Ultradeep Oxidative Desulfurization Of Model Oil With V-substituted Keggin Typed Polyoxomolybdates Modified Graphene Catalyst

In this paper,V-substituted Keggin typed Polyoxomolybdates(H₅PV₂Mo₁₀O₄₀abbreviation: POVM)modified graphene hybrid materials were prepared by two methods.The catalytic activity of the material in the desulfurization was systematically studied.The main contents and innovative research are as follows:1.Reduction of graphene oxide with ethylenediamine to obtain amine-functionalized graphene hybrids which are immersed in polyoxometalates aqueous solution to prepare POVM-rGO-1.During the process of materials synthesis,as the amount of ethylene diamine and polyoxometalates can be controlled,it is conducive to achieve the highest catalytic effect by controlling the quantity of amine on the surface of the material and the amount of polyoxometalates.It was found that 50 mg GO was dispersed in 10 mL water and 0.1mL ethylenediamine was added.Then,rGO was immersed in 20 mg / mL,10 mL polyoxometalates aqueous solution to obtain the best material?POVM-rGO-1a?.The catalyst can be dispersed in the oil phase,but it will agglomerate after adding hydrogen peroxide.This may have two reasons,on the one hand,the hydrogen bonds are formed between the amine groups on the surface of the catalyst and hydrogen peroxide;on the other hand,the POMs are hydrophilic and hydrogen peroxide solution contains plenty of water.These two reasons cause the catalyst more easily dispeared in the hydrogen peroxide phase.Therefore,acetonitrile is added as an extractant in the system.Acetonitrile can extract a portion of the sulfide from the oil phase,while the oxidant and catalyst are also in the acetonitrile phase forming an extraction-catalytic oxidation desulfurization system.When the sulfide in acetonitrile was oxidized to the corresponding sulfone,a portion of the sulfide is extracted again with the agitation process until completely desulfurization is achieved.Under optimal conditions?10mL 500 ppm model oil,5mL acetonitrile,0.05 g POVM-rGO-1a,0.5mL 30% hydrogen peroxide?,DBT could be completely removed under 60? and 30 min.The catalyst can be separated by centrifugation and maintain high catalytic activity after recycling for five times.2.Using the method of photoreduction,the POVM-rGO-2 was obtained by oxidizing the graphene oxide with the ethylene glycol reduced POVM.Aerobic oxidative desulfurization?10ml 500 ppm model oil?could be catalyzed by POVM-rGO-2?0.1g?under80? and 5h by using isobutyraldehyde as sacrificial reagent.