二氧化碳在孔隙咸水层中多相流动数值模拟研究

There has been a growing concern about the use of fossil fuels and its adverse effects on the atmospheric greenhouse and ecological environment. A reduction in the release rate of CO2 into the atmosphere poses a major challenge to the land ecology of China. The most promising way of achieving CO2 reduction is to dispose of CO2 in deep saline aquifers. Deep aquifers have a large potential for CO2 sequestration in geological medium in terms of volume and duration. Through the numerical simulation of multiphase flow in a porous media, the transformation and motion of CO2 in saline aquifers has been implemented under various temperature and hydrostatic pressure conditions, which plays an important role to the assessment of the reliability and safety of CO2 geological storage. As expected, the calculated results can provide meaningful and scientific information for management purposes. The key problem to the numerical simulation of multiphase flow in a porous media is to accurately capture the mass interface and to deal with the geological heterogeneity. In this study, the updated CE/SE (Space and time conservation element and solution element) method has been proposed, and the Hybrid Particle Level Set method (HPLS) has extended for multiphase flows in porous medium, which can accurately trace the transformation of the mass interface. The benchmark problems have been applied to evaluate and validate the proposed method. In this study, the reliability of CO2 storage in saline aquifers in Daqingzi oil field in Sunlong basin has been discussed. The simulation code developed in this study takes into account the state for CO2 covering the triple point temperature and pressure to the supercritical region. The geological heterogeneity has been implemented, using the well known geostatistical model (GSLIB) on the base of the hard data. The 2D and 3D model have been set up to simulate the CO2 multiphase flow in the porous saline aquifer, applying the CE/SE method and the HPLS method .The main contents and results are summarized as followings. (1) The 2D CE/SE method with first and second –order accuracy has been extended to simulate the multiphase flow in porous medium, which takes into account the contribution of source and sink in the momentum equation. The 3D CE/SE method with the first accuracy has been deduced. The accuracy and efficiency of the proposed CE/SE method have been investigated, using the benchmark problems. (2) The hybrid particle level set method has been made appropriate and extended for capturing the mass interface of multiphase flows in porous media, and the numerical method for level set function calculated has been formulated. (3) The closed equations for multiphase flow in porous medium has been developed, adept to both the Darcy flow and non-Darcy flow, getting over the limitation of Reynolds number to the calculation. It is found that Darcy number has a decisive influence on pressure as well as velocity given the Darcy number. (4) The new Euler scheme for numerical simulations of multiphase flows in porous medium has been proposed, which is efficient and can accurately capture the mass interface. The artificial compressibility method has been used to couple the velocities and pressure. It is found that the Darcy number has determinant effects on the numerical convergence and stability. In terms of the different Darcy numbers, the coefficient of artificial compressibility and the time step have been obtained. (5) The time scale of the critical instability for critical CO2 in the saline aquifer has been found, which is comparable with that of completely CO2 dissolved saline aquifer. (6) The concept model for CO2 multiphase flows in the saline aquifer has been configured, based on the temperature, pressure, porosity as well as permeability of the field site .Numerical simulation of CO2 hydrodynamic trapping in saline aquifers has been performed, applying the proposed CE/SE method. The state for CO2 has been employed to take into account realistic reservoir conditions for CO2 geological sequestration. The geological heterogeneity has been sufficiently treated , using the geostatistical model. (7) It is found that the Rayleigh-Taylor instability phenomenon, which is associated with the penetration of saline fluid into CO2 fluid in the direction of gravity, has been observed in CO2 multiphase flows in the saline aquifer. Development of a mushroom-type spike is a strong indication of the formation of Kelvin-Helmholtz instability due to the developed short wavelength perturbations present along the interface and parallel to the bulk flow. Additional key findings: the geological heterogeneity can distort the flow convection. The ascending of CO2 can induce the persistent flow cycling effects. The results show that boundary conditions of the field site have determinant effects on the transformation and motion of CO2 in saline aquifers. It is confirmed that the proposed method and numerical model has the reliability to simulate the process of the hydrodynamic trapping, which is the controlling mechanism for the initial period of CO2 storage at time scale of 100 years.

