Some new triazole derivatives as inhibitors for mild steel corrosion in acidic medium

Two triazole derivatives, 3,4-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (4-DTM) and 2,5-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (5-DTM) were synthesized, and the inhibition effects for mild steel in 1 M HCl solutions were investigated by weight loss measurements, electrochemical tests and scanning electronic microscopy (SEM). The weight loss measurements showed that these compounds have excellent inhibiting effect at a concentration of 1.0 x 10(-3) M. The potentiodynamic polarization experiment revealed that the triazole derivatives are inhibitors of mixed-type and electrochemical impedance spectroscopy (EIS) confirmed that changes in the impedance parameters (R-ct and C-dl) are due to surface adsorption. The inhibition efficiencies obtained from weight loss measurements and electrochemical tests were in good agreement. Adsorption followed the Langmuir isotherm with negative values of the free energy of adsorption Delta G(ads)(o). The thermodynamic parameters of adsorption were determined and are discussed. Results show that both 4-DTM and 5-DTM are good inhibitors for mild steel in acid media.

基于随机介质理论的多尺度储层非均质性定量描述

Application of long-term exploration for oil and gas shows that the reservoir technology of prediction is one of the most valuable methods. Quantitative analysis of reservoir complexity is also a key technology of reservoir prediction. The current reservoir technologies of prediction are based on the linear assumption of various physical relationships. Therefore, these technologies cannot handle complex reservoirs with thin sands, high heterogeneities in lithological composition and strong varieties in petrophysical properties. Based on the above-mentioned complex reservoir, this paper conducts a series of researches. Both the comprehending and the quantitative analysis of reservoir heterogeneities have been implemented using statistical and non-linear theories of geophysics. At the beginning, the research of random media theories about reservoir heterogeneities was researched in this thesis. One-dimensional (1-D) and two-dimensional (2-D) random medium models were constructed. The autocorrelation lengths of random medium described the mean scale of heterogeneous anomaly in horizontal and deep directions, respectively. The characteristic of random medium models were analyzed. We also studied the corresponding relationship between the reservoir heterogeneities and autocorrelation lengths. Because heterogeneity of reservoir has fractal nature, we described heterogeneity of reservoir by fractal theory based on analyzing of the one-dimensional (1-D) and two-dimensional (2-D) random medium models. We simulated two-dimensional (2-D) random fluctuation medium in different parameters. From the simulated results, we can know that the main features of the two-dimensional (2-D) random medium mode. With autocorrelation lengths becoming larger, scales of heterogeneous geologic bodies in models became bigger. In addition, with the autocorrelation lengths becoming very larger, the layer characteristic of the models is very obvious. It would be difficult to identify sandstone such as gritstone, clay, dense sandstone and gas sandstone and so on in the reservoir with traditional impedance inversion. According to the obvious difference between different lithologic and petrophysical impedance, we studied multi-scale reservoir heterogeneities and developed new technologies. The distribution features of reservoir lithological and petrophysical heterogeneities along vertical and transverse directions were described quantitatively using multi-scale power spectrum and heterogeneity spectrum methods in this paper. Power spectrum (P spectrum) describes the manner of the vertical distribution of reservoir lithologic and petrophysical parameters and the large-scale and small-scale heterogeneities along vertical direction. Heterogeneity spectrum (H spectrum) describes the structure of the reservoir lithologic and petrophysical parameters mainly, that is to say, proportional composition of each lithological and petrophysical heterogeneities are calculated in this formation. The method is more reasonable to describe the degree of transverse multi-scale heterogeneities in reservoir lithological and petrophysical parameters. Using information of sonic logs in Sulige oil field, two spectral methods have been applied to the oil field, and good analytic results have been obtained. In order to contrast the former researches, the last part is the multi-scale character analysis of reservoir based on the transmission character of wave using the wavelet transform. We discussed the method applied to demarcate sequence stratigraphy and also analyzed the reservoir interlayer heterogeneity.

