Super stable oxidation desulfurization catalyst, and preparation method and application thereof

A technology of oxidative desulfurization and catalyst, applied in the direction of physical/chemical process catalyst, chemical instrument and method, organic compound/hydride/coordination complex catalyst, etc. Eliminate problems such as falling off, and achieve the effects of improving catalytic activity, easy recycling, and strong operability

Inactive Publication Date: 2017-03-29
FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although some studies have explored phosphotungstic acid supported in metal-organic frameworks for oxidative desulfurization, such as MIL-101(Cr), the diameter of phosphotungstic acid (~1.2nm) is small

Method used

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  • Super stable oxidation desulfurization catalyst, and preparation method and application thereof
  • Super stable oxidation desulfurization catalyst, and preparation method and application thereof
  • Super stable oxidation desulfurization catalyst, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] (1) Preparation of PTA@UiO-66

[0040] Hydrothermal method, using zirconium tetrachloride (699mg), terephthalic acid (498mg), phosphotungstic acid (1.44g) and DMF (60mL) as raw materials, ultrasonically treated for 20min to obtain a uniformly mixed solution, and heated at 120°C Insulated in an oven for 24 hours, the obtained solid was washed three times with water and ethanol, and dried overnight at 70°C in an oven to obtain 10% PTA@UiO-66. Among them, 10% is the percentage of phosphotungstic acid in the total mass of the catalyst.

[0041] (2) Preparation of blank material UiO-66

[0042] Hydrothermal method, using zirconium tetrachloride (699mg), terephthalic acid (498mg) and DMF (60mL) as raw materials, ultrasonically treated for 20min to obtain a mixed solution, and kept in an oven at 120°C for 24h, the obtained solid After washing with water and ethanol three times each, and drying in an oven at 70°C overnight, UiO-66 was obtained.

[0043] The morphology of PTA...

Embodiment 2

[0045] Performance evaluation of extraction catalytic oxidation desulfurization of PTA@UiO-66 catalyst:

[0046](1) The effect of the molar ratio of hydrogen peroxide to organic sulfur (O / S) on the catalytic activity. Dibenzothiophene was selected as the probe molecule to study the oxidative desulfurization performance of the catalyst. Take 2 mL of a dibenzothiophene / n-heptane mixed solution with a sulfur content of 1000 mass ppm and place it in a reaction tube, then add 2 mL of acetonitrile, and then add 46 mg of catalyst PTA@UiO-66. Add 0, 20, 30, 40, 50, 60 μL of hydrogen peroxide, that is, the O / S ratio is 0, 4, 6, 8, 10, 12, put it in an air bath reaction mold at 70°C and start heating, and after 0.5 hours, the transformation The rates were 0%, 63%, 82%, 93%, 95%, and 99%.

[0047] (2) Effect of reaction time on catalytic activity. Keeping the reaction conditions of step (1) unchanged, change the reaction time, under the condition of O / S ratio of 0, 4, 6, 8, 10, 12, af...

Embodiment 3

[0051] Evaluation of extraction catalytic oxidation desulfurization performance of UiO-66 catalyst:

[0052] (1) The effect of the molar ratio of hydrogen peroxide to organic sulfur (O / S) on the catalytic activity. Dibenzothiophene was selected as the probe molecule to study the oxidative desulfurization performance of the catalyst. Take 2 mL of a dibenzothiophene / n-heptane mixed solution with a sulfur content of 1000 mass ppm and place it in a reaction tube, then add 2 mL of acetonitrile, and then add 46 mg of catalyst UiO-66. Add 0, 20, 30, 40, 50, 60 μL of hydrogen peroxide, that is, the O / S ratio is 0, 4, 6, 8, 10, 12, put it in an air bath reaction mold at 70°C and start heating, and after 0.5 hours, the transformation Rates were 0%, 64%, 75%, 81%, 86%, and 88%.

[0053] (2) Effect of reaction time on catalytic activity. Keeping the reaction conditions of step (1) unchanged, change the reaction time, under the condition of O / S ratio of 0, 4, 6, 8, 10, 12, after 1 hour,...

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Abstract

The invention belongs to the technical field of environmental protection, and in particular, relates to preparation and application of a supported zirconium-based metal organic skeleton catalyst PTA@UiO-66 synthesized by an in-situ hydrothermal method. Because the molecular diameter of phosphotungstic acid (1.2 nm) is larger than a window diameter (0.6 nm) of zirconium-based metal organic skeleton cage holes, phosphotungstic acid is difficult to fall off and easy to recycle. The catalyst has good chemical and thermal stability and can be reused. The catalyst has large specific surface area, can well pre-adsorb reaction substrates and is beneficial for mass transfer effect of the reaction substrates and products. With the highly dispersed catalytic activity center phosphotungstic acid, under a condition without a phase transfer agent, dibenzothiophene in model oil is fully converted into dibenzothiophene sulfone, and dibenzothiophene in the model oil is completely removed. The catalyst is applied in gasoline with about 500 mass ppm, and has the removal rate on organic sulfur reaching 79%. The used raw materials are cheap, the synthesis process flow is simple, the operability is strong, and the catalyst has wide application prospects.

Description

technical field [0001] The invention belongs to the technical field of environmental protection, and in particular relates to the preparation and application of an ultra-stable loaded zirconium-based metal-organic framework oxidative desulfurization catalyst. Background technique [0002] With the development of the global economy, the consumption of gasoline is increasing. The combustion of organic sulfur in gasoline directly leads to an increase in sulfur dioxide emissions, which is harmful to public health. Traditional hydrodesulfurization mainly removes organic sulfur such as mercaptans and sulfides, but it is difficult to remove stubborn organic sulfur such as benzothiophene and dibenzothiophene. Recently developed oxidative desulfurization can be used as a beneficial supplement to hydrodesulfurization, which can have higher catalytic activity at normal pressure and lower temperature. [0003] The steps of oxidative desulfurization are: (1) use oxidant and catalyst to...

Claims

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Application Information

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IPC IPC(8): B01J31/34B01J31/22C10G21/00
CPCB01J31/1691B01J31/2213B01J31/34B01J2531/0241B01J2531/48C10G21/00C10G2300/202
Inventor 王旭生曹荣
Owner FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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