流化床甲醇制烯烃含烃催化剂锁斗分离技术研究及应用

介绍了传统流化床甲醇制烯烃装置中反应器产生的废催化剂回收工艺,分析了反应器产生的废催化剂中含烯烃的原因,说明了废催化剂含烯烃的安全风险和传统回收废催化剂工艺的缺陷。详细介绍了FMTP装置中对废催化剂回收系统的工艺改进、流程设计、操作方法和安全可靠性能。     

重氮乙酸乙酯的连续合成工艺研究

以甘氨酸乙酯盐酸盐和亚硝酸钠为原料,研究了在微通道反应器中重氮乙酸乙酯的连续流合成工艺。考察了亚硝酸钠用量、反应温度、酸用量、停留时间等工艺条件对反应结果的影响。由于该反应为强放热反应,且产物在高温下稳定性差,因此,若采用传统釜式间歇操作容易造成局部过热,存在较大的安全隐患和产物分解的缺陷;普通的管道反应器又难以克服非均相的传质障碍导致收率偏低。微通道反应器在保持良好的传热效率同时,能打破相界面障碍,保证反应液充分混合,非常适合该工艺的开发。利用微通道反应器的上述优点,进行工艺条件的筛选,提高了反应效率并得到较高的收率。     

氟化工专利精选

<正>双氟磺酰亚胺的清洁生产工艺使用间歇反应釜作为预反应装置,微通道反应器作为主反应装置,微通道反应器包含串联的第1温区和第2温区,2个温区均包含多个串联的反应模块;先将氨基磺酸、三氧化硫、氯化亚砜加入间歇反应釜进行反应,得到预反应液,然后将预反应液打入第1温区进行反应,得到双氯反应料液,再将双氯反应料液和氟化氢液体同时打入第2温区进行反应,得到双氟反应料液,经减压精馏,     

乙烯齐聚的连续化反应研究

在四元催化体系间歇釜式反应的基础上,本文对乙烯齐聚的连续化反应进行了系统研究,设计并安装了一套连续化反应装置,包括预反应器,反应器和闪蒸后处理装置。在连续化反应装置上,分别考察了催化剂进料速度,反应压力和催化剂浓度对然齐聚连续化反应的影响,同时获得了连续化反应的最佳反应条件。经过研究发现,该四元催化剂体系的间歇釜式反应的最佳反应条件,也同时是连续化反应的最佳反应条件,齐聚反应的催化活性,Ｃ的选择性     

微反应器内邻氨基苯甲酸甲酯的连续重氮化工艺

邻氨基苯甲酸甲酯（MA）的重氮盐是一种典型的重氮化合物,因其具有高化学选择性可高效合成结构复杂分子被广泛应用于现代有机合成领域。传统半间歇合成工艺中的固有缺陷以及MA重氮盐的潜在爆炸性,限制了其在工业规模上的应用。本文基于此提出了在“心形结构”的高通量微通道反应器内合成MA重氮盐的连续流工艺。在单因素实验的基础上,采用Box-Behnken design（BBD）中心组合原理构建响应面模型对工艺进行优化,研究了不同反应条件之间交互效应对反应的影响并与实验室规模的半间歇合成工艺进行了比较。结果表明,微反应器内连续重氮化合成工艺对降低因素交互效应、提高工艺可控性、抑制平行副反应有显著的效果。经优化后的最佳工艺条件为n(MA)∶n(亚硝酸钠)∶n(盐酸)=1∶1.15∶2.67,反应温度为34.62℃,停留时间为45.07s,在此条件下MA重氮盐收率可达92%,相比于半间歇合成工艺提高了10%。这种新的合成方式可有效解决传统半间歇工艺中重氮化合成体系对温度的高敏感性,避免了反应温度控制困难、高潜在热失控风险带来的安全隐患。     

径向反应器在合成碳酸乙烯酯中的应用

介绍径向反应器在合成碳酸乙烯酯中试装置应用情况。运行结果表明,在一定的工艺条件下,原料在反应器中反应得到了产品碳酸乙烯酯。但是,由于催化剂的寿命问题,使径向反应器不完善,需要进行改进。     

淤浆鼓泡反应器的开发研究 Ⅰ.间歇过程

要求实验室间歇鼓泡反应器能重复间歇搅拌釜中多段温控等优化工艺,当反应过程处于反应动力学控制时,才较易实现。两种反应器获得相同工艺条件的关键操作因素分别是表观气速和桨叶转速。这两种操作因素的临界值,包括保证催化剂完全悬浮,排除外扩散阻力等问题作为操作下限,避免鼓泡液泛作为操作上限,均需在开发研究中进行测定。实现优化工艺需要着眼于催化剂表面有足够的氢浓度,这和要求处于反应动力学控制是一致的。按 Hammer 的三维性能图对淤桨鼓泡反应器的开发放大有较大的参考意义。     

一种处理精对苯二甲酸生产废水的装置及其工艺

正哈尔滨工业大学开发出一种处理精对苯二甲酸生产废水的装置,其包括高温UAFB厌氧反应器和中温UAFB厌氧反应器,高温UAFB厌氧反应器的出水口与中温UAFB厌氧反应器2的进水口相连。此外还开发出一种处理精对苯二甲酸生产废水的工艺,废水进入高温UAFB厌氧反应器,进行第一级厌氧消化反应;废水再进入中温UAFB厌氧反应器,进行第二级厌氧消化反应。该工艺充分结合了高温处理的快速和中温处理的稳定的特性,在第一级处理中快速完成乙酸、苯甲酸等易降解有     

涓流床催化反应过程开发中的实验研究

本文介绍了以生产丁炔二醇的涓流床开发放大为背景所采用三种实验室反应器,即测定本征反应动力学用的间歇搅拌反应釜;测定大颗粒催化剂宏观反应动力学用的连续转框反应器;测定在工业涓流床喷淋密度下的床层反应动力学用的液体外循环微分反应装置.本文用幂函数对三种反应器测定的结果关联了反应速率方程式,比较确切地证实了Satterfield提出的喷淋密度和外部接触效率的关联图,并进一步探讨了温度对外部接触效率的影响.本文还以外循环微分反应装置中测定接近工业涓流床喷淋密度下的外部接触效率,结合用连续转框反应器测定的颗粒动力学模型,在绝热床中试装置中检验,得到比较满意的结果.     

微反应器内苯甲醚连续合成

苯甲醚是一种重要的溶剂和有机合成中间体,以往通过间歇反应合成,存在生产效率低下、操作周期长等问题,亟需开发连续化的生产装置和技术。提出以苯酚钠水溶液和硫酸二甲酯为原料通过连续微反应器合成苯甲醚的方法。该方法利用微混合器和局部收缩的反应管道强化反应物的混合,在近似绝热的反应条件下快速完成反应过程。报道了苯酚钠浓度、反应物流量和反应物摩尔比对于微反应器内苯酚钠转化率和硫酸二甲酯利用率的影响规律。与文献报道的间歇反应进行了对比,揭示了微反应技术的优势。     

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.