Study On Preparation And Deep Desulfurization Performance Of Porous Adsorbent Material Based On Cu(Ⅰ)

Nowadays,fossil fuels are still the most widely used energy materials.However,the widespread use of fossil fuels has also caused serious environmental pollution because the fuel oil contains a large number of sulfides,such as thiophene,mercaptan,and thioether,etc.Therefore,obtaining ultra-low sulfur or sulfur-free fuel oil has become the focus of research today.Hydrodesulfurization is one of the earliest and most widely used clean technologies for fuel oil.However,with the increasingly strict requirements on the sulfur content of fuel oil by environmental laws and regulations,Hydrodesulfurization cannot achieve the purpose of deep desulfurization.Adsorption desulfurization technology has attracted wide attention because of its low cost,relatively mild operating conditions,and high desulfurization efficiency.It also has a good removal effect on refractory sulfur compounds such as thiophene and benzothiophene.However,most adsorbents have a low adsorption capacity for sulfide,so the material adsorption ability becomes the key to the application of adsorption desulfurization.π-complexation adsorption is one of the better adsorption methods currently.The π-complexation adsorbent is prepared by introducing transition metal ions such as Cu+or Ag+into the porous material to improve the adsorption performance.At the same time,since most of the adsorbent materials are mostly microporous,the adsorption capacity of the adsorbent for sulfide is limited.Therefore,this article mainly modified the microporous zeolite molecular sieve and the metal organic framework UiO-66,and introduced Cu(Ⅰ)to synthesize a π-complexation adsorbent with a hierarchical pore structure,and explored the adsorption performance of the two adsorbents on thiophene sulfides.In order to improve the adsorption capacity and adsorption selectivity of the adsorbent to sulfide,the metal-organic framework material UiO-66 with high hydrothermal stability and acid and alkali resistance successfully synthesized in this part,and copper was covalently adsorbed on the defect site of the zirconia compound of UiO-66 by solvothermal method.Powder X-ray diffraction(PXRD),infrared analysis(FT-IR),field emission scanning electron microscopy(SEM),and other Characterization methods showed that the π-complexation adsorbent UiO-66-Cu with monoatomic Cu was successfully prepared.The adsorption capacity of sulfide by the adsorbent was tested by static adsorption in the thiophene simulated oil.The test results showed that the adsorption capacity of sulfide by the modified UiO-66 was much higher than that of the original.When the sulfur content is 450 ppm,the adsorbent has a maximum adsorption capacity of 15 mgS/g,and it has shown good performance in both competitive adsorption and adsorbent cycle performance tests.In material synthesis,the metal-organic framework material HP-UiO-66 with defect structure is synthesized by introducing unstable templates and then removing and introducing Cu into the zirconium’s defect sites oxide clusters of the material.The monoatomic dispersedπ-complexed adsorbent HP-UiO-66-Cu with hierarchical pore structure was synthesized.The static adsorption capacity of the adsorbent was tested in simulated oil containing thiophene and benzothiophene.The results show that in the thiophene simulated oil when the template introduction ratio is 4,the adsorbent has the best adsorption performance.The maximum adsorption capacity is 18 mgS/g for thiophene;in the benzothiophene simulated oil,the adsorption capacity of sulfide up to 34 mgS/g.It can be seen from the results of the cyclic regeneration test of the adsorbent that the modified adsorbent has good regeneration performance,and the adsorption capacity of the adsorbent remains 92%of that of the fresh adsorbent after four regeneration experiments.The pore reaming of FAU zeolite was carried out by acid-base post-treatment method,and then Cu2+is introduced into the material through ion exchange,and it is automatically reduced in a methanol vapor environment.The adsorbent was characterized by powder X-ray diffraction(PXRD),transmission electron microscopy(TEM)and the specific surface area analyzer(BET).The results show that a molecular sieve with a hierarchical pore structure was successfully synthesized,and copper ions were successfully introduced through ion exchange.The static adsorption capacity of the adsorbent was tested in simulated oil containing thiophene and benzothiophene.The results showed that in the simulated oil containing thiophene,HP-CuY has the highest adsorption capacity for thiophene,which is 40 mgS/g;and in the simulated oil containing benzothiophene,HP-CuX has the highest adsorption capacity for benzothiophene,which is 56 mgS/g.Compared with the microporous FAU-type zeolite,the test results have significantly improved adsorption desulfurization performance,and it can be seen from the recycling regeneration test results of the adsorbent that the modified adsorbent has better regeneration performance.