DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN A HOLLOW FIBER MEMBRANE REACTOR†

A hollow fiber membrane reactor, which resembles a tube-and-shell heat exchanger, was developed for homogeneous catalytic reactions with gas reactants and products. The gas stream flows through the tube side while the reaction takes place in the catalyst solution which fills the shell side. The separation load of product from the catalyst solution can be reduced by using a hollow fiber membrane reactor instead of a conventional bubble column reactor. The reactor operates in a plug-flow pattern with a large mass transfer area per unit volume of catalyst solution

This concept was investigated experimentally using the direct oxidation of ethylene to acetaldehyde reaction in an aqueous solution of palladium (H) chloride-cupric chloride with a silicone rubber membrane reactor and a polypropylene membrane reactor. It was experimentally demonstrated that membrane reactors could achieve higher production rates per unit volume of catalyst than the conventional sparged reactor. The experimental data were in good agreement with the predictions by the mathematical model. The conditions under which the membrane reactor will be more advantageous than the conventional sparged reactors can be readily ascertained with the analytical solution of the simplified membrane reactor model.     

A new LCL-lens array with electrodes of interlaced structure to be applied for auto-stereoscopic 3D displays

A new design of the liquid crystal lenticular (LCL) lens array with interlaced electrodes is proposed to realize an auto-stereoscopic 3D display. The structure of interlaced electrodes aims to generate a desired non-uniform electric filed to improve the focusing ability of the LCL-lens array with lower voltage drives. This paper is organized as first to describe the design criteria of a lenticular lens sheet for wide extended graphics array LCD panel. Based on the designed lenticular lens array, an LCL-lens array with proposed interlaced electrodes is next designed. The fabrication and the detailed structure are given. A series of experiments are then conducted and successfully verify the focusing capability and desired 3D display functions, that is, to separate two images to right and left eyes. Also, the developed auto-stereoscopic 3D display is able to adapt to varied viewer locations with favorable imaging quality.     

Mesoporous silica with short-range MFI structure

A new type of mesoporous silica has been prepared which showed 780 m²/g of BET surface area and 0.6 ml/g of primary mesopores narrowly distributed around 4.2 nm. More importantly however, is that it showed short-range zeolite crystallinity as demonstrated by FTIR and XRD analysis, and hydrophobicity as demonstrated by water and n-hexane adsorption.

This material was synthesized via a dual-template, three-step hydrothermal–flocculation–steaming synthesis procedure developed by us recently. Briefly, MFI nanoprecursors (NPs) were first prepared by a low-temperature hydrothermal step using TPAOH as template for zeolite structure, and then flocculated using a surfactant that served as the template for the mesopores. The collected NPs are mesoporous silica exhibiting short-range MFI domains when directly calcined. However, the steaming step promoted the crystallization of the NPs and created uniform mesopores. It was found that almost every detail in these procedures affected the properties of the final product. The most important variables, however, were identified as the duration the flocculants were kept in contact with the liquid phase, and the humidity under which the steaming was conducted. By properly adjusting the procedures, the said mesoporous silica, as well as nanocrystals having high external surface area, could be produced at will.     

Solid-state NMR studies on phase behavior and motional mobility in binary blends of polystyrene and poly(cyclohexyl methacrylate)

The phase behavior and motional mobility in binary blends of polystyrene (PS) and poly(cyclohexyl methacrylate) (PCHMA) have been investigated by solid state ¹³C NMR techniques. The blend miscibility has been studied by examining the ¹H spin-relaxation times in the laboratory frame (T₁^H) and in the rotating frame (T_1ρ^H) for the PCHMA/PS blends with various compositions and pure components. The T_1ρ^H results show that PCHMA and PS are intimately mixed at the molecular level within the blends at all compositions. In addition, according to the results of carbon T_1ρ relaxation time measurements, we conclude that mixing is intimate enough to cause a reduction in local chain mobility for PS, but an increase in side chain mobility for PCHMA.     

Nanosized silica‐supported metallocene/MAO catalyst for propylene polymerization

A nanosized silica particle was used as the support to prepare an Et[Ind]₂ZrCl₂/MAO catalyst for propylene polymerization of polypropylene. The catalyst and the polymer produced were characterized with nitrogen adsorption, ICP, DSC, SEM, TEM, XRD, solution viscometer, ¹³C NMR and optical microscopy. The effects of polymerization temperature and [Al]/[Zr] ratio on catalyst activity and polymer melting point were investigated. Under identical reaction conditions, nanosized catalyst exhibited better polymerization activity than the microsized catalyst (e.g., the former had 64% higher activity than the latter at the optimum polymerization temperature (50°C) and [Al]/[Zr] = 570). DSC results indicated that polymer melting point increased with the increase of [Al]/[Zr] ratio and with the decrease of polymerization temperature. XRD results showed that the percentage of γ crystals increased with decreasing [Al]/[Zr] ratio. Electron microscopic results showed that the polymer particle size increased with increasing polymerization temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2573–2580, 2006     

