Synthesis and characterization of MCM-41-supported nano zirconia catalysts

Series of MCM-41 supported sulfated Zirconia (SZ) catalysts with different loadings (2.5–7.5% wt.) were prepared using direct impregnation method. The acquired solid catalysts were characterized structurally and chemically using X-RD, HRTEM, BET, FT-IR, Raman spectroscopy and TPD analysis. The acidity of the solid catalysts was investigated through cumene cracking and isopropanol dehydration at different temperatures. As the SZ loading increases, the surface acidity of the mesoporous catalysts was enhanced, this was reflected by the higher catalytic activity toward cumene cracking and isopropanol dehydration.     

Ru/MCM-41催化剂上苯的液相加氢反应

 以Si-MCM-41、Al-MCM-41(1) (n(Si)/n(Al)=15)、Al-MCM-41(2) (n(Si)/n(Al)=10)以及用NH4NO3或HAc的醇溶液分别与Si-MCM-41离子交换所得的H-MCM-41(N)和H-MCM-41(H)为载体制备了系列Ru/MCM-41催化剂。采用N2吸附、XRD和H2-TPR表征了负载Ru前后催化剂的结构及Ru在各种载体表面上的分散状态。以0.5%（质量分数）苯的环己烷溶液为模型化合物，在298K、3.0MPa反应条件下，考察了上述催化剂的苯液相加氢反应性能，并与Ru/HY、Ru/H和Pt/MCM-41催化剂进行了比较。结果表明，载体MCM-41的n(Si)/n(Al)和表面化学组成等性质对Ru在其表面上的分散状态、还原性及催化性能均有影响。对苯的转化率与反应时间的关系曲线进行拟合，发现其遵循一级动力学方程，加氢反应速率常数按照Ru/Al-MCM-41(2)41(1)4141(H)41(N)的顺序递增；Ru/Si-MCM-41较高的催化活性来自于Si-MCM-41的高比表面积和Ru的高分散性；由于载体酸性的增加，H-MCM-41负载催化剂的加氢活性进一步提高。     

Na+、K+离子交换对Co-Mo/MCM-41加氢脱硫催化剂的影响

 用偏硅酸钠和正硅酸乙酯作硅源制备了MCM-41（分别记作MCM-41(S)和MCM-41(T)）分子筛，并用Na₂C₂O₄和K₂C₂O₄对MCM-41(S)进行了碱金属离子交换改性。以质量分数0.8 %的二苯并噻吩（DBT）的十氢萘溶液为模型化合物，考察了不同MCM-41担载的Co-Mo硫化物催化剂对DBT的加氢脱硫反应性能。结果表明，MCM-41担载的Co-Mo催化剂加氢活性较低，DBT主要通过直接脱硫反应路径脱硫。其活性顺序为：Co-Mo/MCM-41(T)>Co-Mo/MCM-41(S)>Co-Mo/MCM-41(K)>Co-Mo/MCM-41(Na)。UV-Vis结果表明，部分Co与MCM-41(S)中少量Al发生相互作用，生成了CoAl₂O₄，是造成Co-Mo/MCM-41(S)活性降低的重要因素。而在Co-Mo/MCM-41(K)和Co-Mo/MCM-41(Na)中，除CoAl₂O₄物种之外，碱金属的引入还促进了Co₃O₄物种的形成，使其活性进一步降低。     

Effects of surfactant/silica and silica/cerium ratios on the characteristics of mesoporous Ce-MCM-41

Using the surfactant CTMABr (cetyltrimethyl ammonium bromide) and cerium(IV) sulfate, mesoporous Ce-MCM-41 molecular sieves were produced under a hydrothermal condition with various surfactant/silica (surfactant/Si) and silica/cerium (Si/Ce) ratios. Changes to the structural traits caused by changing the molar ratios of both surfactant/Si and Si/Ce were investigated. XRD (X-ray diffraction), FT-IR (fourier transform infrared spectroscopy), and SEM (scanning electro microscopy) were used for the characterization of prepared mesoporous samples. Among the tested molar ratios, surfactant/Si ratio of 0.5 and 0.2 showed highest values of d_1 0 0 and intensity, respectively, for the Si-MCM-41. XRD analysis also identified a quintessential hexagonal structure of Ce-MCM-41 for the Si/Ce molar ratio higher than 40 (maintaining the surfactant/Si ratio at 0.2). When cerium content was increased to have the Si/Ce molar ratio of 20, the hexagonal structure of Ce-MCM-41 was collapsed due to the structural stress of substituted cerium. FT-IR results confirmed calcination of Ce-MCM-41 and the incorporation of Ce⁴⁺ ions of cerium sulfate into the silica surface with proper removal of the surfactant. Rod-like shape with rounded edges of the prepared Ce-MCM-41 samples was identified by SEM. These results suggest surfactant/Si ratio of 0.2 and Si/Ce ratio of 40 for the production of Ce-MCM-41 with the highest level of crystallinity.     

