STUDIES ON INDIRECT ELECTROLYTIC OXIDATIONS OF p-CYMENE AND ITS CRACKING PRODUCT——TOLUENE

在无隔膜电解槽中,Pb-Sb合金为阳阴电极,Mn2+电解氧化成Mn3+的理想条件为:极板面积比(A+ /A- )为 5∶1,硫酸浓度为 5mol/L,阳极电流密度为 80mA/cm2,Mn2+浓度为1mol/L左右,温度在 25~35℃,电量比值为 1. 20。此时电解电流效率在 60%左右,Mn3+得率超过 70%。Mn3+氧化对伞花烃得到的主要产物为对甲基苯乙酮和枯茗醛,Mn3+与对伞花烃摩尔比为 4∶1时,氧化产物中枯茗醛的选择性相对较高,对甲基苯乙酮和枯茗醛的得率分别为 55. 19%和 31. 64%。Mn3+氧化甲苯得到的主要产物为苯甲醛,合适的氧化条件是Mn3+与甲苯摩尔比为 1∶6,苯甲醛的得率为 73. 67%。电解液经正己烷萃取和活性炭吸附可再生循环使用 8次以上。Reasonable condition for electrolytic oxidation of Mn~(2+) to Mn~(3+) in a diaphragmless electrolytic cell using anodic and cathodic electrodes of Pb-Sb alloy are:5∶1 area ratio of anode to cathode,5 mol/L of sulfuric acid,80 (mA/cm~2) of anodic current density,1 mol/L of Mn~(2+),25-35 ℃ of temperature,1.20 of Coulomb ratio.Current (efficiency) is about 60%,and electrolytic yield is over 70% under the above condition.When the ratio of Mn~(3+) to (p-cymene) is about 4∶1(molar ratio),selectivity of cuminaldehyde in the oxidized products is relatively high.Yields of main oxidized products,namely p-methyl acetophenone and cuminaldehyde are 55.19% and 31.64%,respectively.Suitable condition for oxidation of toluene by Mn~(3+) is that the ratio of Mn~(3+) to toluene is about 1∶6(molar ratio).Yield of benzaldehyde is 73.67%.The electrolytic liquor can be repeatedly used over 8 times by regeneration after (extraction) by n-hexane and adsorption by activated carbon

Analysis of Electrolytic-oxidation Products of Substituted Aromatics by GC-MS (Ⅱ)

采用GC -MS方法 ,分析了3种取代芳烃直接电解氧化的产物 ;从甲苯电解氧化产物中鉴定出7种主要成分 ,从对甲基苯甲醚电解氧化产物中鉴定出6种主要成分 ,从对叔丁基甲苯电解氧化产物中鉴定出6种主要成分 ;根据成分鉴定和含量测定结果 ,解释了以获取目标产物苯甲醛、对甲氧基苯甲醛和对叔丁基苯甲醛为目的的电解氧化反应要求。The GC-MS analyses of electrolytic-oxidation products of three substituted aromatic compounds are reported in this paper. Seven, six and six major constituents have been identified in the electrolytic-oxidation products of toluene, p-methyl anisole and p-tert-butyl toluene, respectively. Since the required target products of electrolytic oxidation for the above three substituted aromatic compounds are benzaldehyde, 4-methoxy benzaldehyde and p-tert-butyl benzaldehyde, our findings on the yields of the oxidation products have been discussed in terms of the extent of electrolysis

PROGRESS ON RESEARCH OF NATURAL ROSEMARY ANTIOXIDANT

迷迭香 (RosmarinusofficinalisL .)是唇形科迷迭香属植物 ,我国南方地区已有大量种植。迷迭香精油是传统的天然香料。从提取精油后的残渣中提取得到的迷迭香提取物 ,具有良好的抗氧化性能 ,是一种天然抗氧化剂。本文综述了国内外迷迭香栽培、迷迭香提取物的主要化学成分和生产工艺及其作为抗氧化剂在油脂和食品中的应用等研究。同时展望了迷迭香提取物在其它领域 ,特别是在医药等领域中的应用前景。Rosemary (Rosmarius officinalis L.), a plant of the family Labiatae, has been planted largely in south region of China. The essential oil of rosemary is a traditional natural perfume. The rosemary extract obtained from the residue after the removal of essential oil is a natural antioxidant that has a good antioxidative activity. Domestic and foreign researches on cultivation of rosemary, main chemical compositions of the extract, manufacture process of rosemary extract, utilization of rosemary extract as antioxidant in fats, oils, and foods were reviewed comprehensively. The prospect of the potential application of rosemary extract in other fields, particularly in the pharmaceutical industry, was discussed.国家林业局林产化学工程重点开放性实验室基金资助项目 (无项目号

