低温吸附法分离氢同位素

液氮温度下用分子筛Y在自行设计的单塔变压吸附装置上进行氢氘气体分离的研究,考察了流量与压力对分离效果的影响,在气体总压力0.40 MPa、总流量129.79 cm3/min与吸附床长度1.0 m时氢氘气体之间的分离因子可达到1.52。然而压力为0.013 9 MPa与0.017 5 MPa时D2与H2在分子筛Y上的平衡吸附量比值仅分别为1.18和1.17。结合平衡吸附和动态分离之间的差异,表明吸附法能够有效分离氢同位素气体的机理是基于动力学效应。     

氢同位素气体的新型动力学吸附模型

将氢同位素气体在多孔吸附剂表面上的吸附脱附过程假设为简单对峙反应,提出了一个适用于体积法计算气体动力学吸附速率常数的数学模型。模型可考察温度与初始压力对动力学吸附速率的影响,且能较好地计算不同压力下氢气与氘气在微孔分子筛4A,5A,Y,10X与介孔分子筛CMK-3,SBA-15上的动力学吸附速率常数。当分子筛孔径为0.5 nm时动力学吸附选择性最大,可高达2.48。介孔分子筛的动力学吸附选择性则较小,表明大孔径的吸附剂不利于氢同位素气体混合物的分离。     

RHO分子筛空分性能评价

RHO分子筛由于独特的孔道结构在O₂/N₂分离方面表现出其特有的性质。采用水热合成法合成Na,Cs-RHO分子筛,进行碱金属离子交换改性,然后利用XRD和SEM对样品进行表征。通过单组分气体吸附实验、Aspen Adsorption软件模拟混合组分穿透曲线实验和双塔PSA空分实验对吸附剂性能进行评价。结果表明:Li-RHO是一种容易通过阳离子调控骨架扭曲程度的分子筛,O₂/N₂平衡分离性能参数最大。穿透曲线实验结果表明,弱吸附组分(N₂)首先穿透吸附床,O₂因强吸附而后穿出,Li-RHO的动力学分离因子很高。Aspen Adsorption模拟结果表明,Li-RHO制得的N₂纯度和回收率最高,可能是一种具有良好应用前景的空分吸附剂。     

模拟移动床吸附分离对甲乙苯工艺

为了实现C9芳烃中对甲乙苯资源的高效利用,以X型分子筛为吸附剂,以混合甲乙苯为原料,采用液相模拟移动床吸附工艺分离对甲乙苯(p-MEB)与邻甲乙苯(o-MEB)、间甲乙苯(m-MEB)。在操作温度为75℃、操作压力为0. 25 MPa的条件下,在液相模拟移动床吸附分离装置上考察了操作条件对p-MEB吸附分离过程的影响规律,获得优化的p-MEB吸附分离工艺条件为:模拟移动床区域分布采用6-3-4-3模式,切换时间900 s,分配比1. 1,循环比3. 5,脱附剂比9. 3。对于pMEB质量分数为20. 78%的C_9芳烃,优化分离工艺条件下得到的p-MEB质量分数为94. 52%,回收率达到90. 86%。     

结构化5A分子筛吸附床结构及工艺参数对N2/H2吸附性能的影响

利用吸附等温线获得动力学参数,建立了CFD模型,模拟了氢气/氮气在结构化5A分子筛吸附床中的吸附过程,研究了吸附剂层片间距、吸附剂厚度等结构参数和吸附压力、进气流量等工艺参数对混合气吸附效果的影响。结果表明：减小层片间距和吸附剂厚度可显著提高传质系数和床层利用率。增大吸附压力可提高床层利用率,但会减小传质系数。进气流量对传质系数的影响不明显,但当流量较大时,吸附容量和床层利用率均呈减小趋势。结构化5A分子筛吸附剂吸附性能良好。     

5A分子筛分离工业异己烷中低含量正己烷

采用5A分子筛对工业异己烷进行吸附分离,既可纯化异己烷,又可得到高纯的正己烷。测定了吸附穿透曲线,分析了吸附温度对穿透吸附量、传质区长度以及床层利用率的影响,探讨了水置换法脱附再利用吸附剂的方法。试验结果表明:常压下,在60~90℃,5A分子筛对正己烷的吸附穿透曲线均为"S"型;70℃时正己烷的穿透吸附量及饱和吸附量最高;对于低浓度正己烷,温度对吸附传质区长度、床层利用率影响不大;采取水置换脱附法可以有效多次再生5A分子筛。5A分子筛对2-甲基戊烷、3-甲基戊烷吸附作用很小,吸附分离中异己烷的损失量小。     

