流化催化裂化反应器的技术进展

介绍并讨论了近期开发的流化催化裂化反应器,包括两段串联反应器、双提升管反应器、下行式反应器、多段进料反应器以及新型提升管反应器端口结构技术。以新型反应器为核心技术的各种催化裂化新工艺可以有效地提高催化裂化反应的转化率和选择性,减少非理想产品产率,也可以改善产品质量,生产环境友好的清洁燃料油品。此外新型提升管反应器端口结构还可以抑制设备结焦,延长流化催化裂化(FCC)装置的开工周期。     

高密度下行床-提升管耦合反应器内的气固流动行为

在新提出并建立的“下行床-提升管”耦合循环流化床装置上进行了实验研究,研究结果表明,与提高一次风率相比,提高二次风率（二次风与一、二次风之和的比值）,有利于提高颗粒循环量.当颗粒循环量达到400 kg•m^-2•s^-1时,第一提升管出口处的固含超过了20％,此时下行床内充分发展段的固含超过了5.5％,即高浓度颗粒充满了整个循环流化床系统,并且第一提升管内的颗粒径向浓度分布趋于均匀.     

下行式循环流化床用于催化裂化过程的数学模拟

采用十一集总动力学,结合气固流体力学行为和轴、径向扩散行为,建立了适合于提升管及下行式循环流化床催化裂化的数学模型,采用此模型对催化裂化过程计算的结果表明,下行床内目的产品选择性显著高于提升管,但在与工业提升管相同的操作条件下,下行床内原料转化率较低,优势不能发挥。适当增加下行床长度、增大床径、使物料循环反应、增加剂油比、提高反应温度或反应压力等可以改善下行床的反应效果。下行床用于催化裂化过程,与之较匹配的应该是具有更高活性的催化剂,研制新型高活性催化剂也是下行床推向工业的重要措施之一。     

下行床反应器热试装置设计与开发

气固并行向下流动的下行床反应器比提升管具有气固接触时间短、气固速度及浓度径向分布更为均匀、气固轴向返混大大减少、易实现高固气比操作等特点。在下行床反应器小型热试装置开发过程中,为发挥下行床的技术优势,重点研究和解决了反应器出入口结构、原料雾化、高温高流通量下固体循环量测量与控制等几个关键性的工程问题,为下行床反应器的热试研究和应用开发提供了基础。     

提升管和下行床在催化裂化过程中的比较

在综合考虑流动、反应、传质的基础上,建立了适用于模拟提升管和下行床反应器中催化裂化过程的二维返混模型,并利用正交配置法进行数值求解,得到了各产物在两种反应器内的不同浓度分布规律。这处结果源于两者流动结构和混合状况的差异。和提升管相比,由于下行床内的气固两相流动更接近平推流,气固速度和颗粒浓度径向分布均匀,气固轴向返混小,因而可得到更高的汽油收率。     

提升管-下行床耦合反应器内颗粒混合行为

引　言循环流化床中气固两相的流动有两种不同的方式 :提升管中为气固并流上行的逆重力场运动 ,下行床中为气固并流下行的顺重力场运动 .其差异表现为提升管内颗粒浓度、速度以及气体速度在径向上严重的不均匀 ,颗粒浓度概率密度分布以及速度的瞬时信号都表明了颗粒团 -空穴两相结构的存在[1] ,一些研究[2 ,3] 还发现提升管中颗粒的停留时间分布 (ＲＴＤ)曲线存在较大的拖尾甚至出现双峰 ,研究者认为提升管内存在弥散颗粒和颗粒团两种不同的混合机理 ;下行床则比提升管大大改善 ,气固速度、颗粒浓度沿径向分布要均匀得多 ,颗粒的ＲＴＤ曲线…     

重油催化裂化工艺的新进展

介绍了重油催化裂化工艺的新进展,如毫秒催化裂化工艺、下行床反应器催化裂化工艺、两段提升管催化裂化工艺、多产轻质烯烃的催化裂化新工艺、催化裂化汽油改质降烯烃新工艺等,并对重油催化裂化工艺的发展趋势进行了展望。     

高密度下行床相结构分析

在自行设计的一套高密度下行循环流化床中（80 mm ID, 高5.6 m）,对下行床内相结构进行了实验研究.实验结果显示：稀密两相时间分率的径向分布中心区域比较均匀,变化范围在10%～20%之间;轴向密相尺寸在十几毫米之间,密相内颗粒平均浓度为床层浓度的1.7倍,稀相颗粒浓度约为平均浓度的40%.在下行床中,稀密两相的转变是一渐变过程,而提升管内两相的转变是突变.通过比较高密度下行床与高密度提升管内密相特性,发现下行床内的密相因停留时间短、尺寸小和密度低而难以观察到.     

垂直气固并流上行/下行系统完全发展段的混沌研究

针对垂直气固并流上行（提升管）／下行系统（下行床）的完全发展段,使用光纤密度探头测得反映系统局部密度涨落信息的时间序列,利用确定性混沌理论进行分析,获得表征系统自由度的关联维数（D_（ml））和反映系统信息丢失速率的Kolmogorov熵（K_（ml））,并对上行和下行系统做比较研究．研究发现反映局部瞬态行为特征的D_（ml）和K_ml在上行和下行系统中一定的操作条件下具有大致相同的数值,且混沌参数与局部固含率表现出对应关系．同时局部混饨参数的径向分布对应于上行和下行系统存在的典型的径向流动结构．     

提升管-流化床耦合反应器颗粒约束返混区的流动特性及约束作用分析

针对催化汽油辅助反应器改质降烯烃工艺,在一套提升管-流化床耦合反应器大型冷态实验装置上,系统研究了提升管出口段的颗粒流动特性,通过定义约束指数R_i（R_i为颗粒约束返混区实际截面平均固含率与理论截面平均固含率之比）定量反映提升管出口分布器及流化床层的约束作用。结果表明,与常规提升管相比,耦合反应器提升管出口存在一个颗粒约束返混区,其长度主要受表观气速、颗粒循环强度及上部流化床内颗粒静床高度影响;由于出口设置了倒锥形分布器,使得颗粒约束返混区靠近提升管出口区域在表观气速较低和颗粒循环强度较大时,局部固含率最大值出现在量纲 1半径Φ＝0.7处;颗粒约束返混区的约束指数在靠近出口的过程中逐渐增大,气固流动受到分布器及上部流化床层的约束作用亦逐渐增强。     

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.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

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.