五取代茂基稀土配合物-活性碱金属氢化物催化的烯烃加氢反应

提出了一类以五取代茂基稀土金属配合物与活性碱金属氢化物组成的加氢催化体系。实验表明:(C_5Me_4R)_2LnCl_2Li(THF)_2+MH(Ln=Nd,Yb,R=Pr;Ln=Gd,R=Me,Pr;M=K,Na)体系都能催化α-烯烃加氢,其活性较高,如(C_5Me_5)_2GdCl_2Li-NaH体系对1-己烯加氢TON可达40min~(-1)。碱金属氢化物的种类、THF以及温度等对其催化活性均有不同的影响。这类催化剂失活很快,其原因与反应体系中的烯烃有关。

基于证据理论的虚拟力机器人网络控制

将网络与机器人相连,延伸网络的应用领域,可以实现价格低廉的远程监视与操作,而远程控制成功实现的关键在于信息的正确获得。利用Dempster-Shafer对六个超声波传感器所获取的距离信息进行融合,而后连同速度信息提供给弹簧-阻尼器系统以构建虚拟力;力的信息通过编程映射到游戏杆上,变成操纵方向的约束力。通过采用微软公司的带有力反馈的操纵杆作为力觉提示装置控制移动机器人在结构化环境下顺利运行,验证了虚拟力信息获取方法的有效性。

小湾电站坝基岩体卸荷工程地质力学研究

Dam is the key main works in the construction of water power. The success or failure of the construction of the dam mainly depends on the stability of the dam foundation. The double curvature arch dam-XiaoWan Dam is the highest one among the dams with the same type in the world, and the water thrust acted on it reaches ton, so the rock bearing capacity of dam foundation becomes more important. Because of the high and steep valley-side slope, the large scale of excavation and the complex body type of excavation, it is prominent that the problem of stress release of the rock mass in dam foundation. More great attentions should be paid for the stability and the degraded of rock properties of rock mass induced by the stress release. In this paper, the phenomena of stress release of rock mass in XiaoWan Dam foundation and its mechanisms were analyzed based on the collection of data, the detailed field engineering investigations, measurement of the rock mass and the 2D numerical calculations. The rock mass under the foundation is weak-weathered to intact, the quality of which is good. After excavation of the foundation, the rock mass near the slope surface occurred extend, stretch and stick-slip along original textures till the new fracture surface formed. Then platy structure of the rock mass takes on. The rock mass in the dam foundation occur resilience due to stress release towards free faces with the characteristics of time effect and localized deformation. In-situ measurements show that the rock mass near the surface are degraded. The stress release induced by excavation is a process of the interaction between engineering structures and geologic body. The stress release of rock mass in dam foundation is related to the changed degree of geometrical conditions. The rock near excavation surface failed nearly under uniaxial stresses. The bending-breaking mechanism of plate girder can interpret the failure model of the rock mass with platy structure in dam foundation slope. In essence, the stress release is the change of stress field including the change of directions and magnitudes of stress induced by excavation, which can induce the comedown of the safety margin. In this paper, the inducing conditions of stress release were calculated by numerical analyses. Moreover, from the point of view that the change of stress field, the coefficient of K, i.e. the variable load coefficient was proposed. Then the law of the change of it is interpreted. The distributional characteristics of fracture zone were expressed by the coefficient. The stress release of hard rock has the characteristic of localization. The measuring technique of sound wave can not reflect the small cracks in this kind of rock mass due to stress release. So, the spectral analysis method was proposed. At the same time, the application foreground in engineering of the Stockwell Time-Frequency- Spectrum method was discussed with a view to the limitation of it.