旋转轴对称介质中的qP波一阶射线追踪

Elastic anisotropy is a very common phenomenon in the Earth’s interior, especial for sedimentary rock as important gas and oil reservoirs. But in the processing and interpretation of seismic data, it is assumption that the media in the Earth’s interior is completely elastic and isotropic, and then the methods based on isotropy are used to deal with anisotropic seismic data, so it makes the seismic resolution lower and the error on images is caused. The research on seismic wave simulation technology can improve our understanding on the rules of seismic wave propagation in anisotropic media, and it can help us to resolve problems caused by anisotropy of media in the processing and interpretation of seismic data. So researching on weakly anisotropic media with rotated axis of symmetry, we study systematically the rules of seismic wave propagation in this kind of media, simulate the process with numerical calculation, and get the better research results. The first-order ray tracing (FORT) formulas of qP wave derived can adapt to every anisotropic media with arbitrary symmetry. The equations are considerably simpler than the exact ray tracing equations. The equations allow qP waves to be treated independently from qS waves, just as in isotropic media. They simplify considerably in media with higher symmetry anisotropy. In isotropic media, they reduce to the exact ray tracing equations. In contrast to other perturbation techniques used to trace rays in weakly anisotropic media, our approach does not require calculation of reference rays in a reference isotropic medium. The FORT-method rays are obtained directly. They are computationally more effective than standard ray tracing equations. Moreover the second-order travel time corrections formula derived can be used to reduce effectively the travel time error, and improve the accuracy of travel time calculation. The tensor transformation equations of weak-anisotropy parameters in media with rotated axis of symmetry derived from the Bond transformation equations resolve effectively the problems of coordinate transformation caused by the difference between global system of coordinate and local system of coordinate. The calculated weak-anisotropy parameters are completely suitable to the first-order ray tracing used in this paper, and their forms are simpler than those from the Bond transformation. In the numerical simulation on ray tracing, we use the travel time table calculation method that the locations of the grids in the ray beam are determined, then the travel times of the grids are obtained by the reversed distance interpolation. We get better calculation efficiency and accuracy by this method. Finally we verify the validity and adaptability of this method used in this paper with numerical simulations for the rotated TI model with anisotropy of about 8% and the rotated ORTHO model with anisotropy of about 20%. The results indicate that this method has better accuracy for both media with different types and different anisotropic strength. Keywords: weak-anisotropy, numerical simulation, ray tracing equation, travel time, inhomogeneity

