高硫合成气制甲硫醇K2MoO4/SiO2催化剂的研究Ⅰ.镍的促进作用

采用共同浸渍法制备了K2MoO4-NiO/SiO2催化剂,考察了NiO添加量对高硫合成气制甲硫醇K2MoO4/SiO2催化剂性能的影响.活性评价结果表明,添加了NiO的催化剂活性有很大的提高,当Ni/Mo物质的量比为2/9时,CO转化率为72.6%,较未添加NiO的催化剂提高了一倍多.程序升温还原(TPR)表征显示,添加的NiO与Mo有强相互作用,促进了Mo物种的还原.电子自旋共振(ESR)表征显示,反应后的催化剂中可检测到"oxo-Mo(V)"物种和"thio-Mo(V)"物种,K2MoO4-NiO/SiO2催化剂表面主要为"thio-Mo(V)"物种,而K2MoO4/SiO2催化剂表面主要为"oxo-Mo(V)"物种,NiO的添加促进了Mo物种的还原、硫化,可能是造成催化剂活性极大提高的原因.     

NiO/MgO/Al2O3固体碱负载磺化酞菁钴催化剂的制备及表征

采用浸渍法制备了NiO/MgO/Al2O3负载磺化酞菁钴(CoPcS)催化剂,研究了其催化硫醇常温氧化反应性能,并用X射线衍射、BET法和CO2-程序升温脱附等技术进行表征.与MgO/Al2O3-CoPcS催化剂相比,NiO/MgO/Al2O3-CoPcS催化剂具有较高的初活性和良好的稳定性.     

La2O3助剂对Ni/γ-Al2O3/堇青石结构化催化剂催化加氢合成间苯二胺性能的影响

研究助剂La2O3对Ni/γ-Al2O3/堇青石结构化催化剂结构与性能的影响。采用悬浮液涂层法、活性组分浸渍法制备不同La2O3助剂含量的Ni/γ-Al2O3/堇青石结构化催化剂。通过BET、XRD、TPR、XPS对催化剂进行表征,发现不添加La2O3助剂时活性组分以NiAl2O4形式存在,添加La2O3助剂后则以NiAl2O4和NiO两种形式存在,易还原NiO的生成提高了催化剂的活性。添加La2O3助剂还能使催化剂的比表面积降低和孔尺寸增大,活性评价表明助剂La2O3存在适宜添加量,即La含量为3%。同时发现助剂La2O3对选择性的影响大于活性,La2O3具有结构助剂的特点。     

球磨法制备NiO/MgAl2O4催化剂用于低浓度甲烷催化燃烧

用球磨法制备了MgAl_2O_4尖晶石负载的NiO催化剂NiO/MgAl_2O_4,考察了镍源、NiO负载量、球料比、球磨转速、焙烧温度对低浓度甲烷催化燃烧的影响,并用H_2-TPR、BET、XRD、SEM等手段对催化剂进行了表征。结果表明,与沉淀-沉积法或浸渍法相比,球磨法制备的催化剂前驱体与载体的相互作用较弱,焙烧后生成了高活性NiO物种。球磨法制备时,镍盐种类及NiO负载量、球料比、转速以及焙烧温度均会改变载体表面NiO晶粒的大小和结合状态,从而影响其活性。以乙酸镍为镍源、NiO质量分数10%、球料比2∶1、球磨转速400 r/min、经700℃焙烧,制得的NiO/MgAl_2O_4催化剂稳定性和活性较好;600℃下,700℃焙烧制得催化剂的拟一级反应速率常数(k600)为0.489 L/(g·s),高于MgAl_2O_4尖晶石负载的La_(0.8)Ca_(0.2)FeO_3或La_(0.8)Sr_(0.2)MnO_3钙钛矿催化剂。     

Mg、La助剂在镍基甲烷化催化剂中的协同作用

采用浸渍法制备Ni/Al2O3、La-Ni/Al2O3、Mg-Ni/Al2O3和Mg-La-Ni/Al2O3催化剂,讨论Mg和Ni两种助剂的协同作用,通过N2低温吸附、H2-TPR、XRD和SEM等表征方法对4种催化剂进行分析。结果表明,La助剂有利于削弱NiO与载体间的相互作用,降低催化剂中γ-NiO含量,但形成活性较低的α-NiO。Mg能够抑制催化剂中NiAl2O4尖晶石的形成,但Mg的添加会导致催化剂孔道堵塞,使NiO在催化剂表面团聚。Mg能够与NiO形成固溶体,在Mg的协同作用下,可抑制La-Ni/Al2O3催化剂中α-NiO的生成。La能够促进NiO分散,克服Mg-Ni/Al2O3催化剂孔道堵塞的缺陷。活性评价实验结果表明,添加不同助剂的催化剂在不同温度区域的活性不同,La-Ni/Al2O3催化剂低温活性较好,Mg-Ni/Al2O3催化剂高温活性较好,而在Mg和La两种助剂的协同作用下,Mg-La-Ni/Al2O3催化剂活性最高。     

