内循环反应器用于气固反应的动力学研究

设计了一套用于动力学研究的内循环无梯度反应系统,对其进行了无梯度检验,并用乙醇脱水动力学考证了该系统的可靠性.根据微型反应色谱测得的乙醇在HZSM-5分子筛上脱水反应的动力学数据,首次建立了乙醇脱水反应动力学数学模型的幂函数形式,经统计检验表明,该数学模型预测数据与实验数据吻合,模型方程估计的参数值均具高显著性,表明了该数学模型的精确性.该系统实现了在线色谱分析,操作简便迅速,可用于气固反应动力学的研究.     

氧化铝上乙醇脱水制乙烯的动力学

为开发多段绝热床生物质乙醇脱水制乙烯反应工艺,在Φ10 mm等温积分反应器中以自研发的氧化铝为催化剂研究了生物乙醇脱水制乙烯反应动力学。实验在排除内外扩散的影响的条件下,考察了反应温度、反应空速和水醇比对反应的影响,建立了生物质乙醇脱水制乙烯的半理论半经验的幂函数本征动力学模型。模型方程具有统计意义上的可靠性,并与实验结果吻合良好。     

生物乙醇催化脱水制乙烯的动力学研究

采用质量分数3%金属镧改性的HZSM-5分子筛催化剂,考察在较低的反应温度（200～300） ℃、固定床反应器内质量空速、催化剂粒径、反应温度以及反应物分压对乙醇转化率、产物收率和生成速率的影响,确定了乙醇脱水反应的动力学控制区域：质量空速≥20 h^-1,催化剂粒径≤0.7 mm。在此基础上,建立了生物乙醇催化脱水的动力学模型,拟合值和实验值吻合较好。     

绝热固定床反应器的乙醇脱水制乙烯反应工艺

为开发新型生物质乙醇脱水制乙烯反应工艺,采用了上海石油化工研究院开发的氧化铝催化剂,在绝热床反应器中进行了工艺实验优化研究。考察了不同水醇质量比、空速和反应器进口温度等对乙醇转化率和乙烯选择性的影响,应用该实验数据,结合前期建立的该催化剂上的乙醇脱水催化反应本征动力学,对该催化剂上的乙醇脱水催化反应本征动力学方程系数进行校正,计算出关于关键组分的该催化剂的效率因子,建立了更适宜于工业应用的宏观动力学模型,模型计算结果与实验数据吻合较好。相对于等温固定床反应工艺或单段绝热床反应工艺,所研发的氧化铝催化剂上四段绝热床反应工艺的能耗降低,乙醇转化率提高,乙烯选择性得到很大的提高,为工业反应器的优化设计以及放大提供必须的工艺设计数据。     

甲醇在耐高温磺酸树脂催化下的脱水反应动力学

为了开发反应精馏合成二甲醚新工艺,实验在2MPa(G)、120℃～155℃、初始甲醇摩尔分数100%～30%、液空速0.10mL/(min·g催化剂)～0.15mL/(min·g催化剂)条件下,以耐高温磺酸树脂作催化剂,在等温积分反应器内,系统地测定了甲醇脱水生成二甲醚的反应动力学数据。分别用L-H及E-R模型建立了反应动力学方程,并对实验数据进行了拟合。拟合结果表明:在实验范围内,按E-R模型拟合的反应动力学方程与实验结果更吻合。通过对动力学方程进行分析,发现随着反应温度的升高以及甲醇活度与水活度比值的增大,甲醇脱水反应速率都会增大。实验工作可为开发反应精馏合成二甲醚新工艺提供重要的反应动力学数据。     

城市污水处理厂脱水污泥一次好氧发酵过程动力学的研究

目前研究成果表明污泥好氧发酵过程合适的含水率为40％～65％，而一般的城市污水处理厂脱水污泥的含水率在80%左右，把含水率从80％调节到40％～65％范围内需要大量的调理剂，这给实际工程应用带来困难。因此，本文结合脱水污泥好氧堆肥化已经取得的研究成果，利用仓式反应器对脱水污泥在高含水率条件下（〉70％）的一次好氧发酵过程动力学进行研究。试验结果表明：脱水污泥一次好氧发酵过程中的生化反应符合一级反应动力擘模型。     

