Preparation And Adsorption Desulfurization Of Functionalized Cu-BTC

Thiophene-like sulfides in fuel oil emit sulfur oxide(SOx)during combustion,which is an significant hazard to the ecological environment and human health.Traditional hydrodesulfurization(HDS)requires more hydrogen to remove thiophene sulfides and does not guarantee the octane rating of fuel oil.Adsorption desulfurization(ADS)has received considerable attention from researchers because of its mild operating conditions,low production cost and no impact on octane rating.MOFs as desulfuizing adsorbents have the advantages of high specific surface area,good pore size and easy to adjust structure.There has been a lot of research on adsorption desulfurization.Therefore,Cu-BTC was selected as the basic material in this paper,and three kinds of adsorbents were prepared by functionalizing Cu-BTC and used for the removal of TP and BT from fuel oil.Firstly,bimetallic MOFs:Al/Cu-BTC was synthesized by ion doping of Cu-BTC with aluminum nitrate nine-water,and functional adsorbent Al/Cu(Ⅰ)-BTC was prepared by in-situ reduction of Al/Cu-BTC with sodium thiosulfate.The adsorption properties of Al/Cu(Ⅰ)-BTC for TP were investigated by static and dynamic adsorption.The adsorbents were characterized by Scanning Electron Microscopy(SEM),fourier Infrared Spectroscopy(FT-IR),Thermogravimetric Analyzer(TGA),X-ray Photoelectron Spectroscopy(XPS),Specific Surface Area Product Aperture Synthesis Analyzer,etc.The adsorbents showed higher stability and more Cu+ content.The adsorption results of TP showed that Al/Cu(Ⅰ)-BTC-0.28 had a better performance.In the competitive adsorption of thiophene and toluene,the adsorption capacites of static adsorption at 500 ppm and dynamic adsorption at 200 ppm are 18.54 mg S/g and 9.49 mg S/g,respectively.The thiophene adsorption capacity of Al/Cu(Ⅰ)BTC-0.28 can still reach 7.84 mg S/g.The adsorption capacity of the adsorbent was 15.79 mg S/g in TP fuel oil with sulfur content of 500 ppm after four regeneration experiments.Secondly,micromesoporous adsorbent CeO2@HP-Cu-BTC was directly synthesized by solvothermal salicylic acid hybrid Cu-BTC.The ability of adsorbent to remove small molecule thiophene and large molecule benzothiophene was investigated by static adsorption.The crystal structure,morphology and chemical composition of the adsorbent were characterized by XRD,SEM,TEM,EDS and BET.The adsorption results of TP and BT show that CeO2@HP-Cu-BTC-1.5 has a high adsorption capacity for TP and BT with adsorption capacities of 21.17 mg S/g and 35.28 mg S/g,respectively.In the competitive adsorption of benzothiophene and toluene,the adsorption capacity of CeO2@HP-Cu-BTC-1.5 for BT is 28.85 mg S/g.The adsorption of BT decreased by 12.37%after 5 cycles of regeneration using nitrogen purge method.Finally,Cu-BTC composite Ni0.5Zn0.5Fe2O4/AC/Cu-BTC doped with magnetic particles(Ni0.5Zn0.5Fe2O4)and activated carbon(AC)was prepared by a one-pot synthesis method.The effect of activated carbon(AC)doping amount on the adsorption of TP and BT was investigated by static adsorption of TP and BT.The chemical structure and properties of the adsorbents were characterized by SEM,XRD,FT-IR and VSM.The results showed that Ni0.5Zn0.5Fe2O4/AC/Cu-BTC-1.0 had a good adsorption performance on thiophene and benzothiophene,with the adsorption capacity of 14.35 mg S/g and 36.89 mg S/g,respectively.The prepared adsorbent still has good adsorption and desulfurization performance after soaking in water.