Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.

海拉尔盆地贝尔凹陷基岩潜山特征及储层预测

The lithology of the buried hill of Triassic Budate group in Beier depression is epimetamorphic clastic rock and volcanic clastic rock stratum. Recently the favorable hydrocarbon show was discovered in buried hill of base rock, and large-duty industrial oil stream was obtained in some wells in Beier depression. Based on the information of seismos and wells, the tectonic framework, tectonic deformation times and faulted system of the Beier depression are comprehensively studied, then configuration, evolutional history, genetic type and distributed regularity of buried hill are defined. According to observing description and analysis of core sample, well logging and interpretive result of FMI, the lithological component, diagenetic type and diagenetic sequence of buried hill reservoir are confirmed, then reservoir space system of buried hill is distinguished, and vegetal feature, genetic mechanism and distributed regularity of buried hill fissure are researched, at the same time the quantitative relationship is build up between core fissures and fissures interpreted by FMI. After that fundamental supervisory action of fault is defined to the vegetal degree of fissure, and the fissure beneficial places are forecasted using fractal theory and approach. At last the beneficial areas of Budate group reservoir are forecasted by reservoir appraisal parameters optimization such as multivariate gradually regression analysis et. al. and reservoir comprehensive appraisal method such as weighing analyze and clustering procedure et. al. which can provide foundation for the next exploratory disposition. Such production and knowledge are obtained in this text as those: 1. Four structural layers and two faulting systems are developed, and four structural layers are carved up by three bed succession boundary surfaces which creates three tectonic distortional times homology. Three types of buried hill are divided, they are ancient physiognomy buried hill, epigenetic buried hill, and contemporaneous buried hill. 2. Reservoir space of Budate buried hill is mainly secondary pore space and fissure, which distributes near the unconformity and/or inside buried hill in sections. The buried hill reservoir experienced multi-type and multi-stage diagenetic reconstruction, which led to the original porosity disappeared, and multi secondary porosity was created by dissolution, superficial clastation and cataclasis et. al. in diagenetic stage, which including middle crystal pore, inter crystal pore, moldic pore, inter particle emposieu, corrosion pore space and fissure et. al. which improved distinctly reservoir capability of buried hill. 3. The inner reservoir of buried hill in Beier depression is not stratigraphic bedded construction, but is fissure developing place formed by inner fault and broken lithogenetic belt. The fissures in inner reservoir of buried hill are developed unequally with many fissure types, which mainly are high angle fissure and dictyonal fissures and its developing degree and distribution is chiefly controlled by faulting. 4. The results of reservoir comprehensive evaluate and reservoir predicting indicates that advantageous areas of reservoir of buried hill chiefly distributes in Sudeerte, Beixi and Huoduomoer, which comprehensive evaluate mainly Ⅱand Ⅲ type reservoir. The clues and results of this text have directive significance for understanding the hydrocarbon reservoir condition of buried hill in Beier depression, for studying hydrocarbon accumulated mechanism and distributed regularity, and for guiding oil and gas exploration. The results of this text also can enrich and improve nonmarine hydrocarbon accumulated theory.

三峡库区巴东组泥灰岩溶蚀作用与岩体力学性质弱化研究

Abstract The karsrt erosion engineering geology became a highlight problem in recent years, in particularly, the karst erosion of marlite of Badong formation made the rock mechanics weaken in Three Gorges Reservoir area, which reduces the safety of slope. During the immigrant construction, many high slopes have been formed, whose instabilities problems pose serious threats to the safety of the people and properties. The accidents of the slope failure take place now and then. By testing, it has been found that the karst erosion pattern and dissolution rate of marlite are not weaker than that of the pure limestone. Furthermore, owning to the weathering and unloading, the karst erosion of the marlite will reach certain depth of the slope, which is named infiltrated karst erosion. The karst erosion made the rock mass quality of slope or foundation worse in a large scale. The karst erosion geological disasters, taken place or not, has become the main restrictive factors to the social stability and economic development. Thus the karst erosion process and mechanism of marlite of Badong formation are studied as the main content of this dissertation. The weakening characteristic of rock mass mechanics parameters are studied along with the rock mass structure deformation and failure processes in the course of the karst erosion. At first, the conditions and influencing factors of the karst erosion are analyzed in the investigative region, on the basis of different karst erosion phenomenon of the marlite and different failure modes of slope. Then via indoor the karst erosion tests, it is analyzed that the karst erosion will change the rock mass composition and its structure. Through test, the different karst erosion phenomena between micro and macro have been observed, and the karst erosion mechanism of the marlite has been summarized. Damage theory is introduced to explain the feature of dissolution pore and the law of crack propagation in the marlite. By microscope and the references data, it can be concluded that the karst erosion process can be divided into rock minerals damage and rock structural damage. And the percent of karst erosion volume is named damage factor, which can be used to describe the quantify karst erosion degree of marlite. Through test, the rock mechanical properties in the different period of karst erosion are studied. Based on the damage mechanics theory and the test result, the relation between the karst erosion degree of marlite and weakening degree of mechanical properties is summarized. By numerical simulations, the karst erosive rock mass mechanics is verified. The conclusion is drawn as below: to the rock mass of marlite, the karst erosion damage made mechanics parameters variation, the deformation modulus, cohesion, and inter friction angle reduce as the negative exponent with the increasing of the karst erosion volume, however, the Poisson ratio increases as the positive exponent with the karst erosion volume increasing. It should be noticed that the deduced formulations are limited to the test data and certain conditions. It is suitable to the rock mass parametric weakening process after the karst erosion of marlite in Three Gorges Reservoir area. Based on the failure types of marlite slope in the field, the karst erosion and weathering process of rock mass are analyzed. And the evolution law of deformation and failure of the marlite mass is studied. The main failure feature of the marlite slope is the karst erosive structure subsidence mode in Three Gorges Reservoir area. The karst erosive structure subsidence mode is explained as follows: the rock mass undergoes the synthetic influence, such as weathering, unloading, corrosion, and so on, many pores and cavities have been formed in the rock mass interior, the rock mass quality is worsen and the rock mass structure is changed, and then the inherent structure of rock mass is collapsed under its gravity, therefore, the failure mode of compaction and subsidence take place. Finally, two examples are used to verify the rock mass parameters in Three Gorges Reservoir area, and the relationship between the marlite slope stability and the time of karst erosion is proposed.

