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1. 清华大学热科学与动力工程教育部重点实验室
2. 中国计量科学研究院
纸质出版:2026
移动端阅览
王瑞琦, 徐柳, 卿康, 等. 面向高温应用的CO2/H_2O复合工质中低密度区热力学性质高精度预测模型[J]. 热力发电, 2026,(10). DOI: 10.19666/j.rlfd.202601038.
王瑞琦, 徐柳, 卿康, et al. 面向高温应用的CO2/H_2O复合工质中低密度区热力学性质高精度预测模型[J]. Thermal Power Generation, 2026, (10). DOI: 10.19666/j.rlfd.202601038.
【目的】超临界二氧化碳(S-CO
2
)半闭式循环工质主要为CO
2
/H_2O复合工质,其在除压缩与分离过程外多数流程段均处于中低密度区,区域内其热力学性质的精确描述对动力循环至关重要。由于复合工质实验数据缺乏,多参数状态方程的适用温度受限,而半理论的立方型状态方程受结构限制难以达到高精度。相较之下,维里方程具有严格的理论基础,为高温热力学性质预测提供了有效途径。基于此,构建适用于CO
2
/H_2O复合工质的截断维里状态方程,以实现宽温区热力学性质的高精度计算。【方法】针对CO
2
/H_2O复合工质,结合从头算数据建立了满足物理一致性要求的交叉第二维里系数计算式,构建了适用于CO
2
、H_2O纯工质及其复合工质热力学性质计算的三项截断维里方程(VEOS3)。系统评估了VEOS3对pvT(x)性质、比定压热容与声速等热力学性质的预测性能,并结合实验数据对模型的表征效果进行了检验。【结果】以计算偏差不超过1%为标准,VEOS3的有效密度上限在高温区近似保持恒定或随温度线性增长,其有效预测区域随温度升高可拓展至高压。同时,VEOS3能够高精度再现实验数据,对复合工质密度平均计算偏差为0.43%。【结论】VEOS3可在对比密度≤2/3的中低密度区实现CO
2
/H_2O复合工质热力学性质的精确计算,并在高温条件下保持稳定、可靠的外推预测能力,为S-CO
2
半闭式循环提供热力学性质计算的模型支撑。
[Objective
]
The supercritical carbon dioxide(S-CO
2
) semi-closed Brayton cycle has attracted widespread attention due to its high cycle efficiency and potential for near-zero carbon emissions. The working fluid in this cycle primarily consists of the CO
2
/H_2O mixture. Except during the compression and separation processes
the CO
2
/H_2O mixture operates in the low-to medium-density region for most of the cycle. Accurate prediction of thermophysical properties in this region is crucial for the power cycle. Due to the lack of experimental data for the mixture
the applic
able temperature range of multiparameter equations of state is limited
making it difficult to meet the demand for thermophysical property calculations at high temperatures. Computational models based on theoretical foundations have greater potential for extrapolation in the high-temperature region. Among these
semitheoretical cubic equations of state can reasonably describe the trends in thermophysical properties. However
they are limited by their structure and cannot achieve extremely high precision. In contrast
the virial equation of state has a rigorous theoretical foundation and provides an effective approach for predicting thermodynamic properties at high temperatures. On this basis
a truncated virial equation of state applicable to CO
2
/H_2O mixtures is developed to enable high-accuracy calculations of thermodynamic properties over a wide temperature range. [Methods
]
A predictive model that strictly satisfies physical consistency requirements is established for the cross second virial coefficient of the CO
2
/H_2O mixture based on ab initio data. Building upon this
a three-term truncated virial equation of state(VEOS3) is developed to calculate the thermodynamic properties of pure CO
2
pure H_2O
and their binary mixtures. The predictive performance of VEOS3 is systematically evaluated across a range of properties
including pvT(x)
isobaric heat capacity
internal energy
enthalpy
entropy
and speed of sound. The effective range of VEOS3 is determined by comparison with multiparameter equations of state within their respective validity domains. At a given temperature
the maximum density and the corresponding pressure within the region where the absolute relative deviation does not exceed 1% are defined as the effective density limit and effective pressure limit
respectively. The model performance is further validated using experimental data. [Results
]
The results show that the effective density limit of VEOS3 remains approximately constant in the high-temperature regi
on or increases linearly with temperature. As the temperature rises
the effective prediction range of VEOS3 can be extended to higher pressures. Meanwhile
VEOS3 reproduces available experimental data with high accuracy. Here
the average absolute relative deviation(AARD) is used to quantify prediction deviations. For pure CO
2
and pure H_2O
the AARDs of VEOS3 in density
isobaric heat capacity
and speed of sound are 0.14%/0.30%
0.28%/0.82%
and 0.02%/0.16%
respectively. For CO
2
/H_2O mixtures
the AARD in density is 0.43%. [Conclusion
]
VEOS3 can accurately calculate thermophysical properties in the low-to medium-density region
where the reduced density is less than or equal to 2/3. It also maintains stable and reliable extrapolation capability at high temperatures
providing model support for thermophysical property calculations in the S-CO
2
semi-closed Brayton cycle.
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