Pd/TiAl膜的制备研究

采用无电镀技术在多孔TiAl金属问化合物支撑体上制备了Pd膜.用SEM测定Pd膜的表面和断面的形貌,EDS测定从膜层到支撑层元素的组成,结果表明,支撑体表面形成了均匀致密的Pd膜,膜层的主要成分是单质Pd,所制钯膜的厚度为2～3μm.在350℃～500℃的温度范围内考察Pd膜透氢性能,当500℃,0.1 MPa时,H2的渗透系数为4.0×10-6mol·m-2·s-1·Pa-1,H2/N2的分离系数为30.测得本文所制备Pd膜的活化能为10.8 kJ/mol.     

超薄Pd～Cu／Al2O3合金膜的透氢性能

以多孔Al2O3陶瓷管为基体,采用化学镀法分步沉积Pd和Cu金属层,再经高温合金化处理,制备组分不同的Pd-Cu合金膜,膜厚均约为4μm.研究合金膜在100~650℃范围内的透氢性能,考察温度和膜组成对透氢性能的影响.结果表明:H2在膜表面的扩散过程是H2渗透速率的主要控制步骤;温度对膜透氢性能的影响规律因膜组成而异,这可能与合金膜在不同组成、不同温度条件下所呈现的晶相结构有关.     

氧化铝陶瓷管内表面化学镀钯膜及其透氢性能

采用化学镀法,以镀液循环的方式在多孔Al2O3陶瓷管内表面制备了钯膜。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对钯膜的形貌结构进行了表征,研究了蠕动泵转数对钯膜沉积的影响,并考察了钯膜在350～500°C之间的透氢性能。结果表明,随着蠕动泵转数增加,钯沉积量和致密性提高,然而当蠕动泵转数过快(如45r/min)时,钯膜产生缺陷,转数为30r/min时较适宜。随着温度和渗透压力的升高,H2的渗透通量增加,当温度为500°C、渗透压力为1×105Pa时,H2的渗透通量为0.24mol/(m2·s),理想气体分离因子α(H2/N2)为480。     

聚乙烯醇修饰多孔氧化铝载体及其表面化学镀制备透氢钯膜

先采用聚乙烯醇(PVA)对多孔氧化铝载体进行修饰,再通过化学镀制备了透氢性能良好的钯膜。PVA修饰层不仅能够有效改善粗糙载体的表面形貌,而且可通过热处理从钯复合膜中去除,以避免修饰层产生的透氢阻力。采用扫描电子显微镜(SEM)和能谱仪(EDS)分析了钯复合膜的形貌和组成,并测定了其在350~500°C温度范围内的氢气渗透性能。结果表明,钯膜厚度约为6μm,连续、致密,无明显的针孔和其他缺陷。在温度为500°C、渗透压力为100 kPa的条件下,钯复合膜的H_2渗透通量可达0.238 mol/(m~2·s),理想气体分离因子α(H_2/N_2)达956,并且测试进行100 h后其透氢性能依旧保持稳定。     

铸膜液结构对PVC/PMMA合金微滤膜性能的影响

通过高分子合金化,以L-S相转化法制备了PVC/PMMA非对称型合金微滤膜,考察了铸膜液结构对微滤膜结构与性能的影响.结果表明:随聚合物浓度、铸膜液温度升高合金膜水通量降低,平均孔径减小;增大PMMA含量,水通量上升,平均孔径增大;随添加剂量的增加,合金膜水通量上升,平均孔径减小.     

温度对化学镀钯层性能的影响

以Nb49Ni25Ti26氢渗透合金或载玻片为基体,在不同温度下进行化学镀钯。化学镀钯液组成与工艺条件为:PdCl22g/LNaH2PO2·H2O10g/L,38%盐酸4mL/L,NH4Cl27g/L,28%氨水160mL/L,pH9.8±0.2,施镀时间2h。研究了镀液温度对镀速和Pd镀层表面形貌、耐蚀性及氢渗透性能的影响。结果表明,化学镀钯的最佳温度为60°C,此时镀速达到最大[为4.05mg/(cm2·h)],制备的Pd镀层均匀、致密,耐腐蚀性好,具有较强的氢渗透作用。     

