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Method for ultra-deep removal of sulfide in diesel oil by using oxygen as oxidizing agent

An oxidant and sulfide technology, applied in the field of ultra-deep oxidative desulfurization of diesel oil, can solve the problems of highly toxic hydrogen sulfide, increase investment cost, environmental pollution, etc., achieve strong catalytic activity and selectivity, reduce operating costs, and be environmentally friendly.

Inactive Publication Date: 2015-04-08
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] 1. The hydrogenation process requires high-temperature and high-pressure devices, which increases investment costs
[0005] 2. The hydrogenation process also requires the establishment of a hydrogen production device, which further increases the cost
[0006] 3. In the process of hydrogenation, highly toxic hydrogen sulfide is produced, causing environmental pollution
[0007] 4. The hydrogenation process can effectively remove mercaptan, sulfide, thiophene and its derivatives in diesel oil, but cannot effectively remove dibenzothiophene and its derivatives
However, the metal-organic compounds used in this method are dissolved in the oil, which causes problems such as difficulty in catalyst separation and increased oil loss, which increases the operating cost.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Catalyst preparation:

[0031] a. Weigh 4.5g of sodium metavanadate (37mmol) and dissolve it in 25ml of deionized water, stir at room temperature, add 6.2ml, 1.5mmol / l phosphoric acid, adjust the pH to 2-3 with 3mol / l nitric acid, add slowly Excess KCl solution to give K 8 H[PV 14 o 42 ].7H 2 O.

[0032] b. At 40°C, 0.928g (0.5mmol) K 8 H[PV 14 o 42 ].7H 2 O was dissolved in 15ml of pH=2.5 hydrogen chloride solution, another weighed 0.831g (4mmol) of octaalkyltrimethylammonium chloride was dissolved in 6ml of absolute ethanol, and was added dropwise to K under vigorous stirring. 8 H[PV 14 o 42 ] solution, under this temperature, continue to stir 1h, obtain pale yellow precipitate, centrifuge, dry 24h under vacuum condition, get catalyst [(C 8 h 17 )N + (CH 3 ) 3 ] 8 H[PV 14 o 42 ].

Embodiment 2

[0034] Except using 0.727g (3.5mmol) octaalkyl trimethylammonium chloride in step b, prepare with the same method as described in Example 1, get catalyst [(C 8 h 17 )N + (CH3 ) 3 ] 7 h 2 [PV 14 o 42 ].

Embodiment 3

[0036] Except using 0.623g (3mmol) octaalkyl trimethyl ammonium chloride in step b, prepare with the same method as described in Example 1, get catalyst [(C 8 h 17 )N + (CH 3 ) 3 ] 6 h 3 [PV 14 o 42 ].

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PUM

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Abstract

The invention relates to a new method for ultra-deep removal of sulfide in diesel oil by using oxygen as an oxidizing agent. The method comprises the following steps: under a mild operation condition, mixing model diesel oil containing dibenzothiophene or 4,6-dimethyl dibenzothiophene with a catalyst, stirring, introducing oxygen; after the sulfide in the model diesel oil is completely oxidized, stopping the reaction; cooling to room temperature, filtering the model diesel oil, extracting little sulfone in the model diesel oil, recovering the separated catalyst. According to the invention, in the reaction of oxidation removal of dibenzothiophene and its derivatives, extremely high oxidation activity and selectivity are exhibited without the addition of any sacrificial agent, and the content of the sulfide in the model diesel oil can be decreased from 500 ppm to below 10 ppm with the hydrocarbon composition being constant. Oxygen is used as the oxidizing agent, which can reduce cost; no other by-product is generated, which allows the reaction process to be more environment-friendly.

Description

technical field [0001] The invention relates to a method for ultra-deep oxidation desulfurization of diesel oil, more particularly to a method for ultra-deep removal of sulfide in diesel oil using oxygen as an oxidant. Background technique [0002] Sulfur oxides (SO X ) can not only cause acid rain and photochemical smog to endanger human health, but also cause irreversible poisoning of the three-way catalyst of the engine exhaust purification system. In recent years, with the enhancement of human awareness of environmental protection, countries around the world have increasingly stringent restrictions on the sulfur content in fuel oil. In 2005, Europe and other developed countries stipulated that the sulfur content in gasoline should not exceed 30ppm, and the sulfur content in diesel should not exceed 50ppm. By 2010, the sulfur content should be reduced to below 10ppm. On July 1, 2010, my country implemented a fuel sulfur index equivalent to Euro IV (<50ppm) emission s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G53/14
Inventor 李灿蒋宗轩唐南方张永娜林峰
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI