Y型分子筛结构破坏的动力学分析(英文)

Y型分子筛是催化裂化(FCC)的速率控制组分.FCC过程中,催化剂在反应器和再生器中往往面临高温水蒸气存在的苛刻环境.因此,分子筛的热稳定性和水热稳定性是催化剂最为关注的性能之一.由于FCC原料中通常含有V、Ni、Na、Fe等不同数量的金属污染物,会对催化剂造成污染及钝化.进料中存在的卟啉类有机复合物持续不断的沉积在催化剂表面,由于含钒的有机金属卟啉化合物在反应中转化形成V_2O_5,V_2O_5在水热条件下形成H_3VO_4组分,在高温水热气氛下加速分子筛骨架结构水解,破坏了Y型分子筛的晶体结构,从而降低了催化剂活性,影响产品选择性.稀土Y型分子筛在FCC中扮演重要的角色,稀土交换分子筛可以提高催化酸性、裂化活性和热与水热稳定性.此外,Na在高温水蒸气条件下也会对分子筛结构造成破坏.一方面,钠能够中和Y型分子筛B酸中心,降低催化裂化活性;另一方面,水热条件下钠的存在会加速破坏Y型分子筛的结构.有关Y型分子筛结构破坏的机理解释较多,然而该过程的动力学研究鲜有报道.反应动力学不能提供一个直接的反应机理,但是任何反应机理的提出必须符合反应动力学的数据.本文采用离子交换法分别制备了一系列不同Na含量USY,不同稀土含量USY,以及含钠和稀土的USY分子筛,通过固相动力学模型考察了上述Y型分子筛水热结构破坏活化能的变化及钒对其活化能的影响.结果表明,Y型分子筛的结构破坏存在三种路径,分别是脱铝、脱硅和La-O键的断裂.钒加速了分子筛骨架水解速率;钒钠具有协同作用,同时存在时对分子筛破坏作用更加显著;NaOH的形成是速率控制步骤;稀土稳定了分子筛的结构,降低了分子筛的水热脱铝速率;钒与定位于分子筛小笼里稀土作用,破坏分子筛的[RE-OH-RE]~(5+)的RE-O键夺取分子筛的骨架氧,导致骨架结构崩塌.由于稀土本身稳定了分子筛的结构,同时钒稀土作用时形成稳定的REVO_4固定了钒的流动性,因此钒对REY结构的影响是几种因素相互叠加和抵消的结果.     

Corrosion on continuous supercritical water oxidation for polychlorinated biphenyls

Abstract

The corrosion resistance of Hastelloy C-276 and titanium alloy G5 against C1 anion which was generated by supercritical water oxidation (scWO) of 3-chlorobiphenyl (3-PCB) in a flow reactor was investigated over a period of 336 hours at a constant pressure of 30 MPa. The condition of the scWO reaction zone was fixed at 750 K. The concentration of chlorine in the effluent collected after cooling to ambient temperature was about 850 wppm. The Hastelloy C-276 has a nominal ratio of approximately 3.7 Ni/l Cr. The Ni/Cr ratio in the effluent was the same with the nominal ratio, and the Hastelloy C-276 was proved to be corroded on the surface located between the bottom of the reactor and the cooling parts, which are under sub- and near- critical conditions of water. The corrosion rate was found to be 5 to 34mm/y in the zone where the temperature ranged from 543 K to 650 K and the corrosion spread over the whole surface of the alloy; however, one can hardly observe such a serious corrosion except the zone located in the between the reactor and the cooling part.     

Tabu-enhanced iterated greedy algorithm: A case study in the quadratic multiple knapsack problem

Iterated greedy search is a simple and effective metaheuristic for combinatorial problems. Its flexibility enables the incorporation of components from other metaheuristics with the aim of obtaining effective and powerful hybrid approaches. We propose a tabu-enhanced destruction mechanism for iterated greedy search that records the last removed objects and avoids removing them again in subsequent iterations. The aim is to provide a more diversified and successful search process with regards to the standard destruction mechanism, which selects the solution components for removal completely at random.     

基于萨格奈克/双马赫-曾德干涉原理的长途管道破坏预警技术研究

针对现有技术在灵敏度和监测距离上的限制,提出了一种基于萨格奈克/双马赫-曾德干涉原理的分布式光纤传感方案,并对其探测和定位原理进行了分析.结果表明,利用从萨格奈克干涉仪解调出的信号可以判断有无破坏行为的发生,利用两个马赫-曾德干涉仪的输出信号可以实现对破坏行为的定位,从而为长途管道的破坏预警提供了一种较为理想的方法.     