云南岩石圈流变学及多震层孕震环境

The Study on rheology of the lithosphere and the environments of the seismogenic layer is currently the basic project of the international earthquake research. Yunnan is the ideal place for studying this project. Through the multi-disciplinary comprehensive study of petrology, geophysics, seismo-geology, rock mechanics, etc., the depth-strength profiles of the lithosphere have been firstly constructed, and the seismogenic layer and its geophysical and tectonic environments in Yunnan have been systematically expounded in this paper. The related results achieved are of the important significances for further understanding the mechanism of strong earthquake generation, dividing the potential foci and exposing recent geodynamical processes in Yunnan. Through the comprehensive contrast of the metamorphic rocks in early and middle Proterozoic outcropping on the surface, DSS data and experimental data of rock seismic velocity under high temperature and high pressure, the petrological structure of the crust and upper mantle has been studied on Yunnan: the upper, middle and lower crust is composed of the metamorphic rocks of greenschist, amphibolite and granulite facies, respectively or granitoids, diorites and gabbros, respectively, and the upper mantle composed of the peridotites. Through the contrast studies of the heat flow and epicenters of the strong earthquakes, the distribution of the geotemperature and the data of focal depth, the relationship of between seismicity and geothermal structure of the lithosphere in Yunnan has been studied: the strong earthquakes with magnitude M ≥ 6.0 mainly take place at the geothermal gradient zone, and the seismic foci densely distribute between 200～500 ℃ isogeotherms. On the basis of studies of the rock properties and constituents of the crust and upper mantle and geothermal structure of the lithosphere, the structure of the rheological stratification of the lithosphere has been studied, and the corresponding depth-strength profiles have been constructed in Yunnan. The lithosphere in majority region of Yunnan has the structure of the rheological stratification, i.e. the brittle regime in the upper crust or upper part of the upper crust, ductile regime in the middle crust or lower part of the upper crust to middle crust, ductile regime in the lower crust and ductile regime in the subcrustal lithosphere. The rheological stratification has the quite marked lateral variations in the various tectonic units. The distributions of the seismogenic layer have been determined by using the high accurate data of focal depth. Through the contrast of the petrological structure, the structure of seismic velocity, electric structure, geotemperature structure, and rheological structure and the study of the focal mechanism in the seismogenic layer, the geophysical environments of the seismogenic layer in Yunnan have been studied. The seismogenic layer in Yunnan is located at the depths of 3 ～ 20 km; the rocks in the seismogenic layer are composed of the metamorphic rocks of greenschist to amphibolite facies (or granites to diorites); the seismogenic layer and its internal focal regions of strong earthquakes have the structure of medium properties with the relatively high seismic velocity, high density and high resistivity; there exists the intracrustal low seismic velocity and high conductivity layer bellow the seismogenic layer, the geotemperature is generally 100～500 ℃ in the depth range in which the seismogenic layer is located. The horizontal stress field predominates in the seismogenic layer, the seismogenic layer corresponds to the brittle regime of the upper crust or brittle regime of the upper crust to semibrittle regime of the middle crust. The formation of the seismogenic layer, preparedness and occurrence of the strong earthquakes is the result of the comprehensive actions of the source fault, rock constituent, structure of the medium properties, distribution of the geotemperature, rheological structure of the seismogenic layer and its external environments. Through the study of the structure, active nature, slip rate, segmentation of the active faults, and seismogenic faults, the tectonic environments of the seismogenic layer in Yunnan have been studied. The source faults of the seismogenic layer in Yunnan are mainly A-type ones and embody mainly the strike slip faults with high dip angle. the source faults are the right-lateral strike slip ones with NW-NNW trend and left-lateral strike slip ones with NE-NEE trend in Southwestern Yunnan, the right-lateral strike slip ones with NNW trend and left-lateral strike slip ones with NNE trend (partially normal ones) in Northwestern Yunnan, the right-lateral strike slip ones with NWW trend in Central Yunnan and left-lateral strike slip ones with NW-NNW trend in Eastern Yunnan. Taking Lijiang earthquake with Ms = 7.0 for example. The generating environments of the strong earthquake and seismogenic mechanical mechanism have been studied: the source region of the strong earthquake has the media structure with the relatively high seismic velocity and high resistivity, there exists the intracrustal low velocity and high conductivity layer bellow it and the strong earthquakes occur near the transitional zone of the crustal brittle to ductile deformation. These characteristics are the generality of the generating environments of strong earthquakes. However, the specific seismogenic tectonic environments and action of the stress field of the seismic source in the various regions, correspondingly constrains the dislocation and rupture mechanical mechanism of source fault of strong earthquake.

胶东昆嵛山复式花岗岩体的演化—岩石学和锆石U-Pb年代学研究

Kunyushan composite granite pluton is located in northeast part of the Sulu UHP collisional belt, Jiaodong peninsula, eastern China. It is regarded as the boundary of the Jiaodong block and the Sulu UHP collisional belt. The body is unique in the Dabieshan-Sulu UHP collisional orogen for its feature of multiple intrusions of diverse types granitoid rocks in a long span after UHP the collision between the North China and the Yangtze plates in late Triassic. It can be grouped into four series on the basis of petrology and petrochemistry. They are mid-K calc-alkaline granitoids, strongly peraluminous granites, high-K calc-alkaline granitoids and syenitic granite of shoshonitic series. In this thesis, the later three types of rocks are investigated geochronologically in detail. The grain zircon U-Pb isotope dilution dating technique has been employed in this study. Zircon morphology are presented and discussion on the chemical and physical conditions of the granite formation have been carried out in addtion. Strongly peraluminous granites comprises foliated monzogranite and garnet bearing leucogranite. They occupy more than half of the area of the Kunyushan composite body. Three zircon samples of foliated monzogranites have been analyzed, they yield lower intercept ages mainly in the range of 140-150 Ma. The formation of these rocks was likely to be at 700-600 ℃, implied by zircon morphology. Two zircon samples of the garnet bearing leucogranite yield lower intercept ages from 130 Ma to 140 Ma. Zircon morphology indicate that the liquidus temperature of the magma was about 750 °C. Syenitic granite of shoshonitic series occur in the north central part of the body, and the volume is quite small contrast to other types. One zircon sample was chosen from this rock, and yield lower intercept age of 121+1.8/-2.1 Ma. Zircon morphology indicate that the liquidus temperature of this rock is up to 900 °C, which is much higher than others'. High-K calc-alkaline granitoids can be divided into two types on the basis of rock texture and structure. One is Kf-porphyritic monzogranite. It's outcrop is quite small. Zircon ages of one sample constrain the emplacement of this rock at about 112 Ma. The other is medium-grain to coarse-grain monzogranite. Zircons from it yield lower intercept age of 100.5+2.9/-4.6 Ma. The variation of zircon morphology suggest that these two monzogranites were outcomes of a single magma at different stage. The former emplaced earlier than the latter. The liquidus temperature of the magma was about 800 ℃ Inherited zircon is ubiquitous in the Kunyushan composite body. Most of the samples yield upper intercept ages of late Proterozoic. It was considered that only the Yangtze plate underwent a crustal growth during late Proterozoic among the two plates which involved into the UHP collision. Inherited zircon of about 200 Ma can also be observed in strongly peraluminous and high-K calc-alkaline granitoids. Two samples out of eight yield upper intercept ages of Achaean.