南堡油田测试资料综合评价及试油配套工艺技术研究与应用

A series of significant oil-gas exploration progresses have been achieved in Nanpu depression with 1.02 billion ton oil-gas reserves have been proven. It has been confirmed that Nanpu beach has a geologic condition to be a major field based on exhaustive research. This finding, which is integrated reservoir，great reserves, thick oil layer and high productivity in Nanpu depression, is the most excited success in Chinese oil-gas exploration in recent years. This abundant oilfield found is significant to the strategy of oil production stability in the east of China. Nanpu depression exploration is also a crucial exploration project for Petrochina. Based on the comprehensive research on Nanpu formation testing data, we reevaluate and analyze the reservoir property and the structure characteristics, and propose a series of testing technique that are suitable for Jidong oil field development. The results are summarized as follows: 1. The reservoir parameters and characters are defined by formation test data interpretation and systemic dynamic-static data comparison. 2. Based on sources analysis and statistical research related to formation contaminants, some technique measures, which can not only prevent or reduce invasion damage for different formations but also can effectively improve completion efficiency, are proposed. 3. By selecting the testing pressure drawdown, optimum working regulation and flow /shut-in duration, and adopting dynamic-static flow parameters correlation analysis to predict production, an optimum research on working regulation and flow /shut-in duration was accomplished. Optimization formation test principles suitable for any kinds of Nanpu oilfield are established, which can improve test quality, construction efficiency and data recording quality. 4. By reasonable selection of perforating gun and penetrating charge, the perforation penetration has been improved effectively and the flow channel of the oil gas have been expanded, so that the communication between formations and the wellbore is improved better. 5. One joint working procedure which combining formation test, perforation, unloading and stimulation treatment has become the dominant testing technology in the Nanpu offshore Oilfield. This combination technique can implement several procedures using one pipe string, and achieve rapid testing purpose.

中高层大气对低层大气声重波响应的分析

Acoustic Gravity waves (AGW) play an important role in balancing the atmospheric energy and momentum budget. Propagation of gravity wave in the atmosphere is one of the important factors of changing middle and upper atmosphere and ionosphere. The purpose of this dissertation is to study the propagation of gravity wave in a compression atmosphere whit means of numerical simulation and to analyze the response of middle and upper atmosphere to pulse disturbance from lower atmosphere. This work begins with the establishment of 2-D fully nonlinear compressible atmospheric dynamic model in polar coordinate, which is used ton numerically study gravity wave propagation. Then the propagation characteristics of acoustic gravity wave packets are investigated and discussed. We also simulate the response of middle and upper atmosphere to pulse disturbance of lower atmosphere in background winds or without background winds by using this model and analyze the data we obtained by using Fourier Transform (FT), Short-time Fourier Transform (STFT) and Empirical Mode Decomposition (EMD) method which is an important part of Hilbert-Huang Transform (HHT). The research content is summarized in the following: 1. By using a two-dimensional full-implicit-continuous-Eulerian (FICE) scheme and taking the atmospheric basic motion equations as the governing equations, a numerical model for nonlinear propagation of acoustic gravity wave disturbance in two-dimensional polar coordinates is solved. 2. Then the propagation characteristics of acoustic gravity wave packets are investigated and discussed. Results of numerical simulation show that the acoustic gravity wave packets propagate steadily upward and keep its shape well after several periods. 3. We simulate the response of middle and upper atmosphere to pulse disturbance of lower atmosphere in background winds or without background winds by using this model, and obtain the distribution of a certain physical quantity in time and space from earth’s surface to 300km above. The results reveal that the response of ionosphere occurs at a large horizontal distance from the source and the disturbance becomes greater with increasing of height. The situation when the direction of the background wind is opposite to or the same as the direction of disturbed velocity of gravity-wave is studied. The results show that gravity wave propagating against winds is easier than those propagating along winds and the background wind can accelerate gravity wave propagation. Just upon the source, an acoustic wave component with period of 6 min can be found. These images of simulation are similar to observations of the total electron content (TEC) disturbances caused by the great Sumatra-Andaman earthquake on December 26 in 2004. 4. Using the EMD method the disturbed velocity data of a certain physical quantity in time and space can be decomposed into a series of intrinsic mode function (IMF) and a trend mode respectively. The results of EMD reveal impact of the gravity wave frequency under the background winds.