华南震旦纪-寒武纪两期成磷事件及其地球动力学意义

Phosphorus is an important biological and ecological element that to a certain degree constrains ecological environment and nutrient (including carbon) cycling. Marine sedimentary phosphorites are the principal phosphorus supply of the mankind. In the eastern to southern margins of the Yangtze Craton, South China, there are two phosphogenetic events at the Doushantuo stage of the Late Sinian and the Meishucun stage of the Early Cambrian respectively, corresponding two explosion events of life across the Precambrian\Cambrian boundary. Phosphorus ores from the Sinian and Cambrian phosphate in South China can be classified roughly into two categories, namely, grained and non-grained phosphorites. Grained phosphorites, hosted in dolostone type of phosphogenetic sequences and with larger industrial values, occur mainly in margins of the Upper Yangtze Platform, formed in shallow-water environments with high hydraulic energy and influenced by frequent sea-level change. Non-grained phosphorites, hosted principally in black-shale type of phosphogenetic sequences and with smaller industrial values, are distributed mainly in the Jiangnan region where deeper-water sub-basins with low hydraulic energy were prevailing at the time of phosphogenesis. Secular change ofδ~(13)C, δ~(18) O, ~(86)Sr/~(87)Sr values of carbonates from Sinian and Cambrian sequences were determined. A negative abnormal ofδ~(13)C, δ~(18)O values and positive abnormal of 86Sr/87Sr values from the fossiliferous section of the Lowest Cambrian Meishucun Formation implies life depopulation and following explosion of life across the PrecambriamCambrian boundary. Based on a lot of observations, this paper put forward a six-stage genetic model describing the whole formational process of industrial phosphorites: 1) Phosphorus was transported from continental weathering products and stored in the ocean; 2) dissolved phosphates in the seawater were enriched in specific deep seawater layer; 3) coastal upwelling currents took this phosphorus-rich seawater to a specific coastal area where phosphorus was captured by oceanic microbes; 4) clastic sediments in this upwelling area were enriched in phosphorus because of abundant phosphorus-rich organic matters and because of phosphorus absorption on grain surfaces; 5) during early diagenesis, the phosphorus enriched in the clastic sediments was released into interstitial water by decomposition and desorption, and then transported to the oxidation-reduction interface where authigenic phosphates were deposited and enriched; 6) such authigenic phosphate-rich layers were scoured, broken up, and winnowed in shallow-water environments resulting in phosphate enrichment. The Sinian-Cambrian phosphorites in South China are in many aspects comparable with coastal-upwelling phosphorites of younger geological ages, especially with phosphorites from modern coastal upwelling areas. That implies the similarities between the Sinian-Cambrian ocean and the modern ocean. Although Sinian-Cambrian oceanic life was much simpler than modern one, but similar oceanic planktons prevail, because oceanic planktons (particularly phytoplanktons) are crucial for phosphate enrichment related to coastal upwelling. It implies also a similar seawater-layering pattern between the Sinian-Cambrian ocean and the modern ocean. The two global phosphate-forming events and corresponding life-explosion events at the Sinian and Cambrian time probably resulted from dissolved-phosphate accumulation in seawater over a critical concentration during the Earth's evolution. Such an oceanic system with seawater phosphorus supersaturation is evidently unstable, and trends to return to normal state through phosphate deposition. Accordingly, this paper put forward a new conception of "normal state <=> phosphorus-supersaturation state" cycling of oceanic system. Such "normal state <=> phosphorus-supersaturation state" cycling was not only important for the three well-known global phosphate-forming events, also related to the critical moments of life evolution on the Earth. It might be of special significance. The favorable paleo-oceanic orientation in regard to coastal-upwelling phosphorite formation suggests a different orientation of the Yangtze Craton between the Sinian time and the present time (with a 135° clockwise difference), and a 25° anti-clockwise rotation of the Yangtze Craton from late Sinian to early Cambrian. During the Sinian-Cambrian time, the Yangtze Craton might be separated from the Cathaysia Block, but might be still associated with the North China Craton.

Study of adsorption of methylene blue and new methylene blue in liquid-solid interface by slab optical waveguide spectroscopy

A slab optical waveguide (SOWG) has been used for study of adsorption of both methylene blue (MB) and new methylene blue (NMB) in liquid-solid interface. Adsorption characteristics of MB and NMB on both bare SOWG and silanized SOWG by octadecyltrichlorosilane (ODS) were compared. Effect of pH on adsorption on MB and NMB was investigated. Binding rate constant analysis showed that both MB and NMB on bare SOWG demonstrates larger association constants than those on ODS-SOWG. Interactions of NIB and NMB on bare SOWG and ODS-SOWG were analyzed by molecular mechanics calculation method. The binding energy change was in the following order: ENMB-bare > EMB-bare > ENMB-ODS > EMB-ODS. (c) 2004 Elsevier B.V. All rights reserved.

Interface of chip-based capillary electrophoresis-inductively coupled plasma-atomic emission spectrometry (CE-ICP-AES)

An interface of chip-based capillary electrophoresis (CE)-inductively coupled plasma-atomic emission spectrometry (ICP-AES) that is based on cross-flow nebulization has been developed. A polydimethylsiloxane (PDMS) CE-chip with conventional cross channel layout was used. A stainless steel tube was placed orthogonal to the exit of the CE separation channel for cross flow nebulization. A supplementary flow of buffer solution at the channel exit was used to improve nebulization efficiency. Two capillaries were inserted into the CE chip near the inlet of the separation channel for sample and buffer solution injection. Syringe pumps were used to manipulate the flow rate and flow direction of the sample, buffer, and supplementary buffer solution. Peak broadening due to the shape (bulb and tube-shaped) and size of the spray chambers was studied. The smaller tube-shaped spray chamber was used because of smaller peak broadening effect due to aerosol transport. The nebulization and transport efficiency of the CE-ICP interface was approximately 10%. Ba2+ and Mg2+ ions were eluted from the CE-chip within 30 s. Resolution of the Ba2+ and Mg2+ peaks was 0.7 using the chip-based CE-ICP-AES system.