高温高压下两元系H2O-CH4的摩尔体积

利用人造流体包裹体数据和甲烷笼合物熔化温度和压力的实验数据获得了在高温高压下H₂O-CH₄两元系的摩尔体积。并将所得数据与用传统的高温高压设备和状态方程所获得的数据进行了比较。这三组数据均吻合的很好。这表明用人造流体包裹体方法获得流体系统摩尔体积的可行性和已有的状态方程在描述该两元系在高温高压下的摩尔体积的正确性。本项工作对H₂O-CH₄系统高温高压下实验数据的重要补充。同时将已有的状态方程的适用性推广到更高的温度和压力。     

Coupling an equation of state and Henry's Law to model the phase equilibria of gases and brines: Examples in the N2–H2O–NaCl system

We propose a thermodynamic model for the mixing of gases in aqueous sodium chloride solutions valid to high pressures, high temperatures, and high ionic strength solutions. Our model couples Henry's Law with any equation of state to reproduce experimental data in the aqueous-rich liquid and gas-rich vapor region. In our model, the chemical potential of the solute in the brine is related to the chemical potential of the solute in pure water through salting-out coefficients. The model reproduces all crucial phenomena of binary (gas–water) and pseudo-binary (gas–water–salt) vapor–liquid mixtures below their critical point. We applied the model to reproduce the phase behavior of nitrogen in water and NaCl brines. Results and discussions are shown.     

Perturbation theory based equation of state for polar molecular fluids: II. Fluid mixtures

The equation of state (EOS) for 98 pure organic and inorganic fluids formulated by Churakov and Gottschalk (2003) is extended to complex fluid mixtures. For the calculation of the thermodynamic properties of mixtures, theoretical combining rules from statistical mechanics are used. These mixing rules do not involve any empirical parameters. The properties of the fluid mixtures are directly derived from those of the pure constituents. As an example we show that the EOS describes accurately the thermodynamic relations in the H₂O-CO₂ binary at high pressures and temperatures. At subcritical conditions the EOS is able to reproduce accurately the phase relations within mixtures of non-polar fluids. In particular the EOS predicts phase separations within various fluid mixtures of polar and non-polar molecules.     

Ternary system H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-NaCl at high <Emphasis Type="Italic">T</Emphasis>-<Emphasis Type="Italic">P</Emphasis> parameters: An empirical mixing model

New experimental data on the solubility of NaCl in gaseous CO₂ were obtained at pressures (P) of 30–70 MPa and temperatures of 623 and 673 K on experimental equipment making possible to sample a portion of the gas in the course of the experiment. The new measures have demonstrated that the NaCl solubility increases with increasing temperature (T) and pressure and is approximately four to five orders of magnitude higher than the saturated vapor pressure of NaCl at the corresponding temperature. The paper also reports newly obtained experimental data on the equilibrium conditions of the reaction of talc decomposition into enstatite and quartz at a variable H₂O/NaCl ratio in the fluid. The results of the experiments validate the empirical equations previously suggested for H₂O and NaCl activities in concentrated aqueous salt solutions that can be used in describing silica-saturated fluids at high T-P parameters. A new empirical equation is suggested for the Gibbs free mixing energy in the H₂O-CO₂-NaCl ternary system, with the parameters of the equation calibrated against experimental data on phase equilibria in marginal binary systems and on the location of the boundary of the region of homogeneous three-component fluid according to data on synthetic fluid inclusions in quartz.     

Thermodynamic modeling of binary CH4-H2O fluid inclusions

This work reports the application of thermodynamic models, including equations of state, to binary (salt-free) CH₄-H₂O fluid inclusions. A general method is presented to calculate the compositions of CH₄-H₂O inclusions using the phase volume fractions and dissolution temperatures of CH₄ hydrate. To calculate the homogenization pressures and isolines of the CH₄-H₂O inclusions, an improved activity-fugacity model is developed to predict the vapor-liquid phase equilibrium. The phase equilibrium model can predict methane solubility in the liquid phase and water content in the vapor phase from 273 to 623 K and from 1 to 1000 bar (up to 2000 bar for the liquid phase), within or close to experimental uncertainties. Compared to reliable experimental phase equilibrium data, the average deviation of the water content in the vapor phase and methane solubility in the liquid phase is 4.29% and 3.63%, respectively. In the near-critical region, the predicted composition deviations increase to over 10%. The vapor-liquid phase equilibrium model together with the updated volumetric model of homogenous (single-phase) CH₄-H₂O fluid mixtures (Mao S., Duan Z., Hu J. and Zhang D. (2010) A model for single-phase PVTx properties of CO₂-CH₄-C₂H₆-N₂-H₂O-NaCl fluid mixtures from 273 to 1273 K and from 1 to 5000 bar. Chem. Geol.275, 148-160), is applied to calculate the isolines, homogenization pressures, homogenization volumes, and isochores at specified homogenization temperatures and compositions. Online calculation is on the website: http://www.geochem-model.org/.     

