氨基酸功能化磷钨酸盐的制备及其催化氧化脱硫性能

以L-丙氨酸和磷钨酸为原料,合成氨基酸功能化磷钨杂多酸盐([Ala]3PW),并采用XRD、FT-IR对其结构进行表征。以[Ala]3PW为催化剂,过氧化氢作为氧化剂,甲基咪唑四氟硼酸盐([HMIM]BF4)为萃取剂氧化萃取一体法脱除模拟油中的二苯并噻吩(DBT)。考察了反应温度、催化剂加入量、O/S物质的量比、萃取剂加入量、硫化物类型等因素对脱硫效率的影响。结果表明,在模拟油为10mL、[Ala]3PW=0.04g、O和S的物质的量比为6、V([HMIM]BF4)/V(oil)=0.6、反应温度50℃、反应时间180min的条件下,DBT的转化率可达到98.2%。催化剂循环使用4次活性没有明显的降低。     

电拓扑状态预测多氯二苯并噻吩及噻吩砜化合物的气相色谱保留指数

以原子类型电拓扑状态指数(ETSI)有效表征了135 个多氯二苯并噻吩(PCDT)和135 个多氯二苯并噻吩砜(PCDTO₂)的分子结构, 应用基于预测的变量选择与模型化(VSMP)方法建立PCDT 和PCDTO₂ 化合物在DB-5 气相色谱柱上的气相色谱保留指数(RI)与分子结构(ETSI)的定量相关模型, 模型的相关系数r² 分别为0.9939 和0.9729, LOO 交叉验证相关系数 q² 分别为0.9921 和0.9692. 为验证模型稳定性和预测能力, 应用17 个PCDT 和PCDTO₂ 训练集样本构建的QSRR 模型的r² 分别为0.9959 和0.9783, LOO 交叉验证相关系数 q² 分别为0.9921 和0.9740, 说明模型具有良好的稳定性. 以此模型预测外部8 个检验集及110 个预测集的RI 值, 8 个检验集样本的结果表明训练集模型具有良好预测能力.     

Cavitation based cleaner technologies for biodiesel production and processing of hydrocarbon streams: A perspective on key fundamentals,missing process data and economic feasibility – A review

The present review emphasizes the role of hydrodynamic cavitation (HC) and acoustic cavitation in clean and green technologies for selected fuels (of hydrocarbon origins such as gasoline, naphtha, diesel, heavy oil, and crude oil) processing applications including biodiesel production. Herein, the role of cavitation reactors, their geometrical parameters, physicochemical properties of liquid media, liquid oxidants, catalyst loading, reactive oxygen species, and different types of emulsification and formation of radicals, formation as well as extraction of formed by-products are systematically reviewed. Among all types of HC reactors, vortex diode and single hole orifices revealed more than 95 % desulfurization yield and a 20 % viscosity reduction in heavy oil upgrading, while multi-hole orifice (100 holes) and slit Venturi allowed obtaining the best biodiesel production processes in terms of high (%) yield, low cost of treatment, and short processing time (5 min; 99 % biodiesel; 4.80 USD/m³). On the other hand, the acoustic cavitation devices are likely to be the most effective in biodiesel production based on ultrasonic bath (90 min; 95 %; 6.7 $/m³) and desulfurization treatment based on ultrasonic transducers (15 min; 98.3 % desulfurization; 10.8 $/m³). The implementation of HC-based processes reveals to be the most cost-effective method over acoustic cavitation-based devices. Finally, by reviewing the ongoing applications and development works, the limitations and challenges for further research are addressed emphasizing the cleaner production and guidelines for future scientists to assure obtaining comprehensive data useful for the research community.     

Determination of sulfoxide bond dissociation enthalpies of dibenzothiophene S‐oxide derivatives with computational methods

Photodeoxygenation of dibenzothiophene S‐oxide (DBTO) has been suggested as a clean way to generate atomic oxygen in solution. Sulfoxide bond dissociation enthalpies (BDEs) are important to the quantum yield and mechanism of this photodeoxygenation. In this study, BDE of substituted DBTO molecules with various functional groups were determined using M062X/aug‐cc‐pV(T + d)Z and MP2/aug‐cc‐pV(T + d)Z levels of theory. The sulfoxide BDE was determined using an isodesmic reaction. The observed effect of substitution was that functional groups with negative σ_para values (electron donating) strengthen the sulfoxide bond and that substituents with positive σ_para values (electron withdrawing) weaken the sulfoxide bond. The Mulliken charge on sulfur for DBTO and the corresponding dibenzothiophene were identified as a suitable indicator of the predicted S–O BDE. Moreover, steric and hydrogen bonding interactions were found to affect sulfoxide BDE for certain functional groups when located at the 1 or 4 positions of the substituted DBTO. Copyright © 2014 John Wiley & Sons, Ltd.     

Oxidation of sulfides including DBT using a new vanadyl complex of a non‐innocent o‐aminophenol benzoxazole based ligand

Reaction of a non‐innocent o‐aminophenol benzoxazole based ligand HL^BAP with VOCl₃ afforded a vanadyl complex, VOL^BIS (SQ), in which SQ is a 2,4‐di‐tert‐butylsemiquinone produced from hydrolysis of HL^BAP. The crystal structure of VOL^BIS (SQ) exhibits an octahedral geometry with the VO²⁺ center coordinated by two nitrogen and one oxygen atoms of L^BAP and two oxygen atoms of SQ. Electrochemical studies showed quasi‐reversible metal‐centered reduction and ligand‐centered oxidation of complex. The magnetic moment of VOL^BIS (SQ) is consistent with the spin‐only value expected for S = 1/2 system. The neutral species of VOL^BIS (SQ) is EPR active, which is consistent with a paramagnetic electronic ground state (S = 1/2). This result is in accordance with the vanadyl (IV) moiety surrounded by tridentate iminobenzosemiquinonate anion radical (HL^BIS)^?‐ and benzosemiquinone ligand (SQ)^?. The theoretical calculations confirm the experimental results. Furthermore, we present the optimal conditions for maximum efficiency of sulfide oxidation for oxidative desulfurization with hydrogen peroxide and 6 times reusability of catalyst for sulfoxidation of dibenzothiophene.     