火成岩储层裂缝识别、预测理论与方法研究－以济阳坳陷火成岩油藏为例

Since 1970s, igneous reservoirs such as Shang741, Bin674 and Luol51 have been found in Jiyang depression, which are enrichment and heavy-producing. Showing good prospect of exploration and development, igneous reservoirs have been the main part of increasing reserves and production in Shengli oilfield. As fracture igneous reservoir being an extraordinary complex concealed reservoir and showing heavy heterogeneity in spatial distribution, the study of recognition, prediction, formation mechanism and the law of distribution of fracture is essential to develop the reservoir. Guided by multiple discipline theory such as sedimentology, geophysics, mineralogy, petroleum geology, structural geology and reservoir engineering, a set of theories and methods of recognition and prediction of fractured igneous rock reservoir are formed in this paper. Rock data, three-dimensional seismic data, log data, borehole log data, testing data and production data are combined in these methods by the means of computer. Based on the research of igneous rock petrography and reservoir formation mechanism, emphasized on the assessment and forecast of igneous rock reservoir, aimed at establishing a nonhomogeneity quantification model of fractured igneous rock reservoir, the creativity on the fracture recognition, prediction and formation mechanism are achieved. The research result is applied to Jiyang depression, suggestion of exploration and development for fractured igneous rock reservoir is supplied and some great achievement and favourable economic effect are achieved. The main achievements are gained as follows: 1. The main facies models of igneous rock reservoir in JiYang depression are summarized. Based on data and techniques of seism, well log and logging,started from the research of single well rock facies, proceeded by seismic and log facies research, from point to line and line to face, the regional igneous facies models are established. And hypabyssal intrusion allgovite facies model, explosion volcaniclastic rock facies model and overfall basaltic rocks facies model are the main facies models of igneous rock reservoir in JiYang depression. 2. Four nonhomogenous reservoir models of igneous reservoirs are established, which is the base of fracture prediction and recognition. According to characteristics of igneous petrology and spatial types of reservoir, igneous reservoirs of Jiyang depression are divided into four categories: fractured irruptive rock reservoir, fracture-pore thermocontact metamorphic rock and irruptive rock compound reservoir, pore volcanic debris cone reservoir and fracture-pore overfall basaltic rock reservoir. The spatial distribution of each model's reservoir has its features. And reservoirs can be divided into primary ones and secondary ones, whose mechanism of formation and laws of distribution are studied in this paper. 3. Eight geologic factors which dominate igneous reservoirs are presented. The eight geologic factors which dominates igneous reservoirs are igneous facies, epigenetic tectonics deformation, fracture motion, intensity of intrusive effect and adjoining-rock characters, thermo-contact metamorphic rock facies, specific volcano-tectonic position, magmatic cyclicity and epigenetic diagenetic evolution. The interaction of the eight factors forms the four types nonhomogenous reservoir models of igneous reservoirs in Jiyang depression. And igneous facies and fracture motion are the most important and primary factors. 4. Identification patterns of seismic, well log and logging facies of igneous rocks are established. Igneous rocks of Jiyang depression show typical reflecting features on seismic profile. Tabular reflection seismic facies, arc reflection seismic facies and hummocky or mushroom reflection seismic facies are the three main facies. Logging response features of basic basalt and diabase are shown as typical "three low and two high", which means low natural gamma value, low interval transit-time, low neutron porosity, high resistivity and high density. Volcaniclastic rocks show "two high and three low"-high neutron porosity, high interval transit-time, low density, low-resistance and low natural gamma value. Thermo-contact metamorphic rocks surrounding to diabase show "four high and two low" on log data, which is high natural gamma value, high self-potential anomaly, high neutron porosity, high interval transit-time and low density and low-resistance. Based on seismic, well log and logging data, spatial shape of Shang 741 igneous rock is described. 5. The methods of fracture prediction and recognition for fractured igneous reservoir are summarized. Adopting FMI image log and nuclear magnetic resonance log to quantitative analysis of fractured igneous reservoir and according to formation mechanism and shape of fracture, various fractures are recognized, such as high-angle fracture, low-angle fracture, vertical fracture, reticulated fracture, induced fracture, infilling fracture and corrosion vug. Shang 741 intrusive rock reservoir can be divided into pore-vug compound type, pore fracture type, micro-pore and micro-fracture type. Physical properties parameters of the reservoir are computed and single-well fracture model and reservoir parameters model are established. 6. Various comprehensive methods of fracture prediction and recognition for fractured igneous reservoir are put forward. Adopting three-element (igneous facies, fracture motion and rock bending) geologic comprehensive reservoir evaluation technique and deep-shallow unconventional laterolog constrained inversion technique, lateral prediction of fractured reservoir such as Shang 741 is taken and nonhomogeneity quantification models of reservoirs are established.