港西地区河流相砂岩油藏剩余油分布研究

The Gangxi oil field has reached a stage of high water production. The reservoir parameters, such as reservoir physical characteristics, pore structure, fluid, have obviously changed. This thesis therefore carries out a study of these parameters that control reservoir characteristics, physical and chemical actions that have taken place within the reservoirs due to fluid injection, subsequent variations of reservoir macroscopic physical features, microscopic pore structures, seepages, and formation fluid properties. This study rebuilds a geologic model for this oil field, establishes a log-interpreting model, proposes a methodology for dealing with large pore channels and remnant oil distribution, and offers a basis for effective excavation of potential oil, recovery planning, and improvement of water-injection techniques. To resolve some concurrent key problems in the process of exploration of the Gangxi area, this thesis carries out a multidisciplinary research into reservoir geology, physical geography, reservoir engineering, and oil-water well testing. Taking sandstone and flow unit as objects, this study establishes a fine geologic model by a quantificational or semi-quantificational approach in order to understand the remnant oil distribution and the reservoir potential, and accordingly proposes a plan for further exploration. By rebuilding a geological model and applying reservoir-engineering methods, such as numerical simulation, this thesis studies the oil-water movement patterns and remnant-oil distribution, and further advances a deployment plan for the necessary adjustments and increase of recoverable reserves. Main achievements of this study are as follows: 1. The Minghazhen Formation in the Gangxi area is featured by medium-sinuosity river deposits, manifesting themselves as a transitional type between typical meandering and braided rivers. The main microfacies are products of main and branch channels, levee, inter-channel overflows and crevasse-splay floodplains. The Guantao Group is dominantly braided river deposit, and microfacies are mainly formed in channel bar, braided channel and overbank. Main lithofacies include conglomerate, sandstone, siltstone and shale, with sandstone facies being the principal type of the reservoir. 2. The reservoir flow unit of the Gangxi area can be divided into three types: Type I is a high-quality heterogeneous seepage unit, mainly distributed in main channel; Type II is a moderate-quality semi-heterogeneous seepage unit, mainly distributed in both main and branch channels, and partly seen within inter-channel overflow microfacies; Type III is a low-quality, relatively strong heterogeneous seepage unit, mainly distributed in inter-channel overflow microfacies and channel flanks. 3. Flow units and sedimentary microfacies have exerted relatively strong controls on the flowing of underground oil-water: (1) injection-production is often effective in the float units of Type I and II, whilst in the same group of injection-production wells, impellent velocity depends on flow unit types and injection-production spacing; (2) The injection-production of Type III flow unit between the injection-production wells of Type I and II flow units, however, are little effective; (3) there can form a seepage shield in composite channels between channels, leading to inefficient injection and production. 4. Mainly types of large-scale remnant-oil distribution are as follows: (1) remnant oil reservoir of Type III flow unit; (2) injection-production well group of remnant oil area of Type III flow unit; (3) remnant oil reservoirs that cannot be controlled by well network, including reservoir featured by injection without production, reservoir characterized by production without injection, and oil reservoir at which no well can arrive; (4) remnant oil area where injection-production system is not complete. 5. Utilizing different methods to deal with different sedimentary types, sub-dividing the columns of up to 900 wells into 76 chronostratigraphic units. Four transitional sandstone types are recognized, and contrast modes of different sandstone facies are summarized Analyzing in details the reservoirs of different quality by deciphering densely spaced well patterns, dividing microscopic facies and flow units, analyzing remnant oil distribution and its effect on injection-production pattern, and the heterogeneity. Theory foundation is therefore provided for further excavation of remnant oil. Re-evaluating well-log data. The understanding of water-flood layers and conductive formations in the Gangxi area have been considerably improved, and the original interpretations of 233 wells have changed by means of double checking. Variations of the reservoirs and the fluid and formation pressures after water injection are analyzed and summarized Studies are carried out of close elements of the reservoirs, fine reservoir types, oil-water distribution patterns, as well as factors controlling oil-gas enrichment. A static geological model and a prediction model of important tracts are established. Remaining recoverable reserves are calculated of all the oil wells and oil-sandstones. It is proposed that injection-production patterns of 348 oil-sandstones should be adjusted according to the analysis of adaptability of all kinds of sandstones in the injection-production wells.