污泥处理经济评价和污泥堆肥中氧气监测与动态分析

With the continually increase both in the amount of wastewater disposal and in the treatment rate, more and more sewage sludge has been produced. An economic estimate was taken on the different sewage sludge disposal and treatment technologies, and led to the conclusion that compost is an effective way to make sewage sludge harmless, stable and resourceable. Normally, there are several ways to treat sewage sludge, such as landfill, compost, incineration and so on. These technologies will cost 300-1000 Y per ton of sludge. Among those ways, landfill is the cheapest one and operates easily, however, it just postpones the pollution instead of eventually eliminating the pollution; The amount of the sludge will reduce dramatically after incineration, while incineration will take a very high investment in the beginning, at the same time, it's very hard to maintain running; Sewage sludge will be resourceful after composting treantment, thus makes up the treatment cost, makes composting is the most economical way. Compost production is safe when correctly used, compost is a important way to treat sewage sludge. Oxygen is an important control factor in aerobic composting that has great effects on temperature and microorganisms. The gas gathering and transfering system of an online oxygen monitoring system for composting were bettermented to prolong the monitoring system's running period. The oxygen concentration changes in various aerobic composting stage were studied, and conclusions came to that oxygen concentration changes much faster in the oxygen concentration increasing stage than that in the declining stage; the better the aerobic condition is, the sooner the monitoring system starts to work. The minimal oxygen concentration during a ventilation cycle often falls at the beginning, then ascends in the composting period; at the same time, oxygen concentration changes fast in the early composting stage(temperature increasing stage), much slower in the middle stage(continouns thermophilic stage),and seldom changes in the late composting stage(temperature declining stage). With the help of the oxygen realtime-online monitoring system, oxygen concentrations was measured. During the composting period, water contents was analyzed after sampled. It's found that water contents (WC) and Oxygen concentration can both influence the composting process, and the control rule varies in the various composting stages. Essentially, the rule that water and oxygen control the composting process comes from water counterchecks the oxygen transferring to the composting substrate. The most influential factor to the WC and to the oxygen is the components in the composting pile. In the temperature increasing stage, seldom microorganisms exist in the composting pile with low activity, thus oxygen can meet with microorganisms' need, and WC is the dominant factor. In the high temperature (continouns thermophilic) stage, composting process is controlled by WC and oxygen, essentially by WC, at the same time, their influence somehow is not remarkable. In the temperature declining stage, WC and oxygen influence the composting process little. It's also found that the composting process will differ even if under the same components, thus to equably mix the components can avoid WC focusing in some place and let the composting pile to be aerobic. In one sentence, aerobic state is the most important factor in the composting process, suitable bulking material will be useful to the composting control.

黄骅坳陷大港探区油气资源潜力与资源结构预测

Facing the problems that Dagang region of Huanghua Depression has high exploration degree and its remaining resource potential and structure are not clear, the theory of Petroleum Accumulation System (PAS) is applied to divide and evaluate the oil/gas systems quantitatively. Then, the petroleum accumulation systems are taken as units to forecast and analyse the oil/gas resources and their structure using statistical methods of sampling analysis of discovery process model and generalized pareto distribution model. The exploration benefit of the unit is estimated using exploration simulation methods. On the basis of the above study, the resource potential of Huanghua Depression is discussed.Huanghua Depression can be diveded into four petroleum accumulation systems, i.e. North PAS5 Middle Qibei PAS, Middle Qinan PAS and South PAS. Each PAS can be diveded futher into several sub- PASs. Using the basic princple of Analytical Hierarchy Process, the method of quantitative evaluation of PAS is established. Then the elements and maturity of PAS are evaluated quantitatively.Taking migration and accumulation units and sub-PASs as prediction units, sampling analysis of discovery process model and generalized pareto distribution model are applied comparatively to forecast the resource structure of eight migration and accumulation units in six PASs of medium-high exploration degree. The results of these two methods are contrasted and analyzed. An examination of X2 data of these two models from exploration samples shows that generalized pareto distribution model is more effective than sampling analysis of discovery process model in Huanghua Depression. It is concluded that minimum and maximum size of reservoir and discovery sequence of reservoirs are the sensitive parameters of these two methods.Aiming at the difficult problem of forecast in low exploration degree, by analysis of relativity between resource parameters and their possible influential geological factors, forecast models for resource parameters were established by liner regressing. Then the resource structure is forecasted in PASs of low exploration degree.Based on the forecast results, beginning with the analysis of exploration history and benefit variation, the exploration benefit variation of the above PASs is fitted effectively using exploration simulation method. The single well exploration benefit of remaining oil resource is also forecasted reasonably.The results of resource forecast show that the total oil resources ofHuanghua Depression amount to 2.28 b illion ton. By the end o f 2 003, the accumulative total proved oil reserve is 0.90 billion ton and the remaining oil resources is 1.38 billion ton. The remaining oil resource is concentrated in Kongdian-Dengmingshi, Banqiao-Beidagang, Qidong-Yangerzhuang and Baidong-Qizhong sub-PASs.