超临界水的热力学模拟:一种可用到4273K、2GPa的立方型状态方程

根据水的高精度热力学模型IAPWS-95和IAPWS-IF97产生的压力-体积-温度(PVT)数据,本文建立了超临界水的一种高精度立方型状态方程。在723.15~2273.15K和0~1.4GPa范围内,该方程的平均体积偏差只有0.26%;在此范围之外,直到4273.15K和2GPa,方程的平均体积偏差不到2%。该方程在精度和适用范围方面均明显优于以前的立方型方程。在可比的温压条件下,该方程也明显优于一些常用的多参数非立方型方程(多数是高次维里型方程)。本文根据上述立方型方程和有关的热力学原理导出了膨胀系数、压缩系数、逸度系数、剩余焓和剩余熵的解析表达式,其计算结果与IAPWS-95模型的结果均吻合得很好。在此基础上很容易计算出许多其它的热力学性质。     

Thermodynamics of NaOH(aq) in hydrothermal solutions

Apparent molar volumes and osmotic coefficients of NaOH solutions, calculated from critically evaluated literature data on volumes and vapor pressures, were used to fit the Pitzer equations to yield ion-interaction parameters as a function of temperature and pressure. These parameters allow the calculation of osmotic and activity coefficients from 0–350°C, saturation pressure to about 400 bars and 0–10 molal NaOH, and volumetric properties at saturation pressure over the same temperature and concentration range. Because the parameters for osmotic and activity coefficients above 300°C are based on less precise data, and because of possible ion-pairing above this temperature, calculated values above 300°C are considered only as best estimates available at this time. Partial molar volumes at infinite dilution calculated for NaOH are combined with literature data for NaCl, HCl, and H₂O to yield the pressure dependence of the ionization of water to 200°C, and are also combined with the potentiometric data of Sweeton et al. (1974) on the ionization of water to calculate the infinitely dilute partial molar volume of HCl to 300°C. Specific volumes of NaOH solutions at saturation pressure and up to 350°C are also calculated and tabulated.     

Water flow and swelling pressure in non-saturated bentonite-based clay barriers

The water uptake of 10 and 20% bentonite—sand mixtures and of 100% pure bentonite was studied experimentally. The results were compared with calculated water content distributions to study the usefulness of the diffusion equation. The relation between the swelling pressure and the degree of saturation of a bentonite was also studied.     

Rietveld定量方法在蒸发岩矿物组分分析中的精确度评价和误差来源

Rietveld物相定量分析(RQPA)方法在地质学中已有大量应用,在蒸发岩定量分析中,对精确度的评价和误差控制是提高分析质量的重要因素。本文对人工配制和野外采集的样品(石膏和钾盐)进行RQPA分析,并与化学分析结果对比,评价其精确度并分析其主要的误差来源。结果表明:人工配制的氯化钠-氯化钾二元物相的绝对误差为0.4%~0.9%;氯化钠-氯化钾-碳酸钙三元物相的绝对误差为0.1%~1.2%;二元物相样品10次分析的标准偏差为0.702%,相对标准偏差为1.74%(氯化钾)和1.17%(氯化钠);野外采集的石膏和钾盐样品的RQPA分析结果与化学分析结果具有很好的一致性。表明RQPA方法在蒸发岩矿物组分定量分析中具有较高的精确度,其误差主要来源于样品性质、样品制备、测试条件和精修过程等。RQPA方法具有减弱择优取向效应、无需纯样以及提高数据利用率等优点,与化学分析技术联用在蒸发岩矿产勘探、储量评价以及工业应用中具有广泛的前景。     

