减压渣油超临界流体萃取馏分在多孔有机膜中的扩散规律

利用超临界流体萃取分馏技术将大港减渣分离成16个窄馏分和1个萃余残渣,选择第3#、6#、9#、12#、15#窄馏分和残渣作为研究对象,运用隔膜池分别测定了308 K下各个油样通过额定孔径为15、50、80和1000 nm 4种聚碳酸酯膜有效扩散系数和平均有效扩散系数。结果显示,大港减渣窄馏分及萃余残渣在膜孔中的有效扩散系数随着实验的进行逐渐降低,表明它们是由一定尺寸分布的组分构成的复杂混合物。随着馏分变重和膜孔直径的降低,各馏分的有效扩散系数均逐渐降低。受阻扩散因子的计算结果表明窄馏分和萃余残渣在15、50和80 nm 3种膜片中的扩散均受到不同程度的阻碍。窄馏分在50和80 nm膜孔中的受阻程度较小,而在15 nm膜孔中的受阻程度相对较大。萃余残渣在这3种膜孔中均存在较为明显的扩散阻力,在15 nm膜孔中的受阻程度尤其严重。受阻扩散因子关联结果表明,在重油分子尺寸和孔径比值相同的条件下,窄馏分和萃余残渣的扩散受阻程度并不相同,分析认为这可能是两者分子构型的差异造成的。     

不同形貌AuAg/SBA-15的微波可控合成及其催化性能研究

采用微波辅助合成的方法制备出不同形貌的AuAg/SBA-15催化剂。表征结果表明:AuAg合金纳米粒子被限域在SBA-15介孔分子筛的孔道中,增强了活性组分与载体间的作用力,提高了催化剂的稳定性。4-硝基苯酚还原性能结果表明:催化剂的孔径和孔道结构对其催化性能具有重要的影响,其中具有短孔道和大孔径的片状AuAg/SBA-15表现出较好的扩散性能,并在4-硝基苯酚还原反应中具有较高的活性。     

重油分子的孔内受限扩散研究进展

随着常规石油资源日趋紧张和原油重质化,重油加氢处理过程越来越受到重视。由于重油分子在催化剂孔道中的受限扩散阻力影响着催化加氢反应速率和催化剂的利用率,因此研究重油分子在催化剂孔道中的内扩散行为及规律对指导加氢催化剂优化设计和加氢催化剂有效利用具有重大意义。本文介绍了重油分子孔内受限扩散研究的膜池法、吸附-扩散法和扩散-反应动力学法,指出相较于膜池法和吸附-扩散法,由扩散-反应动力学法研究所得结果更能反映在反应条件下重油孔内的受限扩散行为及规律,具有更广泛的应用价值;并简述了重油分子孔内扩散受限因子的研究进展,分析了用于重油孔内扩散行为及规律研究的多孔材料,指出孔结构均一的模型催化剂是一种利于扩散研究的理想多孔材料。     

NO与NH_3在不同构型分子筛催化剂中吸附和扩散的分子模拟

基于巨正则蒙特卡洛和分子动力学,对NH_3-SCR反应体系中吸附质分子(NO与NH_3)在不同拓扑结构沸石分子筛(LTL、FER、LEV、BEA、MOR、FAU、CHA和MFI)上的吸附和扩散特性进行系统研究。结果表明,对于全硅分子筛而言,其分子筛的拓扑结构影响NO与NH_3在分子筛上的吸附,综合吸附量及吸附作用能发现,MFI和LEV分子筛对NO具有较优的吸附特性;MFI和BEA分子筛对NH_3具有较优的吸附特性。研究了Si与Al物质的量比对BEA分子筛吸附性能影响,结果表明,随着Si与Al物质的量比降低,分子筛自由体积逐渐增加,进而有助于分子筛催化剂对NO和NH_3的吸附。采用分子动力学模拟计算NO与NH_3在不同构型全硅分子筛上的扩散系数,发现具有三维直通道且孔径较大的分子筛催化剂有利于NO和NH_3在其孔道内部的扩散,MFI虽然具备三维孔道结构,但由于存在Z型交叉通道,一定程度阻碍了反应物分子的扩散。     

多孔球形催化剂颗粒的随机网络模型

提出了一种多孔球形催化剂颗粒随机网络构造方法,并以等温一级不可逆反应为例,对催化剂孔道网络内发生的反应扩散过程进行了模拟计算。模拟结果表明,计算出的曲折因子既是孔网络配位数的函数,又随Thiele模数的变化而不同,在纯扩散条件下测得的有效扩散系数只能应用于扩散影响不严重的反应扩散区域。同时对在不同的网络模型上的模拟结果进行了分析,并对各自得出的结论之间存在的分歧进行了解析。     

