Method for removing sulfur-containing compound from carbon fuel by catalytic oxidation

A technology for catalytic oxidation and hydrocarbon fuel, applied in the petrochemical field, can solve the problems of high price of oxidant, difficult extraction and separation, high cost, and achieve the effect of continuous operation, obvious desulfurization effect and overcoming high cost.

Inactive Publication Date: 2007-08-01
EAST CHINA NORMAL UNIV
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Problems solved by technology

Although its oxidation effect is better and the desulfurization rate is higher, the H 2 o 2 Oxidants such as oxidants are expensive and used in large amounts, subsequent extraction and separation are more difficult, and the amount of extractant used is large and the cost is high
In fact, the oxidation of olefins (one of the main components of gasoline) present in large quantities in real fuel oils [Catalysis Today, 117(2006) 199-205] can lead to H 2 o 2 The rapid consumption of oxidants may make it difficult to oxidize trace amounts of sulfur compounds; in addition, the existence of trace amounts of impurities such as nitrogen-containing organic compounds in real fuel may also lead to poisoning of the catalyst system

Method used

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  • Method for removing sulfur-containing compound from carbon fuel by catalytic oxidation

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Experimental program
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Effect test

Embodiment 1-3

[0021] With 1.5wt%Pd / CeO 2 As a catalyst [synthesis details: Applied Catalysis B, 53 (2004) 77-85], isooctane containing 1000 μg / g sulfur (benzothiophene is the sulfur source) The hourly space velocity is 3.21, 15.29 and 17.41h respectively -1 Under the condition, the O 2 / S ratio, the results are shown in Figure 1. From the results in Figure 1, it can be seen that the best O on the catalyst to achieve the maximum desulfurization rate 2 / S ratio is about 30; at 3.21, 15.29 and 17.41h -1 Under the heavy hourly space velocity, the desulfurization rates are >99%, 98% and 95%, respectively. After identification by PFPD chromatography and mass spectrometer, the sulfur-containing gas in the reaction tail gas is SO 2 . o 2 The selectivity is above 30%.

[0022] 1.5wt%Pt / CeO 2 The same results as in Examples 1-3 were also obtained on the catalyst.

Embodiment 4-6

[0024] 1.5wt%Pt / CeO 2 As a catalyst [synthesis see: Journal of Catalysis, 229 (2005) 499-512], isooctane containing 1000 μg / g sulfur (benzothiophene as sulfur source) is used as raw material, under normal pressure, O 2 / S ratio 30, raw material oil heavy hourly space velocity 15.29h -1 Under the same conditions, the change of benzothiophene removal rate with time at 150, 200, 250, and 300°C was investigated, and the results are shown in Figure 2. It can be seen from the results in Figure 2 that the optimum reaction temperature on this catalyst is ~300 °C; at lower reaction temperatures, the catalyst will be deactivated rapidly.

Embodiment 7-8

[0026] 5wt%Cu / CeO 2 As a catalyst [synthesis details see: Applied Catalysis B, 28 (2000) 113-125], isooctane containing 1000 μg / g sulfur (benzothiophene as sulfur source) is used as raw material, under normal pressure, O 2 / S ratio 17, raw material oil heavy hourly space velocity 40h -1 Under the conditions, the removal rate of sulfur reaches >99% at 300°C, O 2 The selectivity of sulfur is 61.7%; the removal rate of sulfur reaches 97% at 280 ° C, O 2 The selectivity was 59.9%. At normal pressure, O 2 / S ratio 17, raw material oil weight hourly space velocity 80h -1 Under these conditions, the removal rate of sulfur reaches ~70% at 300°C.

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Abstract

The invention relates to a catalytic oxidation method for removing sulfur-containing compound from hydrocarbon fuel, belonging to petroleum chemical industry field. The method takes air as oxidant, continuously oxidates the sulfur compound in hydrocarbon fuel in catalytic reactor at 150- 350 Deg. C and normal pressure into sulfoxide Sox, and the percentage of desulfurization reaches above 90%. The invention is characterized in that the post treatment for extraction of desulfurized hydrocarbon fuel is not complicated, and the process can be carried out continuously, it takes air as oxidant, which reduces cost, and it overcomes problems of high cost of hydrodesulphurization, loe efficiency of adsorption desulphurization, wastewater treatment and separation.

Description

technical field [0001] The invention relates to a method for catalytically oxidizing and removing sulfur-containing compounds in hydrocarbon fuels, belonging to the field of petrochemical industry. technical background [0002] The increasingly stringent environmental protection requirements have made the world's oil refining industry face the severe challenge of producing clean hydrocarbon fuels with low sulfur content. According to the plan of the US Environmental Protection Agency, the sulfur content of gasoline is required to be less than 30 μg / g in 2006, and the sulfur content of diesel is less than 15 μg / g; the European Union and Japan plan to impose stricter restrictions on sulfur content. In response to new environmental protection requirements, the world's major oil companies and scientific researchers are devoting themselves to the research and development of new technologies for the removal of sulfides in economical and efficient hydrocarbon fuels. Among them, ne...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G27/04
Inventor 路勇王亚高立达毛继平薛青松刘晔何鸣元
Owner EAST CHINA NORMAL UNIV
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