Oxidation kinetics for <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11 and <Emphasis Type="Italic">trans</Emphasis>-10,<Emphasis Type="Italic">cis</Emphasis>-12 isomers of CLA

The autoxidation processes of the cis-9,trans-11 (c9,t11) and trans-10,cis-12 (t10,c12) isomers of CLA were separately observed at ca. 0% RH and different temperatures. The t10,c12 CLA oxidized faster than the c9,t11 isomer at all tested temperatures. The first half of the oxidation process of t10,c12 CLA obeyed an autocatalytic-type rate expression, but the latter half followed first-order kinetics. On the other hand, the entire oxidation process of c9,t11 CLA could be expressed by the autocatalytic-type rate expression. The apparent activation energies and frequency factors for the autoxidation of the isomers were estimated from the rate constants obtained at various temperatures based on the Arrhenius equation. The apparent activation energies for the CLA isomers were greater than those for the nonconjugated n−6 and n−3 PUFA or their esters. However, the enthalpyentropy compensation held during the autoxidation of both the CLA and PUFA. This suggested that the autoxidation mechanisms for the CLA and PUFA were essentially the same.     

ZnS/ZnO异质结构的制备及其光催化性能

以醋酸锌、硫脲为原料,采用简单的一步溶剂热法合成了花状Zn S微球,并分别在550、600和650℃下进行高温氧化处理,获得了Zn S/ZnO异质结构半导体材料。利用XRD、SEM、EDS、表面积分析仪、拉曼光谱仪和UV-Vis对材料的形貌、结构、比表面积和光学性质进行了测定,并以罗丹明B(Rh B)为模型污染物考察了样品的光催化性能。结果表明:原位合成的样品为立方相Zn S微球,经过550℃高温氧化1 h后,由于O原子的进入,生成少量ZnO,经过600℃高温氧化1 h后形成了Ⅱ型异质结构Zn S/ZnO,经过650℃高温氧化1 h后,样品基本上成为ZnO。随着高温氧化温度的升高,样品的禁带宽度整体呈下降趋势。光催化结果显示:Zn S/ZnO异质结构具备较优的光催化性能,紫外光照射40 min,Rh B降解率达到98.5%。     

CFD simulations of quenching process for partial oxidation of methane:Comparison of jet-in-cross-flow and impinging flow configurations

A new quenching process using the cold pyrolysis gas has been proposed for the partial oxidation (POX) of methane to recover the heat.The mixing of hot product gas and cold pyrolysis gas in milliseconds is critical to this new approach.Two most widely-used rapid mixing configurations,i.e.the jet-in-cross-flow (JICF) and impinging flow configurations,are compared in terms of mixing and quenching performances using computational fluid dynamics (CFD) coupled with detailed reaction mechanism Leeds 1.5.The mixedness,residence time distribution,temperature decreasing rate and loss ratio of acetylene during the quenching are systematically studied.The results show that the impinging flow has a more uniform mixing and narrower residence time distribution than the JICF.However,the temperature decreasing rate of the mainstream is faster in the JICF than in the impinging flow.The loss ratio of acetylene in the quenching process is 2.89％ for the JICF and 1.45％ for the impinging flow,showing that the impinging flow configuration is better and feasible for the quenching of POX of methane.     

4-羟基-5(4′-氯苯基)双环[4,4,0]-1-氮杂癸烷的合成

以 4′ 氯哌醋甲酯为原料,研究了作为潜在的治疗可卡因滥用症的药物———4 羟基- 5- (4′- 氯苯基 )双环 [4,4, 0]- 1 氮杂癸烷的合成。4′- 氯哌醋甲酯首先用乙酸酐在室温下进行乙酰基化,然后在 -70℃下经二异丙基胺锂(LDA)作用关环得中间产物(±)- threo -2, 4 -二氧代- 5- (4′- 氯苯基)双环[4, 4, 0] -1 氮杂癸烷,产率 60%。中间体先用硼氢化钠在甲醇中室温下选择性地将酮羰基还原,粗产物经V(石油醚)∶V(乙酸乙酯) =1∶1重结晶后,在四氢呋喃中于回流温度下用乙硼烷 四氢呋喃络合物进一步还原酰胺基,得到(±) threo 4α 羟基- 5 -(4′- 氯苯基 )双环[4, 4, 0]- 1 氮杂癸烷,两步产率为 67%。所得α位羟基产物经过Swern氧化,然后在四氢呋喃中在 -78℃下用三(仲丁基)硼氢化钾选择性还原,立体专一性地得到 (±) threo- 4β 羟基- 5 (4′- 氯苯基 )双环 [4, 4, 0]- 1 氮杂癸烷,氧化 还原反应总产率为 70%。     

碳纳米管及C60和石墨氧化动力学机理函数的分析

The oxidation of carbon nanotubes, C60 and graphite was studied by thermogravimetric (TG) analysis and differential thermal analysis (DTA) technique, and the oxidation kinetic models of three carbon materials studied were analyzed by mechanism-function method. The results indicate that three carbon species adopt different oxidation mechanisms due to their different structures. The oxidation of carbon nanotubes with cylindrical structure follows contracting volume reaction mechanism [R3 mechanism, 1 - (1 -α)1/3 = kt], indicating that the oxidation of carbon nanotubes takes place from the ends to the center. For graphite with planar sandwich structure, the oxidation starts at the edges initially and gradually moves toward the center, which corresponds to contracting area phase boundary reaction mechanism [R2 mechanism, 1 - (1 - α)1/2 = κt]. The oxidation of C60 with spherical structure,however, is complex and apparently cannot be illustrated with a single kinetic model. The values of apparent activation energy for C60 determined using Kissing method is 91kJ·mol-1.     

焦袂康酸的合成工艺研究

在有机碱醋酸钠存在下,以糠醇为原料,用氯气氧化扩环后水解法制备了焦袂康酸,研究了回流温度、回流时间、反应体系、水解液pH值和萃取剂等因素对产率的影响,得出其合成优化条件为：氯化反应介质体积比V（MeOH）：V（H2O）=1．5：1,回流温度80℃,回流时间1、5h,将水解液的pH值调到2．5,用CH2Cl2作为萃取剂,产率可达64．9％。同比在没有醋酸钠存在下反应,产率仅为25.4%。     

TNT和有机染料废水的光催化氧化动力学特性

利用光催化氧化技术能有效处理各类有机废水,具有高效、低选择性和不产生二次污染的特点,探讨了循环式浆态光催化反应器中有机染料和TNT模拟生产废水的光催化氧化特性以及光催化氧化动力学。基于羟基自由基生成、扩散以及羟基自由基与污染物分子的反应,建立了相应的光催化氧化动力学模型。结果表明,采用光催化氧化技术去除有机染料和TNT效果明显。光照时间为6h时,在一定的初始TNT浓度下,模拟红水中TNT去除率达90％以上。对不同染料和TNT不同初始浓度下的光催化氧化反应动力学研究表明,此过程符合拟一级动力学。所提出的光催化氧化动力学模型能够很好地描述有机染料和TNT的光催化氧化过程。