Enhanced anthocyanin production by repeated-batch culture of strawberry cells with medium shift

Repeated-batch cultures of strawberry cells (Fragaria ananassa cv. Shikinari) subjected to four medium-shift procedures (constant LS medium, constant B5 medium, alternation between LS and B5 starting from LS and alternation between LS and B5 starting from B5) were investigated for the enhanced anthocyanin productivity. To determine the optimum period for repeated batch cultures, two medium-shift periods of 9 and 14 days were studied, which represent the end of the exponential growth phase and the stationary phase. By comparison with the corresponding batch cultures, higher anthocyanin productivity was achieved for all the repeated-batch cultures at a 9-day medium-shift period. The average anthocyanin productivity was enhanced 1.7-and 1.76-fold by repeated-batch cultures in constant LS and constant B5 medium at a 9-day shift period for 45 days, respectively. No further improvement was observed when the medium was alternated between LS (the growth medium) and B5 (the production medium). Anthocyanin production was unstable at a 14-day shift period regardless of the medium-shift procedures. The results show that it is feasible to improve anthocyanin production by a repeated-batch culture of strawberry cells.

Continuous oxygen ion transfer medium as a catalyst for high selective oxidative dehydrogenation of ethane

An oxygen permeable mixed ion and electron conducting membrane (OPMIECM) was used as an oxygen transfer medium as well as a catalyst for the oxidative dehydrogenation of ethane to produce ethylene. O2- species transported through the membrane reacted with ethane to produce ethylene before it recombined to gaseous O-2, so that the deep oxidation of the products was greatly suppressed. As a result, 80% selectivity of ethylene at 84% ethane conversion was achieved, whereas 53.7% ethylene selectivity was obtained using a conventional fixed-bed reactor under the same reaction conditions with the same catalyst at 800 degreesC. A 100 h continuous operation of this process was carried out and the result indicates the feasibility for practical applications.

Formulation of a basal medium for primary cell culture of the marine sponge Hymeniacidon perleve

Marine sponge cell culture is a potential route for the sustainable production of sponge-derived bioproducts. Development of a basal culture medium is a prerequisite for the attachment, spreading, and growth of sponge cells in vitro. With the limited knowledge available on nutrient requirements for sponge cells, a series of statistical experimental designs has been employed to screen and optimize the critical nutrient components including inorganic salts (ferric ion, zinc ion, silicate, and NaCl), amino acids (glycine, glutamine, and aspartic acid), sugars (glucose, sorbitol, and sodium pyruvate), vitamin C, and mammalian cell medium (DMEM and RPMI 1640) using MTT assay in 96-well plates. The marine sponge Hymeniacidon perleve was used as a model system. Plackett-Burman design was used for the initial screening, which identified the significant factors of ferric ion, NaCl, and vitamin C. These three factors were selected for further optimization by Uniform Design and Response Surface Methodology (RSM), respectively. A basal medium was finally established, which supported an over 100% increase in viability of sponge cells.