有序介孔碳载金属催化剂用于择形催化

择形催化在精细化学合成等领域发挥着重要作用。有序介孔材料具有相对大的孔径以及规整的孔道结构,探究其在有机合成中择形催化性能具有重要意义。本研究考察了有序介孔碳载AuPd合金催化剂的孔径对苄醇选择氧化和喹啉选择加氢反应中分子尺寸选择催化性能的影响。结果表明：有序介孔碳催化剂介孔孔径与反应物分子尺寸之间存在明显的正依存关系。苯甲醇和喹啉等尺寸较小的底物分子可扩散进入3.5 nm的介孔孔道,在合金表面反应;而尺寸较大的分子如2-甲基苄醇和3,5-二叔丁基苄醇,内扩散受到限制,几乎不能发生转化。当孔径扩大至5.0nm时,2-甲基苄醇可扩散进入孔道,催化氧化的转化频率(TOF_Pd)可达307 h^-1;进一步扩大孔径至6.0 nm,尺寸更大的分子如3,5-二叔丁基苄醇也能被氧化,TOF_Pd达到140 h^-1。     

基于分形理论的油页岩有效扩散系数研究

以直径为1.6—2 mm柳树河油页岩为原料,采用扫描电镜法与氮吸附法得出油页岩吸附-脱附等温线,孔径分布曲线等;分析了油页岩内部孔隙结构,计算出孔道弯曲分形维数与孔隙面积分形维数,并研究油页岩内部的有效扩散系数。结果表明:油页岩吸附-脱附曲线属于Ⅲ型等温线,是一种典型的二端都开放的管状毛细孔型结构的多孔物质;其含有较发达孔隙,孔径分布为0.4—40 nm;油页岩孔道弯曲分形维数越小,孔道越平坦,孔隙面积分形维数为2.464;油页岩有效扩散系数与其内部结构和操作温度有关,温度越高,粒径越小,有效扩散系数越大。     

混凝土孔结构及其分形维数与氯离子扩散性能的关系

氯离子扩散系数是研究海洋环境下混凝土结构耐久性的重要参数之一。通过开展不同水胶比混凝土的压汞试验和盐雾扩散试验,研究了混凝土内部孔隙率、孔径分布及临界孔径对氯离子扩散系数的影响规律。结合Menger海绵体模型,建立孔体积分形维数与氯离子扩散系数的关系。结果表明:孔隙率和临界孔径与无量纲化氯离子扩散系数的相关性很高,可作为反映混凝土氯离子扩散性能的重要参数;通过数学分析计算得到的孔表面分形维数分布在2.56~3.86之间,孔体积分形维数分布在2.85~2.98之间;基于压汞法和分形理论计算得到的孔体积分形维数可以作为评价氯离子扩散系数的指标,在孔径小于10 nm、10～100 nm、100～1 000 nm以及大于1 000 nm四类区间,氯离子扩散系数随孔体积分形维数的增加而下降。     

SBA-15/酶纳米反应器的扩散和动力学

将猪胰脂肪酶固定于不同孔径SBA-15载体的孔道内,将已固定酶的尺寸分布均一的一维孔道看作纳米反应器,研究了酶催化水解反应的内扩散和动力学特征。蒂勒模数和有效扩散系数随孔径尺寸的变化以及动力学参数和内扩散之间的关系说明:当孔径小于9.4nm时,内扩散限制明显;孔径大于10.9nm时,内扩散对酶催化水解过程的影响减小。     

在不同构型分子筛催化剂中吸附和扩散的分子模拟

基于巨正则蒙特卡洛和分子动力学,对NH₃-SCR反应体系中吸附质分子（NO与NH₃）在不同拓扑结构沸石分子筛（LTL、FER、LEV、BEA、MOR、FAU、CHA和MFI）上的吸附和扩散特性进行系统研究。结果表明,对于全硅分子筛而言,其分子筛的拓扑结构影响NO与NH3在分子筛上的吸附,综合吸附量及吸附作用能发现,MFI和LEV分子筛对NO具有较优的吸附特性;MFI和BEA分子筛对NH₃ 具有较优的吸附特性。研究了Si与Al物质的量比对BEA分子筛吸附性能影响,结果表明,随着Si与Al物质的量比降低,分子筛自由体积逐渐增加,进而有助于分子筛催化剂对NO和NH₃的吸附。采用分子动力学模拟计算NO与NH₃在不同构型全硅分子筛上的扩散系数,发现具有三维直通道且孔径较大的分子筛催化剂有利于NO和NH₃在其孔道内部的扩散,MFI虽然具备三维孔道结构,但由于存在Z型交叉通道,一定程度阻碍了反应物分子的扩散。     

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.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

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.     

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.     

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。