钨酸铋的制备及其催化氧化脱硫性能  

Preparation and Its Catalytic Oxidative Desulfurization Properties of Bismuth Tungstate

作　　者：陈婵 陈婧 林海 单书峰 曾兴业[1] CHEN Chan;CHEN Jing;LIN Hai;SHAN Shufeng;ZENG Xingye(Key Laboratory of Inferior Crude Oil Processing of Guangdong Provincial Higher Education Institutes,Maoming 525000,China;Zhanjiang Customs Technical Center,Zhanjiang 524022,China)

机构地区：[1]广东石油化工学院劣质油加工广东省高校重点实验室,广东茂名525000 [2]湛江海关技术中心,广东湛江524022

出　　处：《石油学报（石油加工）》2023年第2期407-415,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：广东省基础与应用基础研究基金项目(2020A1515110729,2021A1515010278);广东省普通高校特色创新项目(2018KTSCX149);青年创新人才项目(2018KQNCX158);广东石油化工学院博士启动项目(2020bs002)资助。

摘　　要：催化氧化脱硫法因反应条件温和、可高效深度脱除燃料油中二苯并噻吩(DBT)类硫化物,是一种有潜力的非加氢脱硫方法。以钨酸钠和五水合硝酸铋为原料,采用直接沉淀法和水热法制备钨酸铋(Bi_(2)WO_(6))。采用傅里叶变换红外光谱(FT-IR)、X-射线衍射(XRD)、电子扫描显微图像(SEM)、能量色散X射线光谱(EDS)和N2等温吸附-脱附等分析方法对其结构、组成、表面形貌和比表面积进行表征。分别以DBT、苯并噻吩(BT)、4-甲基-二苯并噻吩(4-MDBT)和4,6-二甲二苯并塞吩(4,6-DMDBT)为代表性硫化物,以正癸烷为溶剂、十四烷为内标物配制含硫模拟油,以制备的Bi_(2)WO_(6)为催化剂、过氧化氢(H_(2)O_(2))为氧化剂、乙腈(CH_(3)CN)为萃取剂构建催化氧化脱硫体系,系统地考察了其催化氧化脱硫性能。结果表明,水热法制备的Bi_(2)WO_(6)(BWO-2)表现出较优的脱硫性能。在反应温度为60℃下,其对含DBT的模拟油在75 min时脱硫率达到99.7%。动力学拟合结果表明,BWO-2对DBT模拟油的催化氧化脱硫反应符合一级动力学方程,其反应活化能为55.45 kJ/mol。Catalytic oxidative desulfurization method can deeply and efficiently remove dibenzothiophene(DBT)sulfur-containing compounds in fuel oil due to its mild reaction conditions.It is a non-hydrodesulfurization method with potential application value.The samples of bismuth tungstate(Bi_(2)WO_(6))were prepared using sodium tungstate and bismuth nitrate pentahydrate as raw materials by direct precipitation method and hydrothermal method.Their structure,composition,surface morphology and specific surface area were characterized by means of X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),and N2isotherm adsorption-desorption method.Taking DBT,benzothiophene(BT),4-methyldiphenylpropythipphere(4-MDBT),and 4,6-dimethyldiphenylpropythipphere(4,6-DMDBT)as representative sulfur compounds,the sulfur-containing simulated oil was made up by using n-decane as solvent and n-tetradecane as internal standard.A catalytic oxidation desulfurization system was constructed through the prepared Bi_(2)WO_(6)as catalyst,hydrogen peroxide(H_(2)O_(2))as oxidant and acetonitrile(CH_(3)CN)as extractant,and the desulfurization performance was systematically investigated.The results indicated that Bi_(2)WO_(6)(BWO-2)prepared by hydrothermal method has excellent desulfurization performance.The desulfurization rate of BWO-2 for simulated oil containing DBT reached 99.7%in 75 min at the reaction temperature of 60℃.The kinetic fitting results indicated that the catalytic oxidation desulfurization of DBT simulated oil by BWO-2 accords with the first-order kinetic equation,and its activation energy is 55.45 kJ/mol.

关 键 词：钨酸铋 水热法 催化氧化脱硫 过氧化氢 

分 类 号：TE65[石油与天然气工程—油气加工工程]