基于GIS 的乌江流域（ 贵州境内）非点源污染评价

　　水是人类生存不可或缺的资源，水环境污染问题愈来愈受到人们的重视。随着对点源污染控制能力的提高，非点源污染问题成为当前研究中的热点，而对非点源污染进行定量化研究的最直接、最有效的途径就是建立模拟模型。基于此热点问题，本文选择乌江流域（贵州境内）作为研究区，在ArcGIS 平台上建立了一个简单、快速评价流域非点源污染的方法，它考虑流域的空间异质性，且只需很少的参数。该方法用一个分辨率较高的栅格数字高程模型（DEM）将整个流域划分成100 m×100 m 的格网，计算每个栅格里产生的地表径流量和非点源污染负荷。通过模拟流域地表水流，追踪每个栅格中的水流流向，模拟非点源污染物在流域河网中的运动过程。该方法能计算一个区域水文系统年均非点源污染物的负荷，并能估算出由非点源污染在河网中产生的各污染物浓度值。 　　通过本项研究，能识别出流域内非点源污染严重区域，还可以快速模拟土地利用变化对流域非点源污染的影响，从而为流域今后的规划和综合治理提供科学依据。通过系统的研究，本文主要研究成果如下： 　　1. 建立了乌江流域（贵州境内）非点源污染数据库（空间数据库和属性数据库），这不仅有力地支撑了研究区非点源污染评价研究，同时对于在研究区开展其它方面的研究也是一个有力的支撑。 　　2. 基于Arc Hydro Tools 和DEM 自动提取的流域河网与1:25 万数字水系相比较，两者在总体上吻合较好，特别是两者的主干河道基本重合，这正是在DEM基于GIS 的乌江流域（ 贵州境内） 非点源污染评价预处理中用AGREE 算法将主干河网与DEM 融合的效果；但也有少部分地区（地形平坦处，地形坡度≤3°或受人类活动影响较大的区域）两者存在较大差异，如将红枫湖、百花水库等湖泊水库区描述成河道了，在东干渠和西干渠处，由于人工河渠改变了水流的自然方向，使得提取河网与实际河网差别很大。 　　3. 以流域内的5 个水文站为子流域出口，分别描绘相应子流域，比较自动提取流域面积与实际量测结果，结果表明自动提取的子流域面积与实际量测子流域面积非常接近，相对误差在9％以内，能达到1:25 万数据的精度要求。 　　4. 以流域内5 个子流域的地表径流量，降雨量和土地利用百分比为输入参数，利用多元回归分析工具建立流域降雨径流模型，结果表明模拟相对误差在7%以内，证明所建降雨径流模型能满足模拟需要，模拟精度较高。 　　5. 流域出口处的年均非点源总氮（TN）和总磷（TP）输出通量分别为40309 ton 和2607 ton。从流域内各大支流控制的子流域来看，野济河流域由于其中的耕地面积大（占流域面积的51.21％），以3.03％的流域面积分别贡献了4.08％和3.95％的非点源总氮（TN）和总磷（TP）负荷；而湘江流域，由于其中的林地面积占主导地位（占流域面积的68.94％），以8.45％的流域面积只分别输出了6.40％和6.06％的非点源总氮（TN）和总磷（TP）负荷。因此，对非点源污染的控制要从耕地和草地着手，需要优先治理的流域为野济河流域、三岔河流域、猫跳河流域、偏岩河流域、乌江下干流流域。 　　6. 模拟的非点源总氮（TN）和总磷（TP）浓度值在流域上游明显大于下游。比较水质监测点浓度值与对应的模拟浓度值，可以发现在贵阳站和湘江站的观测值大大超过模拟值：贵阳站的总氮（TN）浓度观测值为9.37 mg/l，模拟值为2.94mg/l，总磷（TP）浓度观测值为0.68 mg/l，模拟值为0.19 mg/l；湘江站的总氮（TN）浓度观测值为5.77 mg/l，模拟值为1.98 mg/l，总磷（TP）浓度观测值为0.27 mg/l，模拟值为0.13 mg/l。另外在思南站的总磷（TP）的观测值也大大超过模拟值，观测值为0.44 mg/l，模拟值为0.14 mg/l。观测值与模拟值之间这种巨大的差异可能暗示在这两处存在明显的总氮（TN）点源污染。而贵阳站和湘江站刚好分别位于贵阳市和遵义市市区的下游，贵阳市和遵义市是流域内最大的两个工业城市。对于观测值小于模拟值的情况，主要有两种可能的原因：①某种土地利用类型的EMC 平均值赋得过高了，或②非点源污染物在随水流运动过程中损失了一部分，如沉淀或分解等。