非耦联吸附塔新变压吸附工艺的实验研究

通过提氢实验研究一种新的变压吸附工艺.变压吸附流程的主要特征是通过中间均压罐打开吸附塔之间由均压步骤形成的耦联,从而实现了各塔操作的独立性,并提供了降低吸附压力的可能性.以H₂/N₂/CH₄（60/10/30）混合气模拟石油炼厂干气,进行低吸附压力（≤1 MPa）条件下的提氢操作.针对已有变压吸附工艺的不足和新流程特征,确定了新流程的变压吸附循环时序.分别采用普通活性炭（OAC）和高比表面活性炭（SAC）与5A沸石分子筛（ZMS-5A）的组合吸附剂,研究了不同吸附压力下的变压吸附分离效果,证明此种变压吸附新工艺在1 MPa以下、甚至0.4 MPa的低吸附压力下运行,亦可在较高的回收率下达到99.99%的高氢气纯度,并且显示出更强的对偶然性故障的应变能力.     

多孔材料烷烃/烯烃分离技术的研究

以模拟油品为原料,在小型固定床（200 mL）反应器上考察了硅胶、γ-Al₂O₃、13X分子筛、Y分子筛及ZSM-5分子筛等多孔材料对烷烃/烯烃的吸附分离性能;其中硅胶的烷烃/烯烃分离效果最好,在吸附温度为40 ℃、压力为0.5 MPa、解吸剂为正辛烷/甲基环己烷的条件下,烷烃/烯烃分离度最高达到0.81;与其他类型硅胶相比,平均孔径为4~6 nm的B型硅胶传质效果更好,吸附-脱附过程更易趋于平衡。经过焙烧和溶剂再生的吸附剂,与新鲜剂相比,分离效果没有明显的降低。     

5A沸石分子筛低温变压吸附CO2/CH4实验研究

采用静态容积法测量5A沸石分子筛对CO_2和CH_4的单组份等温吸附曲线,采用低温变压测量不同实验参数对5A沸石分子筛分离CH_4/CO_2混合气体的能力影响。静态实验表明,CO_2和CH_4吸附量随温度的降低而上升,-30℃时CO_2和CH_4在吸附剂上的饱和吸附量最高:分别为4.94 mmol/g和3.0 mmol/g;动态试验表明,增加吸附压力会降低分离效果,减小混合气体分离系数;降低吸附温度有利于CH_4/CO_2分离,提高混合气体分离系数。     

变压吸附法提纯煤层气中甲烷研究进展

低浓度煤层气直接排放既造成能源浪费,又带来严重的温室效应,变压吸附法提纯低浓度煤层气是解决煤层气排放的有效利用途径。总结了变压吸附技术对CH_4/N_2体系煤层气中CH4分离的研究进展,包括变压吸附分离机理和相应的变压吸附提纯工艺路线,分析了2种工艺的优缺点,讨论了多孔吸附材料,如活性炭、碳分子筛、沸石分子筛和金属有机骨架材料对CH_4/N_2吸附分离效果的研究进展和存在的问题。基于平衡效应分离的变压吸附技术,在CH_4/N_2体系分离实际应用中遇到瓶颈,原因在于现有吸附剂平衡分离系数太小,提浓幅度有限;其次,CH_4在平衡效应里作为强吸附组分被优先吸附,产品气必须通过抽真空的方式解吸获得,必须采取多级压缩和增加置换步骤,因而能耗相对较高。基于动力学效应的分离,可在塔顶直接获得富集的带压产品气;同时免去多级压缩的能量消耗,相对平衡效应分离具有显著优势,但需要在第一级加压,处理接近爆炸限浓度煤层气有一定安全隐患。活性炭吸附容量大,处理能力强,价格低廉,是一种典型的平衡分离型吸附剂,但分离系数较低,存在气体循环量大、效率低,提浓幅度窄等缺点,如何通过孔径调控和表面改性提高活性炭的平衡分离系数将是今后研究的重点。现有报道效果较好的动力学吸附剂主要以碳分子筛为主,但价格高昂,工业推广受限,选择合适的廉价原料、改变现有间歇式生产工艺、进一步开发高效、廉价的动力学/N2的重要方向。沸石分子筛会优先吸附CH_4,与动力学效应优先吸附N_2相反,降低了分子筛对CH_4/N_2的分离选择性。所以硅铝分子筛/钛硅分子筛多在分离高浓度CH4含量的天然气、油田气方面表现优异,针对低浓度煤层气CH_4的提纯应用较少,未见工业应用报道。金属有机骨架材料的出现提供了新的发展思路,但其在CH_4/N_2的吸附平衡和动力学研究以及变压吸附分离方面研究较少,还有待进一步深入研究,解决材料的稳定成型和放大仍是需要突破的技术瓶颈。未来变压吸附提纯工艺将是平衡效应和动力学效应的组合工艺,开发低压下变压吸附分离工艺将具有更好的经济性和安全性;低成本、大容量、高选择性吸附剂开发仍是未来吸附剂的重点发展方向;同时吸附剂寿命以及再生性能有待深入研究。     

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.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.     

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.