and formic acid in a mass ratio of 3.3:1 were added to the reactor, and 0.10g of heteropolyacid quaternary ammonium salt phase transfer catalyst M-3 was added simultaneously. The reaction temperature is 50°C. After 1.5 hours of reaction, the catalytic cracked gasoline and peroxyformic acid are separated to obtain 32.76 mL of catalytic cracked diesel oil with a sulfur content of 55.2 μg / g, and the desulfurization rate is 92%. The used heteropolyacid quaternary ammonium salt phase After the transfer catalyst was regenerated, it was applied to the fuel oil desulfurization process again to obtain 32.4 mL of FCC diesel with a sulfur content of 69 μg / g, and the desulfurization rate was 90%.

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Abstract

This invention discloses a method for removing sulfur-containing compounds from fuel oil by phase-transfer catalytic oxidation. The method comprises: preparing six types of heteropolyacid quaternary ammonium salts as the phase-transfer catalysts from quaternary ammonium salts and phosphomolybdic acid/tungstophosphoric acid, mixing the phase-transfer catalysts, fuel oil, and peroxyformic acid oxidant (prepared from H2O2 and formic acid at a weight ratio of 3.5:(1-1.5)), reacting at 25-55 deg.C under ultrasonication for 1-2 h, and separating fuel oil and peroxyformic acid to obtain desulfurized fuel oil. The method avoids adsorption and extraction procedures due to the heteropolyacid quaternary ammonium salts phase-transfer catalysts, and has such advantages as simple process, and high reaction rate. The catalyst has such advantages as no toxicity and no pollution, and is recyclable and environmentally friendly.

Description

technical field [0001] The invention relates to a method for removing sulfur compounds in fuel oil by phase transfer catalytic oxidation, and belongs to the technical field of oil product refining in the petrochemical industry. Background technique [0002] The rapid development of the petroleum industry and the automobile industry has made great contributions to social progress, but the highly corrosive SO 2 The discharge of acid rain is the direct cause of environmental pollution caused by acid rain, and it also causes CO, NO x etc. increase. Producing clean, low-sulfur fuel oil has become a top priority for the refining industry. The sulfur content in catalytic cracking oil products in my country accounts for 80-95% of the total sulfur content in gasoline. Therefore, it is of great significance to carry out research on FCC oil desulfurization technology. At present, domestic and foreign fuel oil desulfurization methods can be divided into two categories: hydrodesulfur...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G27/12B01J31/04
Inventor 任红威赵地顺刘冉
Owner HEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY
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