New progress in R&D of lower olefin synthesis

This paper gives a brief review of R&D researches for light olefin synthesis directly and indirectly from synthesis gas in the Dalian Institute of Chemical Physics (DICP). The first pilot plant test was on methanol to olefin (MTO) reaction and was finished in 1993, which was based on ZSM-5-type catalyst and fixed bed reaction. In the meantime, a new indirect method designated as SDTO (syngas via dimethylether to olefin) was proposed. In this process, metal-acid bifunctional catalyst was applied for synthesis gas to dimethylether(DME) reaction, and modified SAPO-34 catalyst that was synthesized by a new low-cost method with optimal crystal size was used to convert DME to light olefin on a fluidized bed reactor. The pilot plant test on SDTO was performed and finished in 1995. Evaluation of the pilot plant data showed that 190-200 g of DME were yielded by single-pass for each standard cubic meter of synthesis gas. For the second reaction, 1.880 tons of DME or 2.615 tons of methanol produced 1 ton of light olefins, which constitutes of 0.533 ton of ethylene, 0.349 ton of propylene and 0.118 ton of butene. DICP also paid some attention on direct conversion of synthesis gas to light olefins. A semi-pilot plant test (catalyst 1.8 1) was finished in 1995 with a CO conversion > 70% and a C(2)(=)-C(4)(=) olefin selectivity 71-74% in 1000 h. (C) 2000 Published by Elsevier Science B.V. All rights reserved.

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts were investigated by the TPR (temperature programmed reaction) method, and the active sites were studied by CO-TPD, TPSR (temperature programmed surface reaction of preadsorbed CO by H-2) and XPS techniques. The TPR results indicated that ethanol and acetaldehyde might be formed through different intermediates, whereas ethanol and methanol might result from the same intermediate. Results of CO-TPD, TPSR, and XPS showed that on the Rh-based catalyst, the structure of the active sites for the formation of C-2-oxygenates is ((RhxRhy+)-Rh-0)-O-Mn+ (M=Mn or Zr, x>>y, 2 less than or equal ton less than or equal to4). The tilt-adsorbed CO species is the main precursor for CO dissociation and the precursor for the formation of ethanol and methanol. Most of the linear and geminal adsorbed CO species desorbed below 500 K. Based on the suggested model of the active sites, detailed mechanisms for the formation of acetaldehyde and ethanol are proposed. Ethanol is formed by direct hydrogenation of the tilt-adsorbed CO molecules, followed by CH2 insertion into the surface CH2-O species and the succeeding hydrogenation step. Acetaldehyde is formed through CO insertion into the surface CH3-Rh species followed by hydrogenation, and the role of the promoters was to stabilize the intermediate of the surface acetyl species. (C) 2000 Academic Press.

Post-grafting preparation of large-pore mesoporous materials with localized high content titanium doping

A new post-grafting process, consisting of two steps of substrate preparation and sol - gel post-grafting, has been developed to prepare titanium-doped mesoporous SBA-15 material with a double-layered structure and locally concentrated titanium content at the inner pore surface. With this novel technique, the single phased and originally ordered mesostructures can be well conserved; in the conventional direct synthesis they can be partially damaged when the frameworks are doped with high content heteroatoms. Titanium species exist in an isolated, tetrahedral structure and are localized at the pore surface; this is beneficial to both reactant access and product release. Characterization with XRD, N-2 adsorption/desorption isotherms, HREM/ EDS, ICP, UV - Vis, and the newly developed UV - Raman spectroscopy confirm these results. Preliminary catalytic tests with the selective epoxidation of cyclohexene show good catalytic activity. Among them, sample TiSBA-15-10 with a Si : Ti molar ratio of 10 shows a TON value of 75 and a highest product ( epoxide) yield of 55%.