Axial coordination effects of pyridine on the electrochemistry of (TPP)Co in 1,2-dichloroethane solution

The electrochemistry of (TPP)Co in the presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. With the addition of pyridine to the solution, the reduction peaks of the axial complex compounds, (TPP)Co(III)(Py) and (TPP)Co(III)(Py)(2) were observed. It was found that the reduction peak of Co(II)/Co(I) shifted to about -1.20V (SCE) with the increase of added pyridine. The new reduction peak may be attributed to the direct reduction of the axially complex (TPP)Co(II)(Py).

STUDY OF THE ELECTRODE PROCESS OF HEMOGLOBIN AT A POLYMERIZED AZURE A FILM ELECTRODE

The electrochemically polymerized azure A film electrode is reported. The resulting film on a platinum electrode surface was analyzed with electron spectroscopy for chemical analysis (ESCA). The heterogeneous electron transfer processes of hemoglobin at the polymerized azure A film electrode have been investigated using in situ UV-visible spectroelectrochemistry. The formal potential (E-degrees') and electron transfer number (n) of hemoglobin were calculated as E = 0.088 V versus NHE (standard deviation +/- 0.5, N = 4) and n = 1.8 (standard deviation +/- 0.5, N = 4). Exhaustive reduction and oxidation electrolysis are achieved in 80 and 380 seconds, respectively, during a potential step between -0.3 and +0.3 V. A formal heterogeneous electron-transfer rate constant (k(sh)) of 3.54(+/- 0.12) X 10(-6) cm/s and a transfer coefficient (alpha) of 0.28(+/- 0.01) were obtained by cyclic voltabsorptometry, which indicated that the poly-azure A film electrode is able to catalyze the direct reduction and oxidation of hemoglobin.

螺旋桨驱动UUV推进系统研究

为了实现水下机器人(UUV,Unmanned Underwater Vehicle)的高精度控制,深入研究了螺旋桨驱动UUV推进系统各个环节运行机理,并建立了它们各自的数学模型,包括PWM模块、直流永磁电机、螺旋桨、舵的数学模型。多功能仿真试验和湖试试验的系统响应曲线基本吻合,一方面表明本文建立的推进系统模型的正确性,另一方面体现了在多功能仿真平台上调试的控制策略和控制器参数具有很大的可信度。

