硫茚萃取精馏分离的模拟计算

采用Aspen plus软件模拟计算硫茚的萃取精馏,并通过了实验的校核。然后,通过对相同操作条件下不同萃取剂的硫茚萃取精馏模拟,预测了不同萃取剂在实际萃取精馏中的分离效果,选取了合适的高选择性的萃取剂,得到了少量实验的验证,达到事半功倍的效果。     

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。     

复合SiO2-WO3催化剂的制备、表征及氧化脱除苯并噻吩性能

 采用溶胶-凝胶法制备了SiO₂-WO₃催化剂,并采用XRD、FT-IR、BET、TG-DTA等方法对催化剂进行表征。以苯并噻吩(BT)为模型化合物,H₂O₂为氧化剂,考察了催化剂的活性元素、制备方法、n(W)/n(Si)和焙烧温度对其催化氧化脱硫活性的影响。结果表明,W的引入降低了SiO₂的比表面积,SiO₂-WO₃催化剂中W的主物相为WO₃。在以W为活性组元,且n(W)/n(Si)为0.1时,500℃焙烧得到的SiO₂-0.1WO₃催化剂具有最好的催化脱硫活性。在模拟油20 mL、催化剂SiO₂-0.1WO₃用量0.04 g、n(H₂O₂)/n(S)为15.9、乙腈/模拟油体积比0.3、65℃反应60 min的条件下,苯并噻吩模拟油脱硫率可达99.3%。     

High surface area MoO3/MgO: preparation by the new slurry impregnation method and activity in sulphided state in hydrodesulphurization of benzothiophene

High surface area MoO₂/MgO was prepared by the reaction of MgO (250–300 m² g⁻¹) with a slurry of ammonium heptamolybdate in methanol or anhydrous ethanol at the alcohol boiling point. The low solubility of ammonium heptamolybdate was sufficient for its gradual transport to the support surface: molybdena species were deposited and ammonia was evolved. Catalytic activities in the hydrodesulphurization of benzothiophene of the MoO₃/MgO samples were comparable to the activity of the reference commercial MoO₃/Al₂O₃ catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

金属有机骨架化合物[Cu2（OH）（2,2＇-bipy）2（BTC）·2H2O]n的脱硫性能研究

采用水热法合成出金属有机骨架化合物[Cu2（OH）（2,2’-bipy）2（BTC）·2H2O]n晶体,以此化合物为吸附剂,在常温常压下通过固定床动态吸附实验,考察了其对模型油中的噻吩和苯并噻吩的脱除效果.结果表明,该吸附剂对噻吩、苯并噻吩的饱和吸附容量分别为2.32％,1.20％;采用4A分子筛与吸附剂分层装填的方法可有效解决模型油中的溶解水对吸附脱硫效果的影响;用甲苯对吸附饱和的吸附剂进行再生,再生率达到98％.     

庚烯与H2S在酸性催化剂上反应机理研究I-硫醇等生成机理

 为了研究催化裂化汽油中硫化物的生成机理,在小型固定流化床(FFB)装置中考察了不同质量分数的庚烯与H₂S在固体酸催化剂上的反应.结果表明, 庚烯与H₂S的反应主要生成噻吩类硫化物、部分硫醇、少量硫醚和痕量四氢噻吩等硫化物；庚烯质量分数越高,生成硫化物的量越多; 噻吩类硫化物中生成量最大的甲基苯并噻吩的生成量也随着庚烯质量分数增加而线性增长.烯烃在催化剂B酸活性中心上吸附形成正碳离子, 正碳离子与H₂S结合生成硫醇,硫醇的生成遵循正碳离子机理.硫醇与烯烃反应生成硫醚.当反应温度为400～500℃,庚烯与H₂S反应中,生成硫醇、硫醚的反应均为放热反应,硫醇的平衡收率较低,硫醚的平衡收率更低一些.     

PEG-HPMo/SiO2介孔材料的制备及其催化氧化脱除模型油中苯并噻吩的研究

分别以聚乙二醇(PEG6000)及正硅酸乙酯(TEOS)为模板剂和硅源,采用沉淀法制备了SiO2负载型磷钼酸(HPMo)催化剂PEG-HPMo/SiO2,对催化剂进行了FT-IR、XRD、FE-SEM等表征。采用NLDFT平衡模型对吸附-脱附等温数据进行处理,计算了催化剂的孔径分布及比表面积。研究结果表明:催化剂PEG-HPMo/SiO2含有HPMo的Keggin结构且具有较高的脱硫活性。当催化剂用量0.06g、H2O2用量0.04mL、反应温度70℃、反应时间35min时,10mL模型油中的苯并噻吩(BT)基本被完全脱除;催化剂重复使用6次后,催化剂的催化活性没有明显降低。     

过氧化叔戊醇对苯并噻吩类衍生物的氧化

Homogeneous oxidation using an oil-soluble oxidant, tert-amyl hydroperoxide (TAHP), for ultra-deep desulfurization was performed under mild conditions in the presence of molybdenum oxide catalysts. Dibenzothio-phene (DBT), benzothiophene (BT) and 4, 6-dimethyl-dibenzothiophene (DMDBT), which are the refractory sulfur compounds for hydrodesulfurization (HDS), were employed as model substrates for a simulated diesel fuel. Activ-ity of molybdenum oxide supported on a macroporous weak acidic resin was investigated. The mass conversion of DBT reached near 100% at 90°C and a TAHP/DBT molar ratio of 3 with 1% of molybdenum oxide supported on Amberlite IRC-748 resin for 1 h. It was further found that the activities of the model substrates decreased in the or-der of DMDBT＞DBT＞BT. In the flow oxidation using TAHP as the oxidant, mass conversion of DBT increased remarkably from 61.3% to 98.5% when dropping the weight hourly space velocity (WHSV) from 40 h－1 to 10 h－1. A series of experiments dealt with selectivity of this oxidation using TAHP revealed that the model unsaturated compounds, i.e. 4, 6, 8-trimethyl-2-nonylene, and 2-methylnaphthalene did not affect the oxidation of DBT. Car-bazole had nearly no effect on the conversion of DBT using TAHP, but had some influence on the one using tert-butyl hydroperoxide (TBHP). The mass conversion of DBT decreased remarkably from 75.2% to 3.6% when the content of carbazole increased from 0 to 500 μg•g－1. In the flow oxidation using TAHP as the oxidant, the con-centration of DBT in model fuels was reduced from 500 µg•g－1 to 7.2 µg•g－1 at WHSV of 10 h－1, and then reduced to 3.8 µg•g－1 by adsorption of Al2O3.     

球形活性炭的制备及其对苯并噻吩的吸附研究

以122型弱酸性酚醛系阳离子交换树脂为炭前驱体,经过炭化和CO2活化,制备球形活性炭(SAC).利用热重分析、扫描电镜、红外光谱和低温N2吸附对材料进行表征.结果表明:制得的球形活性炭比表面积达到799.567 m2/g,孔容为0.969 cm3/g,对苯并噻吩的吸附硫容达到10.3mg/g.用Freundlich和Langmuir模型对吸附平衡数据进行拟合发现:球形活性炭对苯并噻吩的吸附更符合Freundlich模型,表明球形活性炭的吸附活性位不均匀分布;分别用准一级(PFO)、准二级(PSO)、修正的准n级(MPnO)和混阶(MOE)四种动力学速率方程对吸附动力学数据进行拟合,MPnO最适合描述球形活性炭吸附苯并噻吩的动力学过程.