Equilibrium and kinetic studies of the extraction of chelated copper(II) anions with Aliquat 336

The equilibrium and kinetics of solvent extraction of Cu²⁺ from aqueous solutions containing equimolar EDTA with Aliquat 336 in n‐decanol and kerosene at 298 K were investigated. The concentrations of Cu²⁺ (8–50 mol m^?3), Cl^? (5–60 mol m^?3), and Aliquat 336 (20–100 mol m^?3) were varied. A semi‐empirical model with three parameters was proposed to describe the equilibrium behavior, in which the non‐idealities in both aqueous and organic phases were considered. Over the ranges studied, the model agreed reasonably well with the experimental data (standard deviation, 15%). The forward and backward reaction rate constants were determined as (5.31 ± 0.16)×10^?6 m^9/4 mol^?3/4 s^?1 and (2.62 ± 0.09)×10^?7 s^?1, respectively, at 298 K. An interfacial reaction mechanism was proposed, which revealed that the reaction between the chelated anions and trimeric amine molecules at the interface was rate limiting. The derived rate laws were consistent with the experimental results. © 2002 Society of Chemical Industry     

Capillary and slit flow behavior of concentrated solutions of a rod-like polymer

This paper is concerned with the flow behavior of isotropic solutions of the rod-like polymer, poly(p-phenyleneterephthalamide) (PPT), in 100 percent sulfuric acid. Studies include entry flow visualization in a slit die and solution fracture, and die swell in capillaries and a slit die. It was observed that solutions of PPT exhibit nearly negligible die swell, a slip-stick type of fracture that disappears at high shear rates, and radial entry flow patterns similar to Newtonian fluids. Fracture was associated with the plateau in the shear stress vs shear rate curve. Because values of the wall shear stress (τ_w.) obtained from capillary measurements were in good agreement with those obtained from a cone-and-plate rheometer and values of the loss modulus (G″) obtained from small-strain dynamic oscillatory measurements, it is believed that the rheological properties lead to the flow instability. These results are in agreement with the predictions of a recent theory by Doi and Edwards for concentrated solutions of rod-like molecules. Data are also presented for a flexible chain polyamide, nylon 6,6, in 100 percent H₂SO₄ for the purpose of comparing the flow characteristics of rigid and flexible chain polymers.     

Li NMR, ionic conductivity and self-diffusion coefficients of lithium ion and solvent of plasticized organic-inorganic hybrid electrolyte based on PPG-PEG-PPG diamine and alkoxysilanes

Organic-inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO₄ via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by weight). The cross-linked hybrid network shows no solvent exudation and retains a large amount of plasticizer over 70 wt.% in stable state. The in situ built in silica network provides the hybrid electrolytes with good mechanical properties. The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 4.0 × 10⁻³ S/cm at 30 °C. Variable temperature ⁷Li-{¹H} magic angle spinning (MAS) NMR demonstrated that the Li⁺ cations can be complexed by the polymer network as well as by the plasticizing solvents, but not with the incorporated silica network. Furthermore, the ⁷Li chemical shift change indicated a progressive change in the lithium coordination from lithium-polymer to lithium-solvent with increasing temperatures. The role of the solvents and the mobility of the lithium ions were investigated by pulsed gradient spin echo (PGSE) NMR measurements to elucidate the behavior of the ionic conductivity.     

基于融合特征的虚假评论检测方法

针对现有虚假评论检测方法未充分利用用户历史行为中蕴含的动态信息,首先利用时序分析模型从这些动态信息中挖掘能够刻画用户行为的动态特征;其次,融合这些动态特征与用户层面静态特征发现可疑用户,并将用户可疑概率传播至用户所发表评论得到评论可疑概率;最后,融合评论可疑概率与评论层面静态特征形成融合特征,使用PU-Learning分类策略实现虚假评论的检测。真实数据集上的实验表明,本文方法的性能优于现有方法。     

嵌入式视觉的测距系统设计

行车操作人员在实际操作过程中,会出现对与之相邻障碍物之间的距离太近而不能及时规避情况,导致碰撞事故的发生.针对这一问题,笔者构建了以ARM11微处理器为核心,以USB摄像头为图像采集设备的测距系统,在基于机器视觉和图像处理的基础上,将单目视觉和激光技术相结合,考虑对应点匹配和单个特征点提取误差对测量结果影响,将激光点作为特征点的单目视觉测距的方法.实验结果表明,该系统能有效的测量与障碍物的距离,测量准确,可靠性高且满足实时性要求.