核-壳结构多酸/磁性铈铁纳米复合氧化物@SiO2吸附-氧化脱硫性能

水热法合成了铈铁纳米复合氧化物,采用化学沉积法在其表面包裹SiO₂制备核-壳结构磁性材料,以其为载体负载H₂O₂结合Keggin结构磷钼酸(HPMo)制备了HPMo-H₂O₂/CeFe_xO_y@SiO₂吸附-氧化脱硫催化剂。 采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线粉末衍射(XRD)、氮气吸附脱附(BET)、³¹P魔角核磁共振(MAS-NMR)和X射线光电子能谱(XPS)等对催化剂的结构进行表征。 结果表明,SiO₂将CeFe_xO_y包裹形成核-壳结构纳米复合材料,以其为载体负载HPMo-H₂O₂后Keggin型多酸的骨架结构保持,并产生少量过氧化磷钼酸盐活性物种。 不同催化剂对有机硫化物二苯并噻吩(DBT)的吸附脱硫和氧化脱硫性能,均呈现出HPMo-H₂O₂/CeFe_xO_y@SiO₂＞CeFe_xO_y@SiO₂＞CeFe_xO_y的活性顺序,多酸的引入大大提升了其对大分子有机硫化物的吸附和氧化脱除性能,催化氧化脱硫活性的提高源于多酸分子“假液相”反应过程的结果。 在反应温度60 ℃,反应3 h,m(油)∶m(催化剂)=35∶1,n(O)∶n(S)=10∶1的条件下,对DBT氧化脱除率达到99.4%。 制备的磁性核-壳结构氧化脱硫剂有理想的氧化脱除DBT的循环使用性能,并且可通过外加磁场进行简单分离,是一类制备方法简单、催化活性高且稳定性好的绿色环保型催化剂。     

核黄素光敏化氧化二苯并噻吩的研究

以二苯并噻吩(DBT)的正辛烷溶液模拟柴油、水为溶剂、空气中的O<,2>为氧化剂和核黄素(RF)为光敏剂,研究了DBT在15 W紫外杀菌灯照射下的光化学氧化.结果表明,反应的最佳条件为:核黄素浓度20mg/L,空气流速80-100 mL/min.在该反应条件下反应2 h后,DBT的脱硫率为60%.核黄素是通过O<,2>...     

模拟油品氧化脱硫及反应动力学研究

在H₂O₂/WO₃/ZrO₂氧化体系中对以甲苯为溶剂、二苯并噻吩(DBT)为模型含硫化合物的模拟油品(硫的质量分数为1540×10^-6)进行了氧化脱硫研究,考察了反应温度、反应时间、氧化剂加入量、催化剂用量对DBT转化率的影响。实验结果表明,在反应温度50℃,反应时间90min,氧化剂加入量油/H₂O₂的体积比为20∶1和催化剂用量0.02g/mL的适宜氧化脱硫条件下,96%以上的DBT氧化为容易分离脱除的二苯并噻吩砜(DBTOs);同时研究了DBT氧化反应动力学,得知DBT氧化反应为一级反应,表观活化能E_a为55.37kJ/mol,指前因子A为3.35×10⁷min^-1。     

Ni2P/SiO2/堇青石整体式催化剂的制备及加氢脱硫性能

以硝酸镍为镍源、磷酸为磷源,与硅溶胶按一定比例混合,制成混合物浆料,然后采用浸渍法将混合物浆料负载于处理好的堇青石蜂窝陶瓷载体上,经过干燥、焙烧后制得含磷化镍前驱体的整体式催化剂,再经氢气气氛下程序升温还原,制得一系列不同镍含量的磷化镍/SiO2/堇青石整体式催化剂.采用XRD、N2吸脱附和SEM等现代分析测试手段对催化剂的结构进行了表征.以二苯并噻吩为模型含硫化合物,对催化剂的加氢脱硫活性进行了评价.结果表明,磷化镍/SiO2/堇青石整体式催化剂中,Ni含量小于3.2wt%时,磷化镍在堇青石表面高度分散,Ni含量大于6.4wt%时,催化剂的活性相是Ni2P,催化剂的平均孔径在3.6nm左右.催化活性层平均厚度约为20μm.在液时空速(LHSV)为1.9 h-1时,Ni含量为12.8wt%的催化剂具有最高的加氢脱硫活性,在360℃时二苯并噻吩的转化率为92.0%,联苯的选择性为69.8%,环己基苯的选择性为30.2%,反应主要按直接脱硫机理进行.     

纳米MoS_2催化剂的合成及其在加氢脱硫反应中的应用

通过羰基钼和升华硫反应制备了晶片层数为3～5,比表面积为71m2/g的纳米MoS2催化剂,并考察了其催化十二硫醇或二苯并噻吩的加氢脱硫活性.结果表明,在3.0MPa初始氢气压力下,该催化剂在200C和280C就可使十二硫醇和二苯并噻吩转化接近100%.