固载杂多酸的钒基超稳Y型分子筛制备及其氧化脱硫性能  

Preparation and oxidation desulfurization performance of V-HUSY zeolite supported heteropolyacids

作　　者：张津津 张旭斌[1] 王富民[1] 邴常浩 秦志强 ZHANG Jinjin;ZHANG Xubin;WANG Fumin;BING Changhao;QIN Zhiqiang(School of Chemical Engineering and Technology,Tianjin University,Tianjin 300350,China;Shandong Fuyu Petrochemical Co.,Ltd.,Dongying 257200,Shandong,China)

机构地区：[1]天津大学化工学院,天津300350 [2]山东富宇石化有限公司,山东东营257200

出　　处：《精细化工》2025年第2期362-369,401,共9页Fine Chemicals

基　　金：国家自然科学基金项目(22002052、21978198、22211540711)。

摘　　要：以氢型超稳Y型分子筛(HUSY)为载体、偏钒酸铵和磷钨酸水合物(HPW)为原料,采用脱铝补位法制备了固载杂多酸的钒基超稳Y型分子筛(V-HUSY/HPW)。通过XRD、FTIR、UV-Vis、TEM、SEM、N_(2)吸附-脱附及ICP-OES对其进行了表征。将V-HUSY/HPW用于二苯并噻吩(DBT)模拟油氧化脱硫反应,考察了V和HPW添加量对脱硫率的影响,测试了催化剂的循环稳定性,推测了氧化脱硫反应的机理。结果表明,V物种引入到HUSY骨架内部,HPW通过浸渍法负载在HUSY表面;V和HPW添加量分别为0.1 mmol和0.5%(以V-HUSY质量计,下同)时制备的V-HUSY0.1/HPW0.5具有最佳氧化脱硫性能。在V-HUSY0.1/HPW0.5用量为0.10 g、DBT模拟油(DBT质量浓度360 mg/L)20 mL、氧化剂叔丁基过氧化氢15.8μL、60℃、20 min的条件下,模拟油脱硫率为99.5%。催化剂经6次循环使用后,DBT模拟油的脱硫率仍可达98.3%;在氧化脱硫过程中,羟基自由基是最主要的活性物种,可将DBT转化成极性更强的砜类物质保留在催化剂孔结构中,无需萃取即可实现一步深度脱硫。Using H-type ultra-stable Y zeolite(HUSY)as support,and ammonium metavanadate as well as phosphotungstic acid hydrate(HPW)as raw materials,vanadium-based ultra-stable Y zeolite loaded with heteropolyacid(V-HUSY/HPW)was prepared by dealuminized complement method,and characterized by XRD,FTIR,UV-Vis,TEM,SEM,N_(2)adsorption-desorption and ICP-OES.The effects of V and HPW amount in V-HUSY/HPW on the desulfurization rate of dibenzothiophene(DBT)model oil were analyzed,while the cycling stability of the catalysts was evaluated and the oxidative desulfurization mechanism was speculated.The results showed that V species were introduced into the HUSY skeleton,while HPW was loaded on the surface of HUSY by the impregnation method.V-HUSY0.1/HPW0.5 prepared from 0.1 mmol V and 0.5%HPW(based on the mass of V-HUSY,the same below)showed the best oxidation desulfurization performance.The desulfurization rate of the model oil was 99.5%under the conditions of V-HUSY0.1/HPW0.50.10 g,DBT model oil(DBT mass concentration 360 mg/L)20 mL,oxidant tert-butyl hydroperoxide 15.8μL,60℃and 20 min.After 6 cycles,the desulfurization rate of DBT model oil was still up to 98.3%.During the oxidative desulfurization process,the hydroxyl radical was considered the main active species,which converted DBT into more polar sulfone and then retained in the pore structure of the catalyst,so that a one-step in-depth desulfurization could be achieved without the need of extraction.

关 键 词：杂原子分子筛 磷钨杂多酸 超稳Y型分子筛 氧化脱硫 二苯并噻吩 催化技术 

分 类 号：TQ426[化学工程]