Destruction of polylactic acid microcapsules under ultrasound irradiation

Hollow microcapsules have been considered for potential applications as drug or gene carriers. This paper describes an investigation into the mechanical properties of microcapsules with a biocompatible polylactic acid (PLA) shell that can be destroyed using ultrasound irradiation. The microcapsules had a radius of 1 to 25 μm and a shell thickness of 100 nm to 3 μm, and their response to ultrasound pulses with a center frequency of 700 kHz to 2 MHz was investigated. It was found that approximately 50% of capsules with a radius of 20 μm were destroyed using pulses with a pressure amplitude of 50 kPa and a frequency of 700 kHz, which is close to the resonance frequency of the capsules.     

脉冲强激光破坏Hg0.8Cd0.2Te晶片材料的机理分析

 利用光学金相显微镜对TEA-CO₂脉冲强激光辐照的Hg_0.8Cd_0.2Te晶片表面进行了观察。在单脉冲能量为37.5 J，能量密度为937.5 J/cm²的强激光辐照下，晶片表面呈现出熔融迹象和大量的微裂纹，微裂纹密度从激光辐照区中心向外逐渐减少，裂纹沿晶体的(111)面扩展。随着脉冲连续作用次数的增加，晶片表面熔融更加剧烈，裂纹数目、裂纹深度和宽度都有所增加。分析认为：HgCdTe晶片的破坏与激光辐照能量、脉冲连续作用次数、激光场强分布、激光热应力、激光支持的燃烧波和物质的蒸发波等冲击波有关。     

ON PROPERITIES OF A SERIAL SERVICE SYSTEM OF TWO SERVICE COUNTERS WITH FINITE WAITING SPACE

（喻小军）（罗荣桂）ＯＮＰＲＯＰＥＲＩＴＩＥＳＯＦＡＳＥＲＩＡＬＳＥＲＶＩＣＥＳＹＳＴＥＭＯＦＴＷＯＳＥＲＶＩＣＥＣＯＵＮＴＥＲＳＷＩＴＨＦＩＮＩＴＥＷＡＩＴＩＮＧＳＰＡＣＥ￥ＹｕＸｉａｏｊｕｎ；ＬｕｏＲｏｎｇｇｕｉ（ＷｕｈａｎＵｎｉｖｅｒｓｉｔｙｏ...     

Modeling of deformation processes in rock massif in the vicinity of underground goafs considering the formation of discontinuity zones

The construction of mechanical-mathematical model and numerical method for the deformation processes of rock massifs with goafs and underground structures is very complex and also important task in modern rock mechanics. In this study, the mechanical-mathematical model is developed for rock massif in vicinity of underground goafs considering the internal block-layered structure of the rock massif. A new constitutive model is introduced in this study to describe the negative Poisson's ratio for the lock-layered structure. Two types of defining equations systems for studying the state of a rock massif taking into account the block-layered structure are described.Finally, several examples are given using the present mechanical-mathematical model.     

Thermostimulated creep in amorphous polyolefins. I

The thermostimulated creep of two amorphous polyolefins having the repeating unit ─(CH₂)_mC(CH₃)2─, where m = 2 and 3, was investigated from 77° to 350°. Two relaxation processes are distinguished: a secondary relaxation is observed at 138 and 113°, respectively, for m = 2 and m = 3; a primary relaxation is found around the glass transition. These relaxations have been resolved in their elementary components. From the data acquired, the mechanical losses have been calculated and compared with data from an inverted torsional pendulum. The activation energy found for the secondary relaxation—0.26 eV at 138° K for the amorphous polyolefin with m = 2 and 0.19 eV at 113° K for the polyolefin with m = 3—confirms that this relaxation mode is associated with restricted backbone motion.     

基于附加环结构的分布式光纤传感系统研究

研究了一种使用2×2耦合器将附加环耦合到萨格奈克主环上的分布式光纤传感预警系统.采用单模光纤和脉冲光源,在时域上提取光不同次经过附加环的干涉光束多重响应.理论推导和仿真试验证明,比较多重响应的幅度能够探测发生在主环里因外界破坏事件引起的振动所在位置.提出了准确定位的数学模型,其定位方法与外界作用的频率特性无关.