降解含硫杂环芳烃中度嗜盐菌的筛选及降解特性研究

从胜利油田石油污染土壤中筛选分离出6株对二苯并噻吩具有降解能力的中度嗜盐菌,其中SL-4菌株的降解效果最好,在底物浓度为50 mg·L-1、培养基盐度为5％条件下对二苯并噻吩的降解率达到37.2％.通过单因素实验考察了底物初始浓度、pH值、温度、氮磷比对SL-4菌株降解效果的影响.正交实验结果表明：氮磷比是影响SL-4菌株降解效果的主要因素,其次是pH值和温度;SL-4菌株的最佳培养条件为：pH值7.5、温度25℃、氮磷比6∶1.     

硫化型NiMo加氢催化剂制备与表征

以四硫代钼酸铵溶液和硝酸镍溶液为浸渍液,根据活性组分Ni和Mo浸渍顺序的不同,采用真空饱和浸渍法制备了MN系列和NM系列 NiMoS/γ-Al₂O₃催化剂。在固定床加氢中试反应装置上研究了NiMoS/γ-Al₂O₃催化剂对二苯并噻吩加氢反应的催化性能,结果表明,NiMoS/γ-Al₂O₃催化剂对二苯并噻吩加氢反应具有良好的活性和选择性。Ni助剂的加入,有利于二苯并噻吩加氢反应的活性和选择性。MN-0.3为最优NiMoS/γ-Al₂O₃催化剂。在空速10 h^-1、反应压力2.0 MPa、氢油体积比300∶1、氢气预处理温度320 ℃和反应温度300 ℃条件下,催化剂对二苯并噻吩加氢反应转化率达83.9%,加氢反应活性较高。     

钨酸锰催化氧化脱除模拟油硫化物

通过直接沉淀法制备钨酸锰,采用高温煅烧和双氧水活化的钨酸锰为催化剂,过氧化氢为氧化剂,咪唑氟硼酸盐离子液体为萃取剂,氧化脱除模拟油中的二苯并噻吩(DBT)。研究了反应时间、反应温度、催化剂的加入量、氧化剂用量、萃取剂类型、硫化物类型等因素对催化氧化脱硫的影响,同时考察催化剂/萃取剂脱硫体系循环使用性能。结果表明,最优工艺条件为:反应温度为50℃,H2O2加入量为0.3 m L,催化剂为0.03 g,以咪唑氟硼酸盐为萃取剂,反应时间为60 min时,二苯并噻吩的脱除率可达90%。催化剂/离子液体回收重复使用5次,催化活性无明显下降。     

Modeling of dibenzothiophene oxidative desulfurization using response surface methodology

The effect of reaction temperature, mixing speed and oxidant to catalyst volume ratio, including their interactions on the oxidative desulfurization of dibenzothiophene by using response surface methodology was studied. Hydrogen peroxide was used as oxidant and acetic acid as catalyst. The obtained model accurately predicts conversion of dibenzothiophene and the best conversion of 98.7% was observed at temperature 70°C, mixing speed of 1250 rpm and oxidant to catalyst volume ratio of 1:1. At high temperatures, a major limitation of the desulfurization process is the mass transfer and the high mixing speed is needed to achieve an efficient process.     

Ni2P/SiO2催化剂的制备及加氢脱硫性能

以次磷酸镍为原料在氮气气氛中进行低温固相反应,制备Ni2P/SiO2催化剂。用X射线衍射（XRD）、N2吸附脱附和透射电子显微镜（TEM）等分析测试技术对催化剂结构进行表征, Ni2P/SiO2 (负载质量分数为20%)催化剂的比表面积是226.2 m2/g,其活性组分在二氧化硅载体上具有良好的分散性,颗粒大小为5~8 nm。以二苯并噻吩（DBT）为模型化合物,在微型固定床反应器上对催化剂的加氢脱硫性能进行评价, 反应温度为340 ℃,氢压2.0 MPa,Ni2P 负载质量分数为20%时,催化剂对二苯并噻吩的转化率为99.1%,其直接脱硫 (DDS)与加氢脱硫(HDS)的选择性之比为4.5。结果表明,磷化镍（Ni2P）催化剂具有较高的加氢脱硫活性和选择性。     

Mo/REHY催化剂的加氢脱硫性能

将钼酸按溶液与REHY等体积浸渍和焙烧,制备了Mo/REHY催化剂,采用XRD和NH3-TPD对其进行表征.以质量分数0.6%的二苯并噻吩/正癸烷溶液为模型反应物评价其加氢脱硫性能.结果表明,不同焙烧温度制备的Mo/REHY催化剂,归属于REHY的晶相峰保持完好,金属活性组分Mo进入REHY体相超笼,引起REHY分子筛...     

负载金属离子ZSM-5分子筛膜脱除苯并噻吩-二苯并噻吩的性能

采用水热合成法制备ZSM-5分子筛膜,并通过负载金属离子对其进行改性。通过X线衍射仪(XRD)、扫描电子显微镜(SEM)对所制备的膜进行表征。将所制得的ZSM-5分子筛膜经过负载金属离子改性后用于模拟汽油中苯并噻吩、二苯并噻吩二元硫化物的分离,考察负载离子种类、负载离子浓度和操作温度对二元硫化物竞争吸附和渗透通量的影响,并应用软硬酸碱理论(HSAB)分析吸附能力的强弱。结果表明:当Ag+浓度为0.2 mol/L时硫化物的分离因子最高可达1.31;随着操作温度的升高,ZSM-5分子筛膜渗透通量逐渐增大而分离因子逐渐减小。     

Synthesis,crystal structure and desulfurization properties of zig-zag 1D coordination polymer of copper(II) containing 4-methoxybenzoic acid ligand

ABSTRACT

Combustion of fuels containing organosulfur compounds has resulted in the emission of sulfur oxides (SO_x) into the atmosphere, therefore, causing serious environmental and health hazards. Herein, slightly distorted octahedral zig-zag 1D coordination polymer of copper(II) [Cu(4-mba)₂(H₂O)₃] was synthesized by reacting copper sulfate pentahydrate with a carboxylate-containing ligand (H-4mba?=?4-methoxybenzoic acid) and employed for sulfur compound uptake. The ligand coordinates to the copper(II) atom via two pairs of deprotonated ligating atoms (carboxylate oxygens) and two water molecules. Structural characterization also reveals that interplay of O–H···O, N–H···O, C-H···O and C–H···π interactions between lattice and coordinated water and ligands significantly contribute to the crystal packing leading to the formation and strengthening of three-dimensional supramolecular assembly. The complex, [Cu(4-mba)₂(H₂O)₃], show potential for desulfurization of fuel with an observed adsorption capacity of 9.6?mg/g at 32°C for 6?h. DFT calculations further revealed a transfer of electron sulfur-containing compounds and the complex, [Cu(4-mba)₂(H₂O)₃], thus leading to a stronger pi–pi interaction.     

二苯并噻吩合成方法的改进

对文献报道的由联苯和硫在AlCl3催化下反应合成二苯并噻吩(DBT方法中的提纯过程作了改进，大大简化了提纯步骤，使制备DBT的时间缩短了一半，产率为63．4％，经提纯后的成品含量达99．7％，其纯度、外观、晶相均优于进口试剂，但成本远低于进口试剂。产品用FT-IR、LRS、XRD和^1H NMR表征结果与文献报道完全相符合。