摘要
以Bi(NO_(3))_(3)·5H_(2)O、H_(2)WO_(4)和[(NH_(4))_(6)Mo_(7)O_(24)]·4H_(2)O为原料,氧化石墨烯(GO)为载体,通过水热-退火法制备了GO负载钨酸-钼酸铋的复合催化剂(WO_(3)-Bi_(2)MoO_(6)@GO)。采用XRD、FTIR、SEM和N_(2)等温吸附-脱附对催化剂进行了表征。将WO_(3)-Bi_(2)MoO_(6)@GO用于催化氧化模拟油(正癸烷)中的模型硫化物苯并噻吩(DBT),以脱硫率为指标,考察了反应温度、光源、催化剂用量、萃取剂(乙腈)用量、氧化剂(H_(2)O_(2))用量对WO_(3)-Bi_(2)MoO_(6)@GO的催化氧化脱硫性能的影响,并考察了催化剂的循环、回收催化稳定性,推测了WO_(3)-Bi_(2)MoO_(6)@GO的催化氧化脱硫机制。结果表明,在反应温度为40℃、15 A氙灯照射下、WO_(3)-Bi_(2)MoO_(6)@GO用量0.020 g、乙腈用量为5 mL、H_(2)O_(2)用量为0.12 mL、反应时间75 min时,硫质量浓度为200 mg/L的模拟油的脱硫率>99.0%;WO_(3)-Bi_(2)MoO_(6)@GO的光热协同催化氧化脱硫反应的机制是,氧化剂将从油相转移到乙腈相的DBT氧化为极性更大的砜类化合物,实现模拟油中硫化物的高效脱除;WO_(3)-Bi_(2)MoO_(6)@GO循环使用4次后,脱硫率在75和180 min均约47%,不再具有循环使用能力,一次回收的WO_(3)-Bi_(2)MoO_(6)@GO脱硫率在75 min时为74.1%,WO_(3)-Bi_(2)MoO_(6)@GO的表面因吸附砜类化合物而导致循环使用性能下降,回收过程中有少量活性组分流失。
Graphene oxide(GO)supported tungstate and bismuth molybdate composite catalyst(WO_(3)-Bi_(2)MoO_(6)@GO)was prepared by hydrothermal-annealing method using Bi(NO_(3))_(3)·5H_(2)O,H_(2)WO_(4)and[(NH_(4))_(6)Mo_(7)O_(24)]·4H_(2)O as raw materials,GO as substrate.The catalyst obtained was then characterized by XRD,FTIR,SEM and N_(2) isothermal adsorption and desorption,and used for the catalytic oxidation of model sulfide benzothiophene(DBT)in simulated oil(n-decane).The effects of reaction temperature,light source,catalyst amount,extraction agent(acetonitrile)and oxidant(H_(2)O_(2))on the catalytic oxidation desulfurization performance of WO_(3)-Bi_(2)MoO_(6)@GO were analyzed,with the recycling stability evaluated and catalytic mechanism deduced.The results showed that both the desulfurization rate of the model oil samples with mass concentration of 200 mg/L reached>99.0%under the reaction conditions of temperature 40℃,under irradiation of 15 A xenon lamp,catalyst dosage 0.020 g,acetonitrile dosage 5 mL,H_(2)O_(2)dosage 0.12 mL and reaction time 75 min.The mechanism for photothermal synergistic oxidative desulfurization reaction of WO_(3)-Bi_(2)MoO_(6)@GO was that DBT,which was continuously transferred by the oxide agent from the oil phase to the acetonitrile phase,was oxidized to more polar sulfone compounds,thus leading to the efficient removal of sulfide in the simulated oil.After WO_(3)-Bi_(2)MoO_(6)@GO was recycled for 4 times,the desulphurization rate was only about 47%both at 75 and 180 min respectively,indicating that it no longer had the recycling ability.The desulphurization rate of WO_(3)-Bi_(2)MoO_(6)@GO recovered after one cycle was 74.1%at 75 min.The decreased recycle performance of WO_(3)-Bi_(2)MoO_(6)@GO was attributed to the adsorption of sulfone compounds on the surface,and that a small amount of active components are lost in the recovery process.
作者
林程涛
林海
谭智毅
单书峰
曾兴业
LIN Chengtao;LIN Hai;TAN Zhiyi;SHAN Shufeng;ZENG Xingye(Guangdong Key Laboratory of Inferior Oil Processing,Guangdong University of Petrochemical Engineering,Maoming 525000,Guangdong,China;Zhanjiang Customs Technical Center,Zhanjiang 524022,Guangdong,China;Guangzhou Customs Technical Center,Guangzhou 510623,Guangdong,China)
出处
《精细化工》
北大核心
2025年第9期2029-2037,共9页
Fine Chemicals
基金
国家重点研发计划“国家质量基础设施体系”重点专项项目(2021YFF0602603)
广东省基础与应用基础研究基金项目(2024A1515013253)
茂名市科技计划项目(220421084550256)
茂名绿色化工研究院科技创新项目(MMGCIRI-2022YFJH-Y-035、MMGCIRI-2022YFJH-Y-052)
广东石油化工学院博士启动项目(2020bs002)。
关键词
钼酸铋
氧化脱硫
氧化石墨烯
钨酸
复合催化剂
bismuth molybdate
oxidative desulfurization
graphene oxide
tungstic acid
composite catalysts