Molecular dynamics simulation of the CH4 and CH4-H2O systems up to 10 GPa and 2573 K

Based on our previous study of the intermolecular potential for pure H₂O and the strict evaluation of the competitive potential models for pure CH₄ and the ab initio fitting potential surface across CH₄-H₂O molecules in this study, we carried out more than two thousand molecular dynamics simulations for the PVTx properties of pure CH₄ and the CH₄-H₂O mixtures up to 2573 K and 10 GPa. Comparison of 1941 simulations with experimental PVT data for pure CH₄ shows an average deviation of 0.96% and a maximum deviation of 2.82%. The comparison of the results of 519 simulations of the mixtures with the experimental measurements reveals that the PVTx properties of the CH₄-H₂O mixtures generally agree with the extensive experimental data with an average deviation of 0.83% and 4% in maximum, which is equivalent to the experimental uncertainty. Moreover, the maximum deviation between the experimental data and the simulation results decreases to about 2% as temperature and pressure increase, indicating that the high accuracy of the simulation is well retained in the high temperature and pressure region.After the validation of the simulation method and the intermolecular potential models, we systematically simulated the PVTx properties of this binary system from 673 K and 0.05 GPa to 2573 K and 10 GPa. In order to integrate all the simulation results and the experimental data for the calculation of thermodynamic properties, an equation of state (EOS) is developed for the CH₄-H₂O system covering 673-2573 K and 0.01-10 GPa. Isochores for compositions <4 mol% CH₄ up to 773 K and 600 MPa are also determined in this paper. The program for the EOS can be downloaded from www.geochem-model.org/programs.htm.     

Applications of the SW96 formulation in the thermodynamic calculation of fluid inclusions and mineral-fluid equilibria

The SW96 formulation explicit in Helmholtz free energy proposed by Span and Wagner (1996) is the most accurate multifunction equation of state of CO₂ fluid, from which all thermodynamic properties can be obtained over a wide temperature-pressure range from 216.592 to 1100 K and from 0 to 8000 bar with or close to experimental accuracy. This paper reports the applications of the SW96 formulation in fluid inclusions and mineral-fluid equilibria. A reliable and highly efficient algorithm is presented for the saturated properties of CO₂ so that the formulation can be conveniently applied in the study of fluid inclusions, such as calculation of homogenization pressures, homogenization densities (or molar volumes), volume fractions of vapor phase and isochores. Meanwhile, the univariant curves of some typical decarbonation reactions of minerals are calculated with the SW96 formulation and relevant thermodynamic models of minerals. The computer code of the SW96 formulation can be obtained from the corresponding author.     

A Compensated-Redlich-Kwong (CORK) equation for volumes and fugacities of CO2 and H2O in the range 1 bar to 50 kbar and 100–1600°C

We present a simple virial-type extension to the modified Redlich-Kwong (MRK) equation for calculation of the volumes and fugacities of H₂O and CO₂ over the pressure range 0.001–50 kbar and 100 to 1400°C (H₂O) and 100 to 1600°C (CO₂). This extension has been designed to: (a) compensate for the tendency of the MRK equation to overestimate volumes at high pressures, and (b) accommodate the volume behaviour of coexisting gas and liquid phases along the saturation curve. The equation developed for CO₂ may be used to derive volumes and fugacities of CO, H₂, CH₄, N₂, O₂ and other gases which conform to the corresponding states principle. For H₂O the measured volumes of Burnham et al. are significantly higher in the range 4–10 kbar than those presented by other workers. For CO₂ the volume behaviour at high pressures derived from published MRK equations are very different (larger volumes, steeper (P/T)_V, and hence larger fugacities) from the virial-type equations of Saxena and Fei. Our CORK equation for CO₂ yields fugacities which are in closer agreement with the available high pressure experimental decarbonation reactions.     