Direct Electrolytic Oxidation of p-tert-Butyl toluene

The direct electrolytic oxidation of p-tert-butyl toluene in a mixture of sodium fluoborate, acetic acid and methanol using carbon rod as electrode has been studied. The main electrolytic oxidation products, p-tert-butylbenzaldehyde, p-tert-butylbenzyl methyl ether, p-tert-butyl benzaldehyde dimethyl acetal, and methyl p-tert-butylbenzoate were separated and identified by GC/MS. The relation between the oxidation pro- duct and the oxidation time in electrolytic oxidation was examined. The total yield of p-tert-butylbenzaldehyde and p-tert-butyl benzaldehyde dimethyl acetal was over 88% in period of 30 h oxidation.厦门涌泉集团有限公司博士后科研基金资助项

Research advances of electrochemical micro/nanofabrication based on confined etchant layer technique

与机械加工相比, 电化学加工技术具有无刀具磨损、无热效应、无机械损伤、加工效率高等优点, 而且适用于柔性、脆性及超硬材料,; 具备传统方法难以实现的复杂结构加工能力, 因而在航空航天、汽车、微电子等领域有着重要应用, 日益成为一种重要的工业制造技术.; 随着超大规模集成电路(ULSI)、微机电系统(MEMS)、微全分析系统(mu-TAS)、现代精密光学系统等高技术产业的迅速发展,; 功能性结构/器件的微型化和集成化的要求越来越高. 由于传统电化学只适用于金属材料, 为了应对微纳制造的时代要求, 拓展电化学加工的材料普适性,; 1992年田昭武院士提出了具有我国自主知识产权的约束刻蚀剂层技术(CELT). 一般的, 约束刻蚀包括3个步骤:; (1)通过电化学、光化学或光电化学的方法在模板电极表面生成刻蚀剂;; (2)通过后续的均相化学反应或自由基衰变反应将刻蚀剂约束在微/纳米厚度的液层内; (3)将模板电极逼近加工基底,; 当约束刻蚀剂层接触被加工基底时, 通过刻蚀反应实现微纳加工. 最近, 联合课题组通过仪器、原理和方法3个方面的努力, 引入外部物理场调制技术,; 实现一维铣削、二维抛光、三维微/纳结构加工, 大幅提升了CELT的技术水平.Compared with mechanical machining, ECM has several advantages, such as; avoiding tool wear, none thermal or mechanical stress on machining; surfaces, as well as high removal rate. Moreover, ECM is capable of; making complex three-dimensional structures and is appropriate for; flexible, fragile, or fissile materials even materials harder than the; machining tool. Thus, ECM has been widely used for various industrial; applications in the fields of aerospace, automobiles, electronics, etc.; ECM methods can be classified usually as electrolytic machining based on; anodic dissolution and electroforming based on cathodic deposition of; metallic materials. Recently, high technology industry, such as; ultralarge scale integration (ULSI) circuits, microelectromechanical; systems (MEMS), miniaturized total analysis systems (mu-TAS) and; precision optics, has developed more and more rapidly, where; miniaturization and integration of functional components are becoming; significant. Nowadays, the feature size of interconnectors in ULSI; circuits has been down to 20 nanometers, predicted by Moore's law.; Confined etchant layer technique (CELT) was proposed in 1992 to; fabricate three-dimensional micro- and nanostructures (3D-MNS) on; different metals and semiconductors, which has been developed an; effective machining method with independent intellectual property; rights. Generally, there are three procedures in CELT: (1) generating; the etchant on the surface of the tool electrode by electrochemical or; photoelectrochemical reactions; (2) confining the etchant in a depleted; layer with a thickness of micro- or nanometer scale; (3) etching process; when the tool electrode is fed to the workpiece, which applicable for 1D; milling, 2D polishing, and 3D microfabrication with an accuracy at micro; or nanometer scale. External physical-field modulations have recently; been introduced into CELT to improve its machining precision. In this; review, the advances of CELT in principles, instruments and applications; will be addressed as well as the prospects.国家自然科学基金; 机械制造系统工程国家重点实验室开放课题资助项

海域使用管理的若干问题探讨

文章对海域使用管理中遇到的若干问题进行探讨,包括海洋功能区划符合性判别、海域使用论证及用海确权、岸线认定、填海项目竣工海域使用验收等方面内容,以期为海域使用精细化管理提供参考依据。海洋公益性行业科研专项经费资助(200905004

Numerical simulation of bubble dynamics and heat transfer with transient thermal response of solid wall during pool boiling of FC-72

