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

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...

Examples

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.

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...

Examples

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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