饱水度对砂岩模量及强度影响的三轴试验

为研究饱水度和围压对砂岩力学特性的影响,在不同围压和饱水度下开展三轴试验,获得了不同饱水度和围压下巴里坤砂岩的模量、峰值强度和残余强度,分析了饱水度和围压对砂岩模量、峰值强度和残余强度的影响规律,结果表明：（1）围压增加,砂岩的模量也增加,围压与模量之间近似为直线关系;饱水度增加,砂岩模量降低,单轴下饱和砂岩的模量降低50.9%;饱水度与砂岩模量之间近似服从直线或负指数函数关系。（2）饱水度增加,峰值强度下降;单轴条件下饱和砂岩的峰值强度下降了44.2%;饱水度与砂岩峰值强度之间近似服从自然对数关系。（3）强度退化指数可以较好地描述围压对残余强度的影响,巴里坤砂岩的强度退化指数与围压之间近似符合负指数关系;随着饱水度增加,砂岩的残余强度降低。（4）随着围压增加,饱水度对砂岩模量、峰值强度和残余强度的影响都减弱。（5）饱水度在60%以下时,饱水度变化对模量和峰值强度的影响显著,当饱水度超过60%后,模量和峰值强度仍随着饱水度增加而降低,但变化速率趋缓;对于残余强度,则饱水度在80%以下时影响显著。     

Calculating activity coefficients in hydrometallurgy — A review

Recent developments for estimating activity coefficients of electrolytes both in pure and multicomponent aqueous solutions are reviewed with good success generally attained up to saturation. Examples are presented to illustrate applications of these methods in calculating ion concentrations, vapor pressures, and solubility limits, for some problems encountered in hydrometallurgy.     

宽广温压范围内纯流体pVT性质的预测

一个具有 1 9个参数的半经验状态方程 ,可以很容易地转化为关于体积的多项式方程 ,应用起来十分方便。对于气体和超临界流体 ,该方程可以在很宽的温压范围内保持较高的精度。用该方程计算 H2 O、CO2 、CH4、H2 、CO、O2 等流体的 p VT关系 ,结果令人满意。在从常温常压直到 4 0 0 0～ 50 0 0 K和 90～ 60 0 GPa的范围内 ,预测的体积误差为 :平均偏差小于 1 % ,最大偏差小于 6% ,标准偏差小于 1 .5%。     

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (υ₁) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH₄-H₂O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 °C, and pressures up to 37 MPa. The results show that the CH₄υ₁ band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH₄-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell.     

Modeling of unsaturated granular flows by a two-layer approach

Flows of partially saturated grain-fluid mixtures over complex curved topography are commonly observed in nature. However, comprehensive understanding of the physics behind them is to date out of reach. To investigate their dynamic process, a two-layer approach is proposed, in which the fluid-saturated granular layer is overlaid by the pure granular material. More specifically, the lower layer is described by a two-phase mixture theory of density preserving solid and fluid constituents. For the upper layer, the single-phase granular mass is treated as a frictional Coulomb-like continuum, and the dilation effect and the influence of the interstitial air are ignored. The capillarity effects and grains-size segregation are not considered in both the layers. The lower and upper layers interact at an interface which is a material surface for the fluid phase, but across which the mass exchange for the granular phase may take place. The granular mass exchange across the layer interface is parameterized by an entrainment type postulate. In addition, the classical jump conditions are employed to connect both layers at the interface dynamically. Furthermore, we perform the depth-averaged technique for the saturated grain-fluid mixture lower layer and the pure granular upper layer, respectively, to simplify the governing equations established. It is demonstrated that the resulting model equations can be reduced to most of the existing single-layer pure granular flow models and saturated two-phase single-layer debris flow models. Numerical solutions demonstrate that the present two-layer model can describe flows of partially saturated grain-fluid mixtures and the transition process of a saturated grain-fluid mixture into an under-saturated state.     

松辽盆地徐深气田火山岩气藏相态与渗流机理

通过徐深气田天然气气体状态方程( PVT) 性质、天然气饱和水汽量和地层水PVT性质测试及全直径岩芯分析的气藏启动压力、储层流速敏感性和应力敏感性评价, 探讨了火山岩储层渗流机理。结果表明: 徐深气田火山岩气藏中CO₂含量差别较大(最高达86.88% ) , 天然气分子量与CO₂含量呈正相关; 偏差系数、饱和水汽含量及地层水中天然气含量受地层温度、压力、天然气组成及地层水矿化度等影响; 火山岩气藏启动压力与束缚水饱和度和空气渗透率均呈幂指数关系; 储层呈气水两相流特征, 具有弱速敏性和较强的应力敏感性, 易造成储层渗透率伤害以及孔隙结构改变。