Ce助剂对负载型Ni/TiO_2催化剂CO甲烷化性能的影响

通过浸渍法制备了一系列20Ni/xCe-TiO_2催化剂。考察了助剂Ce对于NiO/TiO_2催化剂甲烷化性能的影响,并对Ce助剂的最佳添加量进行了研究。对所制得催化剂进行了活性评价、还原条件测试、寿命测试,并利用SEM对其进行了表征。结果表明,添加助剂Ce可以增加催化剂的使用寿命,提高催化剂分散性,减小催化剂晶粒大小,增加反应活性区间,提高CH_4的选择性。通过对助剂Ce不同添加量的研究发现,20Ni/6Ce-TiO_2催化剂的活性较好,CO转化率可达88.8%,CH_4收率可达99.3%。对20Ni/6Ce-TiO_2催化剂还原条件的研究表明,在500℃TPR还原条件下活性较优。     

Ru改性Ni/Ce_(0.8)Pr_(0.2)O_2催化剂用于乙醇水蒸气重整制氢研究

利用柠檬酸溶胶-凝胶法制备Ru改性的Ni/Ce_(0.8)Pr_(0.2)O_2催化剂,并通过乙醇水蒸气重整反应考察了催化剂的活性及稳定性。探究了Ru改性对Ni/Ce_(0.8)Pr_(0.2)O_2催化剂催化乙醇水蒸气重整制氢的活性及稳定性的影响。通过X射线衍射、氮气吸附脱附、H2-程序升温还原等手段对催化剂结构及性质进行表征。结果表明,Ru的加入有助于降低NiO的还原温度,NiO与Ru作用紧密,因而Ru具有提高催化剂活性及稳定性的作用。在600℃、水与乙醇摩尔比为4、乙醇气相空速为69 900m L/gcat·h时,Ru改性的Ni/Ce_(0.8)Pr_(0.2)O_2催化剂具有较高的乙醇转化率且能得到较好的甲烷及CO_2气相产率。     

MgO前驱体对甲烷部分氧化整体催化剂的影响

研究了以不同MgO前驱体为过渡载体负载NiO的蜂窝陶瓷整体催化剂对甲烷部分氧化制备合成气反应过程的影响.采用X射线衍射(XRD)、H2程序升温还原实验(H2-TPR)和N2吸附等手段表征了前驱体及其负载活性组分NiO后的晶相、还原特性和吸附性能.在反应温度500～800℃、不同空速以及氧气与甲烷物质的量之比(O2/CH4)不同的条件下考察了催化剂活性.结果表明,NiO/MgO-Cl和NiO/MgO-S活性低、失活快;NiO/MgO-N催化剂活性高、稳定性好,这主要是由于前驱体在沉淀过程中形成不同物种,导致焙烧后载体及催化剂表面积和还原特性的差异.NiO/MgO-N催化剂在800℃,质量空速9 723 h-1及O2/CH4为0.5时,CH4转化率87.2%.H2和CO的选择性分别为100%和87.3%.     

低温下花球状Ni/CeO_2催化剂上甲烷水蒸气重整制氢研究

利用水热法制备花状CeO_2,采用浸渍热分解法制备NiO/CeO_2催化剂,NiO纳米颗粒均匀地分布在CeO_2花瓣上,达到了高度的分散,增加了甲烷和水脱氢作用的活性位点。通过XRD、SEM对催化剂进行表征。甲烷水蒸气重整结果表明,该催化剂低温下表现了良好的活性,较高的转化率,较好的稳定性和理想的抗积炭能力。催化剂稳定性超过300 h,550℃时甲烷转化率达到95%。不同水碳比下的催化性能测试结果表明,1.5~2.5的低水碳比为该催化剂的理想范围。因此,该催化剂在低温甲烷水蒸气重整制氢上表现良好,是一种很具潜力的催化剂。     

催化剂Au/NiO/TiO2对富氢中CO催化活性研究

以纳米TiO2做载体用共沉淀法负载不同含量Au和NiO的催化剂,研究了在不同条件下制备的催化剂对富氢气体中CO催化转的转化率与选择性,并表征了合成的催化剂,对催化剂进行了活性评价.结果表明加入NiO有助于催化剂活性的提高,当催化剂的组成为Au(2%)/NiO(5%)/TiO2时,反应溶液pH值在9～11,催化剂的评价温度在30℃催化剂对CO的转化率与选择性最高.     

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.