油气、微生物与砂岩型铀矿形成关系研究——以东胜铀矿床和钱家店铀矿床为例

Sandstone-type uranium deposits are frequently found close to oil fields or uraniferous sandstones contain bitumen or petroleum. However, few evidence has been presented to indicate the association of uranium mineralization with petroleum oxidation. Thus, Dongsheng uranium deposit in Ordos Basin and Qianjiadian deposit in Kailu Basin are taken for examples to solve the puzzle. Integration data from sedimentary petrology, mineralogy, race elements geochemistry, isotope geochemistry and organic geochemistry, the uranium and petroleum sources, and diagenetic paragenesis of the host sandstone are analyzed, and then the genetic relationship between microbes, petroleum and uranium deposits are discussed. The observation under microscope shows that the host sandstone samples from Middle Jurassic Zhiluo Formation in the Dongsheng deposit contained different kinds of metamorphic rock fragments, which should have been derived form outcrops north to this basin. The LREE/HREE ratios of gneiss and amphibolite sampled from outcrops were close to the highest and the lowest LREE/HREE ratios of the sandstones with well-compared chondrite-normalized REE patterns, respectively. So these results consistently indicated that parent rocks of sandstones were mainly contributed from these two kinds of metamorphic rocks. There was very high Th/U ratio for granite gneiss, which was a mainly potential U resource. Hydrocarbon inclusions and adsorbed hydrocarbons are observed under fluorescence microscope in the host sandstone of Dongsheng uranium deposit, suggesting that the sandstones may have been utilized as oil migration pathways. Based on biomarker parameters, it is indicated that the inclusion oils and adsorbed hydrocarbons were marginally mature to mature, and were derived from humic-sapropel type organic matter under poor reducing freshwater to semi-saline environment. The features are similar to those of organic matter extracted from Triassic sandstone and source rock, but are different from that of cretaceous sandstone. Thus, it can be concluded that the inclusion oils and adsorbed hydrocarbons were mainly derived from Triassic lacustrine facies source rock. Observation results under Scanning Electron Microscopy and Electron Microprobe with Energy Spectrum Analysis show that, in Dongsheng area, the main uranium ore mineral is coffinite. The coffinite is intimately intergrown or coexists with pyrite and calcite, thus, the solution during mineralization stage is inferred to be alkaline. The alkaline environment is not favored for uranium to be pre-concentrated by absorption, and then be reduced abiogenetically. δ34S of pyrite and δ13C of calcite indicate that pyrite was formed by bacterial sulfate reduction (BSR) and part of the carbon of calcite has been dirived from oxidation of petroleum, respectively. Additionally, petroleum is found biodegraded. All the lines of evidence consistently indicate that petroleum was involved in uranium mineralization. Coffinite with microbe-like structures is found in the high U sandstone samples and is composed of nanoparticles, indicating the coffinite is biogenic. The conclusion are also supportted by laboratory experiment studies, which have shown that SRB are capable of utilizing U(VI) as the preferred electron acceptor for respiration and reduce U(VI) to U(IV) directly, coupled the oxidaton of organic matter and sulfate reduction. Based on the research results mentioned above, in the Dongsheng area, coffinite is likely to have formed by mixing of brine containing petroleum derived from Triassic with uranium-bearing meteoric water from outcrops north to Ordos Basin. SRB utilize hydrocarbon as carbon source, and directly reduce U(VI) resulting in precipitation of coffinite. The product of metabolism, H2S and CO2, was precipitated as pyrite and calcite during mineralization stage. Petroleum in fluid inclusions and adsorbed type in host sandstone from Lower Cretaceous Yaojia Formation in Qianjiadian uranium deposit, Kailu Basin, are derived from Jurassic Jiufotang Formation in this basin and the uranium mineral consists mainly of pitchblende. The δ34S and δ13C values of pyrite and calcite during mineralization stage indicate SRB have likely degraded petroleum, which is similar to that of Dongsheng deposit. The alkaline environment as indicated by the diagenetic mineral assemblage calcite, Fe dolomite, pyrite and pitchblende deposit suggests that U ore in the Qiangjiajiadian has a similar origin, i.e., direct reduction by SRB. However, less part of pitchblende is intergrown with kaolinite, suggesting the solution during mineralization stage is acidic. The environment is favorable for U(VI) to be adsorded on quartz or other mineral, and then reduced by H2S produced by SRB. Thus, it can be concluded that U(VI) reduction with petroleum oxidation by SRB and other microbes is an important ore-forming mechanism in petroleum-related sandstone-type uranium deposits. The finding is significant in that it provides a theoretical basis for exploration of both uranium and petroleumr.

西峰油田特低渗透油藏渗流机理及开发对策研究

Micro-pore-throat, micro-fracture and low permeability are the most obvious characters of Xifeng ultra-low permeability reservoir, and threshold pressure gradient and medium deformation during the period of oilfield developing results non-linear seepage feature of the formation liquid flowing in the porous medium underground. It is impossible to solve some problems in the ultra-low permeability reservoir development by current Darcy filtration theory and development techniques. In the view of the characters of ultra-low permeability and powerful-diagenesis and fracture up-growth, the paper quantitatively characterizes of through-going scope for reservoir parameters together with some materials such as similarity field outcrop, rock core, drilling, well logging and production dynamic, which provides geological base for further development adjustment. Based on the displacement experiment of different kinds of seepage fluid and oil-water two phases, this paper proves the relationship between threshold pressure gradient and formation permeability in experiment and theory, which is power function and its index is about -1. The variation rule and the mechanism of oil-water two phases threshold pressure gradient are studied. At the same time, based on the experiment of medium deformation, the variation rule of formation physical property parameters and the deformation mechanism are researched, and the influential factors on the medium deformation are analyzed systematically. With elastic unsteady filtration theory, nonlinear mathematical models of the steady and unsteady flow of single phase as well as horizontal well flow and oil-water two phases flow are deduced with the influence of nonlinear factors including threshold pressure gradient and media deformation. The influences of nonlinear factors upon well deliverability and reservoir pressure distribution as well as the saturation variation pattern of oil-water front are analyzed. By means of the researches such as reasonable well pattern, reasonable well array ration, artificial fracture length optimization advisable water flood timing and feasibility of advanced water flooding, it is necessary to find out effective techniques in order to improve development result of this kind of reservoir. This research result develops and improves on low-velocity nonlinear seepage theory, and offers ways to study similar kind of reservoir; it is meaningful to the development of the ultra-low permeability oil and gas reservoir.