Using the Ghost Fluid Method for sharp interface representation, bubble dynamics and heat transfer during single bubble pool boiling of saturated FC-72 are simulated numerically with transient thermal response of the heated SiO2 solid wall. A constant and uniform temperature is fixed on to the bottom surface of the solid wall in the simulations, and thus, both the spatio-temporal averaged heat flux and superheat on the top surface, which contacts the working fluid directly, are dependent variables instead of controllable ones. Multi-cycle simulations are carried out to eliminate the influence of unreal initial conditions. Steady periodical processes of single bubble pool boiling can be reached on the wall with a thickness of 1 mm, while only quasi-steady ones on the wall with a thickness of 5 mm due to the limited simulation time, which results in a smaller thermal penetration depth inside the solid wall compared with its thickness. Comparing with the prediction of the correlation by Zuber for the discrete bubble region and experimental data of single bubble pool boiling, the numerical results of boiling curves in both steady and quasi-steady cases exhibit the same trend. Transient heat conduction inside the solid wall is analyzed in detail. A sharp drop of the wall temperature is evident in the vicinity of the contact line due to violent evaporation in this tiny region. The area of the temperature drop moves with the contact line, resulting in a pseudo-periodical process of heat storage and release inside the solid wall, which exhibits a coupling effect with bubble dynamics and heat transfer. The thermal penetration depth caused by the processes of bubble growth and departure in a single bubble cycle is about 0.5 mm in both steady and quasi-steady cases, which is much small than the heater thickness. (C) 2014 Elsevier Ltd. All rights reserved

中国物理海洋学研究70年：发展历程、学术成就概览

本文概略评述新中国成立70年来物理海洋学各分支研究领域的发展历程和若干学术成就。中国物理海洋学研究起步于海浪、潮汐、近海环流与水团,以及以风暴潮为主的海洋气象灾害的研究。随着国力的增强,研究领域不断拓展,涌现了大量具有广泛影响力的研究成果,其中包括:提出了被国际广泛采用的"普遍风浪谱"和"涌浪谱",发展了第三代海浪数值模式;提出了"准调和分析方法"和"潮汐潮流永久预报"等潮汐潮流的分析和预报方法;发现并命名了"棉兰老潜流",揭示了东海黑潮的多核结构及其多尺度变异机理等,系统描述了太平洋西边界流系;提出了印度尼西亚贯穿流的南海分支(或称南海贯穿流);不断完善了中国近海陆架环流系统,在南海环流、黑潮及其分支、台湾暖流、闽浙沿岸流、黄海冷水团环流、黄海暖流、渤海环流,以及陆架波方面均取得了深刻的认识;从大气桥和海洋桥两个方面对太平洋–印度洋–大西洋洋际相互作用进行了系统的总结;发展了浅海水团的研究方法,基本摸清了中国近海水团的分布和消长特征与机制,在大洋和极地水团分布及运动研究方面也做出了重要贡献;阐明了南海中尺度涡的宏观特征和生成机制,揭示了中尺度涡的三维结构,定量评估了其全球物质与能量输运能力;基本摸清了中国近海海洋锋的空间分布和季节变化特征,提出了地形、正压不稳定和斜压不稳定等锋面动力学机制;构建了"南海内波潜标观测网",实现了对内波生成–演变–消亡全过程机理的系统认识;发展了湍流的剪切不稳定理论,提出了海流"边缘不稳定"的概念,开发了海洋湍流模式,提出了湍流混合参数化的新方法等;在海洋内部混合机制和能量来源方面取得了新的认识,并阐述了混合对海洋深层环流、营养物质输运等过程的影响;研发了全球浪–潮–流耦合模式,推出一系列海洋与气候模式;发展了可同化主要海洋观测数据的海洋数据同化系统和用于ENSO预报的耦合同化系统;建立了达到国际水准的非地转(水槽/水池)和地转(旋转平台)物理模型实验平台;发展了ENSO预报的误差分析方法,建立了海洋和气候系统年代际变化的理论体系,揭示了中深层海洋对全球气候变化的响应;初步建成了中国近海海洋观测网;持续开展南北极调查研究;建立了台风、风暴潮、巨浪和海啸的业务化预报系统,为中国气象减灾提供保障;突破了国外的海洋技术封锁,研发了万米水深的深水水听器和海洋光学特性系列测量仪器;建立了溢油、危险化学品漂移扩散等预测模型,为伴随海洋资源开发所带来的风险事故的应急处理和预警预报提供科学支撑。文中引用的大量学术成果文献(每位第一作者优选不超过3篇)显示,经过70年的发展,中国物理海洋学研究培养了一支实力雄厚的科研队伍,这是最宝贵的成果。这支队伍必将成为中国物理海洋学研究攀登新高峰的主力军