臭氧-乙醇法制取甲醛

<正> 用臭氧与无水乙醇反应制取甲醛未见有报道。经验研究表明在50～85℃时,臭氧与乙醇能发生反应;在反应中,臭氧既是催化剂又是氧化剂。臭氧促进乙醇脱水作用比用浓硫酸或无水三氯化铝降低2.45～5倍的反应温度,为此我们拟出“乙醇→乙烯→臭氧化合物→甲醛”的合成新路线。     

生物乙醇制乙烯初探

原油价格的不断攀升以及生物乙醇的飞速发展已对乙烯产业产生影响,也为乙醇脱水制乙烯技术路线的发展创造了机会。本文初步研究了采用改性HZSM-5催化剂、以生物乙醇溶液为原料制备乙烯。考察了反应温度、乙醇质量空速、乙醇浓度对该反应的影响,得到了优化的工艺条件：反应温度230 ℃,乙醇质量空速1.5～1.7 h－1,乙醇浓度80～150 g/L,乙醇转化率达到99%以上,乙烯选择性达到98%以上。     

不同粒径磷石膏的脱水动力学

为研究粒径对磷石膏脱水反应动力学的影响,测定了流动N₂气氛中,不同粒径磷石膏脱水反应的TG-DSC同步热分析数据。运用Flynn-wall-Ozawa法、Kissinger法和Satava-Sestak法相结合计算动力学参数,得出不同粒径（105～125μm、125～150μm、150～200μm和200～300μm）磷石膏脱水动力学模型,利用动力学方程对不同粒径磷石膏在相同条件下等温热分解进行预测,得出不同粒径、不同温度下磷石膏脱水率与时间的关系。结果表明：当磷石膏粒径由200～300μm减小到105～125μm时,磷石膏第一步脱水活化能从114.62kJ/mol减小到82.55kJ/mol,第二步脱水活化能由96.30kJ/mol减小到78.5kJ/mol。磷石膏脱水活化能随粒径的减小而减小,机理函数均符合Avrami-Erofeev方程。在相同的煅烧温度下,粒径小的磷石膏完全脱水所需时间缩短。     

基于官能团非等活性假设的尼龙66盐溶液聚合动力学模型

尼龙66盐溶液聚合过程属于动力学控制过程。基于官能团非等活性假设,在Mallon酸催化3阶反应动力学模型基础上,引入尼龙盐脱水反应,建立了新的尼龙66盐溶液聚合反应动力学模型,拟合得到了关键反应动力学模型参数,其中盐脱水反应速率常数为8.17×10^-3 kg?mol^-1?h^-1、活化能为19859 cal?mol^-1。与Mallon模型相比,新模型拟合效果更优,可在更宽的温度和水含量范围内准确预测聚合过程的变化。模拟仿真发现,盐脱水反应对聚合过程有重要影响,低温和高水含量下尼龙盐浓度高,聚合效率低;适当提高反应温度或降低初始水含量可以加快尼龙盐脱水反应,从而提高聚合反应效率。新的尼龙盐聚合动力学建模方法不仅适用于尼龙66,也可应用于尼龙1212等盐溶液聚合体系。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料，介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比，介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序，对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Some Large Wood-Boring Beetles in Southeastern USA

Ethanol and α-pinene were tested as attractants for large wood-boring pine beetles in Alabama, Florida, Georgia, North Carolina, and South Carolina in 2002–2004. Multiple-funnel traps baited with (−)-α-pinene (released at about 2 g/d at 25–28°C) were attractive to the following Cerambycidae: Acanthocinus nodosus, A. obsoletus, Arhopalus rusticus nubilus, Asemum striatum, Monochamus titillator, Prionus pocularis, Xylotrechus integer, and X. sagittatus sagittatus. Buprestis lineata (Buprestidae), Alaus myops (Elateridae), and Hylobius pales and Pachylobius picivorus (Curculionidae) were also attracted to traps baited with (−)-α-pinene. In many locations, ethanol synergized attraction of the cerambycids Acanthocinus nodosus, A. obsoletus, Arhopalus r. nubilus, Monochamus titillator, and Xylotrechus s. sagittatus (but not Asemum striatum, Prionus pocularis, or Xylotrechus integer) to traps baited with (−)-α-pinene. Similarly, attraction of Alaus myops, Hylobius pales, and Pachylobius picivorus (but not Buprestis lineata) to traps baited with (−)-α-pinene was synergized by ethanol. These results provide support for the use of traps baited with ethanol and (−)-α-pinene to detect and monitor common large wood-boring beetles from the southeastern region of the USA at ports-of-entry in other countries, as well as forested areas in the USA.