孤北洼陷沙三-沙四段隐蔽油藏形成机制及其预测

Based on the study of sequence stratigraphy, modern sedimentary, basin analysis, and petroleum system in Gubei depression, this paper builds high resolution sequence stratigraphic structure, sedimentary system, sandbody distribution, the effect of tectonic in sequence and sedimentary system evolution and model of tectonic-lithofacies. The pool formation mechanism of subtle trap is developed. There are some conclusions and views as follows. 1.With the synthetic sequence analysis of drilling, seismic, and well log, the highly resolution sequence structure is build in Gubei depression. They are divided two secondary sequences and seven three-order sequences in Shahejie formation. They are include 4 kinds of system traces and 7 kinds of sedimentary systems which are alluvial fan, under water fan, alluvial fan and fan-delta, fan-delta, lacustrine-fan, fluvial-delta-turbidite, lakeshore beach and bar, and deep lake system. Sandbody distribution is show base on third order sequence. 2.Based on a lot of experiment and well log, it is point out that there are many types of pore in reservoir with the styles of corrosion pore, weak cementing, matrix cementing, impure filling, and 7 kinds of diagenetic facies. These reservoirs are evaluated by lateral and profile characteristics of diagenetic facies and reservoir properties. 3.The effect of simultaneous faulting on sediment process is analyzed from abrupt slope, gentle slope, and hollow zone. The 4 kinds of tectonic lithofacies models are developed in several periods in Gubei depression; the regional distribution of subtle trap is predicted by hydro accumulation characteristics of different tectonic lithofacies. 4.There are 4 types of compacting process, which are normal compaction, abnormal high pressure, abnormal low pressure and complex abnormal pressure. The domain type is normal compaction that locates any area of depression, but normal high pressure is located only deep hollow zone (depth more than 3000m), abnormal low pressures are located gentle slope and faulted abrupt slope (depth between 1200~2500m). 5.Two types dynamic systems of pool formation (enclosed and partly enclosed system) are recognized. They are composed by which source rocks are from Es3 and Es4, cap rocks are deep lacustrine shale of Esl and Es3, and sandstone reservoirs are 7 kinds of sedimentary system in Es3 and Es4. According to theory of petroleum system, two petroleum systems are divided in Es3 and Es4 of Gubei depression, which are high or normal pressure self-source system and normal or low pressure external-source system. 6.There are 3 kinds of combination model of pool formation, the first is litholgical pool of inner depression (high or normal pressure self-source type), the second is fault block or fault nose pool in marginal of depression (normal type), the third is fault block-lithological pool of central low lifted block (high or normal pressure type). The lithological pool is located central of depression, other pool are located gentle or abrupt slope that are controlled by lithological, faulting, unconfirmed. 7.This paper raise a new technique and process of exploration subtle trap which include geological modeling, coring description and logging recognition, and well log constrained inversion. These are composed to method and theory of predicting subtle trap. Application these methods and techniques, 6 hydro objects are predicted in three zone of depression.

Theoretical study of the separation mechanism of ionizable compounds in capillary electrochromatography

The migration mechanism of ionizable compounds in capillary electrochromatography (CEC) is more complicated than in high performance liquid chromatography (HPLC) due to the involvement of electrophoresis and the second chemical equilibrium. The separation mechanism of ionizable compounds in CEC has been studied theoretically. The electrochromatographic capacity factors of ions (k *) in CEC and in the pressurized CEC are derived by phenomenological approach. The influence of pH, voltage, pressure on k* is discussed. in addition, the k * of weak acid and weak base are derived based on acid-base equilibrium and the influence of pH on k * is studied theoretically.