钯银合金膜反应器中二甲醚水蒸汽重整体系的透氢性能研究

二甲醚(DME)由于其清洁环保特性成为燃料电池电动汽车的理想氢源之一。在200~300℃温度范围,1.0×105~4.0×105Pa的压力范围内,Pd-Ag-Au-Ni合金膜对H2与Ar和N2的分离系数接近无穷大,同时,膜具有较好的透氢稳定性。通过实验研究了膜反应器中Ar、N2、CO、CO2、H2O和DME等气体存在时对钯银合金膜透氢性能的影响。实验结果表明,Ar、N2、DME基本对透氢性能无影响,CO2、CO、H2O存在时,会影响氢气的渗透性。三者当中,CO2的影响最小,混合气中H2O比CO对透氢性能的影响大,这是由于H2O在钯膜表面有更大的竞争吸附作用。本研究结果为更详细地研究二甲醚水蒸气重整制氢过程提供了重要参考依据。     

多孔膜反应器中丙烷催化脱氢制丙烯的模拟研究

针对丙烷高效脱氢制丙烯的多孔膜反应器构建了无量纲数学模型并进行了模拟研究,考察了催化剂活性、透氢膜性能、操作条件对多孔膜反应器中丙烷脱氢的转化率、丙烯收率、氢气收率和纯度的影响。结果表明,移走产物氢气可以有效提升膜反应器的性能,其性能的提升程度由不同温压条件下催化剂和透氢膜性能共同决定。高活性催化剂是丙烷高效转化的基础,催化剂活性越高,膜反应器内的产氢速率越快;其次,膜的选择性和渗透通量越高,氢气的移除效率越高,可在最大程度上打破热力学平衡的限制,使反应向生成丙烯的方向移动。当多孔透氢膜的氢气渗透率在10^-7~10^-6 mol·m^-2·s^-1·Pa^-1,H₂/C₃H₈选择性达到100时,其丙烷转化率可以与Pd膜反应器内的转化率相当,但分离的氢气纯度低于Pd膜反应器。与传统的固定床反应器相比,膜反应器由于促进了化学平衡的移动,可以在较低的反应温度下获得相当高的丙烷转化率,且丙烷转化率随着反应压力的增加呈现出一个最大值。该模拟研究可为实际生产过程中膜反应器用于PDH反应的高效强化提供有益的技术指导。     

丙酮和丁醛一步法合成甲基正戊基酮研究

以三乙胺为模板剂,采用水热法制备了Pd/SAPO-5双功能催化剂,用于丙酮和丁醛气相一步法合成甲基正戊基酮（MAK）。考察了n(SiO2):n(Al2O3)和反应温度的影响,并用H2-TPR,XRD,SEM,XRF,29Si MAS NMR等手段对催化剂进行表征。结果表明,钯的加入并不改变分子筛的晶体结构;而不同n(SiO2):n(Al2O3)会导致SAPO-5的分子筛晶体结构以及形貌上的差异。在SAPO-5的分子筛结构完整的前提下,Pd/SAPO-5催化活性随n(SiO2):n(Al2O3)的上升而增加。在最佳n(SiO2):n(Al2O3)=1.5、反应温度180℃时MAK的收率高达58.2%,并可持续运行500h以上而不失活。     

CuNi/Al2O3催化剂上乙炔选择加氢的研究

采用浸渍法制备了CuNi/Al2O3催化剂,研究了Ni负载量、Cu负载量及n(Cu)/n(Ni)对催化剂上乙炔选择加氢活性和选择性的影响,以及催化剂的还原性能。结果表明:CuNi/Al2O3催化剂中Cu提高了Ni的还原性,使催化剂具有很高的活性及乙烯选择性。随Cu/Ni原子比的提高,催化剂的活性下降,选择性升高,当Ni的负载量为10%、n(Cu)/n(Ni)=0.5时,在反应温度为50℃、反应压力为0.2 MPa、原料气流量为45 mL/min及H2流量为1.5 mL/min的反应条件下,乙炔的转化率达88.98%,乙烯的选择性达74.01%,乙烯收率为65.86%。     

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.