油藏动态模型和剩余油分布模式

This paper belong to national "973" technological project undertaken by Shengli Oilfield. Work area is composed of turbidite reservoir of S212 and delta reservoir of S283 of Sheng2 unit in Shengtuo Oilfield that has a 36 years water injection development history. Change of the macroscopic, microscopic and filterational parameters and its mechanism have been studied in the 4 water-cut stages i.e. the primary, moderate, high and supper-high stage by using multi-disciplinary theories and approaches, computer techniques and physical simulation comprehensively. Dynamic reservoir models to different water-cut stages have been established. The study of forming mechanism and distribution of residual oil revealed the main types and spatial distribution of residual oil in different water-cut stages and the distribution mode has also been built up. Macroscopic, microscopic and filterational parameters selecting principle, optimizing and selecting standard, matching standard and laws and related database of various dynamic parameters in different water-cut stages have been established, which laid good basis for revealing reservoir macroscopic, microscopic and filterational parameters' dynamic change and residual oil distribution. The study indicated that in general, the macroscopic, microscopic and filterational parameters will slowly increase and become better in both shallow turbidite and delta reservoirs with the increasing of water cut, but different reservoirs have their own characteristics and change laws. Parameters of I~2 unit, whose petrophysical properties are better, increase more quickly than 8~3, whose petrophysical properties are more unfavorable. The changes was relatively quickly in high water-cut stage, while relatively slowly from primary to moderate and from high to supper-high water-cut stage. This paper firstly put forward that reservoir macroscopic, microscopic and filterational parameters are controlled by dynamic geological function of reservoir fluid, which is considered the major reason of reservoir parameters' dynamic changes and residual oil formation and distribution during reservoir development. Physical simulation of filterational parameters verified that forming mechanism and distribution of residual oil in different water-cut stages are also controlled by dynamic geological function of reservoir fluid. The idea of fluid geological function during reservoir development developed the theory of development geology, and has important practical values. This paper firstly constructed dynamic geological and mathematical models and five modes of residual oil distribution in Shengtuo Oilfield, and achieved four-dimensional forecast of residual oil distribution in different watercut stages. Dynamic changes and mechanism of macroscopic, microscopic and fliterational parameters of reservoir and their change process have been revealed. Forecast of residual oil distribution has been achieved by computers. This paper established the related theories, approaches and techniques for residual oil study, characterization and in different water-cut stages, and realized dynamic forecast of residual oil. It gained remarkable economic benefit and social effect in guiding field development. These theories and techniques had important meaningfulness for residual oil prediction in the terrestrial faulted basins not only in Shengli Oilfield but also in the east of China. Furthermore, this study has developed the theory of development geology.

Insight into permeability of protein through microcapsule membranes

The objective of this paper is to analyze the characteristics of protein permeability in alainate-polylysine-alginate (APA) and alginate-chitosan-alginate (ACA) microcapsules by mathematical models based on the balance of chemical potential. The comparison between calculated results and experimental data shows that the models can describe the process of protein diffusion from microcapsule and protein release into microcapsule successfully. The influences of membrane composition on the permeability of ACA microcapsule have been investigated and analyzed. The effect of resistance on the mass transfer is further analyzed theoretically with the aid of mathematical modeling. (c) 2005 Elsevier B.V. All rights reserved.