MOF-199固载过氧化磷钨酸盐催化剂的制备及其在柴油脱硫中的应用  

Preparation of MOF-199 Supported Peroxophosphotungstate Catalyst and Its Application in Diesel Desulfurization

作　　者：高燕[1] 闫苗[1] 赵建社[2] GAO Yan;YAN Miao;ZHAO Jianshe(Department of Chemistry,Xinzhou Normal University,Xinzhou 034000,China;College of Chemistry&Materials Science,Northwest University,Xi′an 710127,China)

机构地区：[1]忻州师范学院化学系,山西忻州034000 [2]西北大学化学与材料科学学院,陕西西安710127

出　　处：《石油学报（石油加工）》2023年第2期349-357,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：山西省基础研究计划资助项目(202103021223359);山西省高等学校科技创新项目(2021L453);忻州师范学院院级项目(2021KY06)基金资助。

摘　　要：采用简易的原位合成法合成了过氧化磷钨酸盐(TBA)_(3)PW_(4)封装于MOF-199孔道内的固载型催化剂(TBA)_(3)PW_(4)@MOF-199,借助电感耦合等离子体(ICP)、傅里叶红外光谱(FT-IR)、X-射线衍射(XRD)、热重分析(TG)、场发射扫描电子显微镜(SEM)及N2吸附-脱附等温曲线(BET)等分析手段对催化剂样品(TBA)_(3)PW_(4)@MOF-199的组成、稳定性及形貌进行了表征。采用含苯并噻吩(BT)、二苯并噻吩(DBT)、4-甲基二苯并噻吩(4-MDBT)和4,6-二甲基二苯并噻吩(4,6-DMDBT)4种硫源的多组分模拟柴油与萃取剂组成的液-液双相系统,以双氧水为氧化剂,对催化剂的脱硫活性进行了探究,并探讨了催化剂用量、氧化剂用量及反应温度对脱硫效率的影响。结果表明:在最佳反应条件(反应温度70℃、催化剂(TBA)_(3)PW_(4)@MOF-199用量40 mg、H_(2)O_(2)用量0.26 mmol、模拟柴油体积0.75 mL及萃取剂[Bmim]PF_(6)体积0.75 mL)下,催化剂(TBA)_(3)PW_(4)@MOF-199的脱硫效率可以在80 min内达到99.9%,同时重复使用8次,脱硫效率仍保持在91%以上。该催化剂优异的催化脱硫活性及稳定性使其在工业应用上具有一定的前景。The supported catalyst(TBA)_(3)PW_(4)@MOF-199 was synthesized using a simple in-situ synthesis method through encapsulating peroxophosphotungstate(TBA)_(3)PW_(4)in the pore of MOF-199.The composition,stability and morphology of the catalyst sample(TBA)_(3)PW_(4)@MOF-199 were characterized by inductively coupled plasma(ICP),Fourier Transform Infrared Spectroscopy(FT-IR),X-ray diffraction(XRD),thermogravimetric analysis(TG),scanning electron microscope(SEM)and N2adsorption-desorption isotherm(BET).Then,a liquid-liquid two-phase system consisting of a multi-component simulated diesel and an extractant was used to explore the desulfurization activity of the catalyst with hydrogen peroxide as oxidant,and the aforesaid simulated diesel contains four sulfur sources including benzothiophene(BT),dibenzothiophene(DBT),4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Moreover,the effects of catalyst amount,oxidant amount and reaction temperature on desulfurization efficiency were also discussed.The results show that the desulfurization efficiency of catalyst(TBA)_(3)PW_(4)@MOF-199 can reach 99.9%within 80 min under the optimal reaction conditions(reaction temperature 70℃;catalyst dosage 40 mg;H_(2)O_(2)dosage 0.26 mmol;model diesel volume 0.75 mL;[Bmim]PF_(6)volume 0.75 mL),and the desulfurization efficiency remains above 91%after repeated use for 8 times.The excellent desulfurization activity and stability of the catalyst endow it with a great prospect in industrial application.

关 键 词：过氧化磷钨酸 金属有机框架 催化氧化 柴油脱硫 

分 类 号：TB333[一般工业技术—材料科学与工程]