Prediction of thermodynamic properties of natural gas mixtures using 10 equations of state including a new cubic two-constant equation of state

In this contribution, 10 equations of state (EoSs) are used to predict the thermo-physical properties of natural gas mixtures. One of the EoSs is proposed in this work. This EoS is obtained by matching the critical fugacity coefficient of the EoS to the critical fugacity coefficient of methane. Special attention is given to the supercritical behavior of methane as it is the major component of natural gas mixtures and almost always supercritical at reservoir and surface conditions. As a result, the proposed EoS accurately predicts the supercritical fugacity of methane for wide ranges of temperature and pressure. Using the van der Waals mixing rules with zero binary interaction parameters, the proposed EoS predicts the compressibility factors and speeds of sound data of natural gas mixtures with best accuracy among the other EoSs. The average absolute error was found to be 0.47% for predicting the compressibility factors and 0.70% for the speeds of sound data. The proposed EoS was also used to predict thermal and equilibrium properties. For predicting isobaric heat capacity, Joule–Thomson coefficient, dew points and flash yields of natural gas mixtures, the predictive accuracy of the EoS is comparable to the predictive accuracy of the Redlich–Kwong–Soave (RKS) EoS or one of its variants. For predicting saturated liquid density of LNG mixtures, however, the accuracy of predictions is between the RKS and Peng–Robinson (PR) EoSs.     

基于CPA状态方程计算水的热力学物性参数

虽然储层多孔介质中不可避免的含有大量的地层水,但在通常的相平衡计算过程中往往都忽略了水的存在;常用的状态方程虽然计算简便,但对某些热力学性质的估算仍存在着较大的偏差;已有的状态方程虽然已进行过修正,但其对含有极性物质(烃类、水、醇等)的体系适用性较差。为此,基于同时考虑分子间物理作用和缔合作用的CPA(Cubic-Plus-Association)状态方程,模拟计算了极性物质——水在饱和与非饱和状态下的热力学性质,对比分析了常用状态方程在计算极性物质热力学物性参数时的不足。计算结果表明:(1)常用的状态方程虽然能较好地计算水的饱和蒸汽压值,但在水的密度和焓值的计算时却呈现出不同的差异性,同时焓值的计算不受体积修正的影响;(2)CPA方程计算的水热力学物性参数与实验数据的平均绝对相对偏差在1%左右。结论认为:对含有极性物质的体系而言,CPA方程是首选的热力学状态方程。对水热力学物性参数的准确估算是对含水气藏流体所处状态的基础把握,对该类气藏的开发和生产具有重要的指导意义。     

地层水对凝析气藏注CO_2相态的影响

常规的凝析气藏衰竭开发和注CO_2开发研究中均忽略了地层水的影响,这与真实情况存在偏差,有可能导致研究结果的不确定性加大。为此,基于CO_2—烃—水相平衡热力学模型,以一个实际近临界凝析气藏为例,通过相态模拟研究了地层水存在对凝析气藏反凝析相态特征和注CO_2相态的影响规律;计算了考虑地层水存在的凝析气定容衰竭反凝析液饱和度和剩余流体组成,以及注CO_2过程中凝析油气相体积分数和CO_2在凝析油气相中体积分数的变化规律。结果表明:1考虑地层水时定容衰竭的反凝析油饱和度更大,剩余流体重组分含量更高;2近临界凝析气藏压力衰竭过程中,由凝析气转变为挥发油的相变发生得更早;3在注CO_2过程中,地层水的存在使得CO_2对凝析油的反蒸发作用降低;4考虑地层水存在时凝析油相体积分数高约14%,CO_2在凝析油中溶解量比不考虑地层水大6%,CO_2含量高和压力较高时差异更明显,同时,地层水的存在也增强了CO_2的溶解封存能力。该研究成果对凝析气藏注CO_2提高采收率和温室气体CO_2埋存评价具有指导意义。