Adsorption Desulfurization Study Of MOFs Complex

With the increasingly stringent environmental regulations,fuel oil desulfurization has become an urgent problem in the world.The traditional desulfurization technology can effectively remove the sulfides which are easy to remove in the fuel oil.But it is difficult to remove the sulfides such as thiophene and its derivatives.The reaction conditions of traditional desulfurization technology are severe and the octane number of the oil is easy to be reduced,which affects the use of gasoline performance.Adsorption desulfurization technology is a means of deep desulfurization.Its operating conditions are mild.It has advantages of less investment in equipment,low energy consumption,easy to regenerate.Adsorption will not change the octane number of oil.So in the field of desulfurization,adsorption desulfurization is good alternative option.The metal organic frame?MOFs?is a new type of porous material with high specific surface area,high porosity and adjustable pore size.It has been widely studied in the field of adsorption desulfurization.In the third chapter,we synthesized HKUST-1 with Cu²⁺ as the metal center and trimesic acid as ligand.GO-s and GO-h were loaded on HKUST-1 and the effects on desulfurization of thiophene were investigated.The samples were characterized by X-ray diffraction,Raman spectroscopy and scanning electron microscopy.The removal efficiency of thiophene by HKGO-s and HKGO-h on the graphene loading of 1%?9%was investigated by static adsorption experiment.Samples are named as HKGO-h?1%?,HKGO-h?5%?,HKGO-s?9%?,HKGO-h?1%?,HKGO-h?5%?,HKGO-h?9%?.Experimental results showed that the adsorption performance for thiophene was the best when the loading was 5%.However desulfurization performance of HKGO-h?5%?was better than HKGO-s?5%?.HKUST-1 has a stronger force on thiophene than n-octane.So in model oil,HKUST-1 adsorbs thiophene obviously.When HKGO-h?5%?and HKGO-s?5%?adsorbs single thiophene,HKGO-h?5%?has stronger force on thiophene.The results show that the thiophene molecule is likely to be present in the pores of HKGO-h?5%?and the thiophene in HKGO-s?5%?is among the pores?away from the surface?.This is also the reason why thiophene adsorption performance of HKGO-h?5%?is better than HKGC-s?5%?.In the fourth chapter,MIL-53?Cr?was synthesized by using Cr³⁺ as the metal center and terephthalic acid?H2BDC?as ligand.MIL-53?Cr?@[Bmim][PF₆]was prepared by loading ionic liquid[Bmim][PF₆]with MIL-53?Cr?as support.The samples were characterized by Fourier transform rnfrared?IR?,wide angle X-ray diffraction?XRD?and N2 adsorption desorption instrument.The adsorption of thiophene sulfur on MIL53?Cr?adsorbents prepared by different treatment methods was investigated by static experiments.It was found that the MIL-5 3?Cr??ht van?treated at 300 ? through N2 has the best adsorption effect.MIL-53?Cr?,MIL-53?Cr?@[Bmim][PF₆]?10%?,MIL-53?Cr?@[Bmim][PF₆]?30%?and MIL-53?Cr?@[Bmim][PF₆]?40%?were measured by static and dynamic adsorption tests.The results showed that the adsorption of thiophene was improved compared with' pure MIL-53?Cr?.Adsorption performance follows as the order:MIL-53?Cr?@[Bmim][PF₆]?10%?>MIL53?Cr?@[Bmim][PF₆]?30%?>MIL53?Cr?@[Bmim][PF₆]?40%?>MIL53?Cr?.It concluded that the optimal loading of[Bmim][PF₆]is 10%.In the fifth chapter,Cu²⁺ as the metal and terephthalic acid?BTC?was used as organic ligand to synthesize[?CH3?NH2]3[?Cu4Cl?3-?BTC?8]9DMA?BTC = 1,3,5-trimesic acid,DMA=N,N-dimethylacetamide?,referred to as Cu-DMA.Cu-DMA@[Bmim][PF₆]was prepared by loading the ionic liquid[Bmim][PF₆]with Cu-DMA as support.The samples were characterized by Fourier transform infrared?IR?,wide angle X-ray diffractometer?XRD?and N2 adsorption instrument.Experiments on static adsorption and dynamic adsorption showed that the ability of composites for removal of thiophenic compound improved well after[Bmim][PF₆]was supported on Cu-DMA.