官能团化MCM-41在分离低碳醇-水混合物中的应用

采用一步法水热合成了介孔材料氯丙基官能团化的MCM-41(Cl(CH2)3-MCM-41)、氨丙基官能团化MCM-41(NH2(CH2)3-MCM-41)、甲基官能团化MCM-41(CH3-MCM-41)和氯丙基官能团化硅胶,并考察了它们作为气相色谱固定相分离低碳醇-水混合物的情况。实验结果表明,Cl(CH2)3-MCM-41能够分离低碳醇-水混合物中的各组分,随水、甲醇、乙醇、异丙醇、正丁醇极性的减小,各分子与Cl(CH2)3-MCM-41的作用力增强,保留时间延长。氯丙基官能团化硅胶、NH2(CH2)3-MCM-41)和CH3-MCM-41均不能分离低碳醇-水混合物,表明介孔材料规则的孔道结构、表面嫁接基团等对低碳醇-水混合物的分离有重要影响。同时考察了Cl(CH2)3-MCM-41的氯丙基负载量对低碳醇-水混合物分离效果的影响,结果表明,当氯丙基的摩尔分数为15%时,分离效果最佳。     

In Situ Formation of a Novel Nanocomposite Structure Based on MCM-41 and Polyethylene

M41S materials are prepared by in situ assembly of inorganic precursors and organic template and can be viewed as nanocomposites of the siliceous phase and organic surfactant. Calcination of these precursors gives the M41S materials that have been used to prepare novel nanocomposite structures, in which the organic phase inside the nano-sized pores is isolated by the nano-sized inorganic pore walls. The nanocomposite structures can be formed by in situ polymerization of monomers inside the channels. Polymerization of ethylene takes place inside the nano-sized pores, producing the desired nanocomposite structure. The resulting polyethylene was found to be a mixture of crystalline and amorphous phases.     

Congestion pricing of multi-modal transportation systems

This paper deals with the pricing and investment decision problem of multi-modal transportation systems in which the congestion is a significant factor in the assessment of system costs. This study approaches this congestion pricing problem with a number of social welfare maximization problems, all of which have the identical structure except financial constraints. One welfare maximization problem examined in this study yields the pricing and investment decision, which can attain the first-best social optimality for multi-modal transportation systems. Other welfare maximization problems show he second-best optimal solutions that can address two policy questions in transportation economics, namely, the cross-subsidy between competing modes and peak-period congestion charges on a single highway link. Received: February 2001/Accepted: December 2001 This work was supported in part by funds from BK21 Research Division of Seoul National University for Social Infrastructure and Construction Technology.     

冷41-平14"L"型水平井轨迹优化与控制技术

冷41-平14井受地面条件的限制,靶前位移小,为保证中间套管和完井管柱的顺利下入,剖面设计为“反向造斜-稳斜-降斜-正向造斜-水平段”的“L”型。简要介绍了冷41-平14“L”型水平井的设计概况,详细介绍了该井井眼轨道优化设计原则和设计结果,以及实钻井眼轨迹连续控制技术。该井精确命中A、B靶,两靶处的井斜角、方位角和垂深等达到了设计要求,在A靶实现了软着陆。该井井眼轨道优化设计和井眼轨迹控制技术为类似水平井的井眼轨道设计和轨迹控制提供了有益的借鉴。     

Optimal estimation of parameters of dynamical systems by neural network collocation method

In this paper we propose a new method to estimate parameters of a dynamical system from observation data on the basis of a neural network collocation method. We construct an object function consisting of squared residuals of dynamical model equations at collocation points and squared deviations of the observations from their corresponding computed values. The neural network is then trained by optimizing the object function.The proposed method is demonstrated by performing several numerical experiments for the optimal estimates of parameters for two different nonlinear systems. Firstly, we consider the weakly and highly nonlinear cases of the Lorenz model and apply the method to estimate the optimum values of parameters for the two cases under various conditions. Then we apply it to estimate the parameters of one-dimensional oscillator with nonlinear damping and restoring terms representing the nonlinear ship roll motion under various conditions. Satisfactory results have been obtained for both the problems.     

Solid-state NMR as a probe of porous catalysts and catalytic processes

The power of solid-state NMR for the interrogation of porous catalytic materials is illustrated using three examples. First, for the investigation of catalytic processes occurring within the confines of a microporous catalyst NMR is shown to reveal both the details of shape-selectivity and the nature of internal surface species. Second, NMR is shown to be a powerful short-range tool to reveal precise structural information on highly disordered microporous titanosilicates. Despite long-range disorder the short-range order is maintained and can be easily studied. Finally, the same utility of probing short-range chemical phenomena is shown to be crucial for the investigation of novel-ordered-amorphous-mesoporous materials known generically as M41S. This class of material is currently one of the most important with potential catalytic application.