Study on the critical properties calculation models of CO2-based binary mixture working fluid

doi:10.11949/0438-1157.20231295

Abstract

Abstract:

Carbon dioxide (CO₂) mixed working fluid is a power cycle working fluid with application potential. Critical parameters are the key basic thermophysical properties of CO₂mixed working fluid, and its accurate calculation and prediction are of great significance. Four types of calculation models were used to calculate the critical temperature and critical pressure of three types of binary mixture working fluids, namely CO₂+HFC, CO₂+HFO and CO₂+HC, and compared with the published experimental measured data and REFPROP database. The applicability of calculation models to each type of CO₂-based binary mixture is analyzed and discussed. The results show that Li method has a simple form, and the calculation formula of mixture's critical temperature is only related to the critical temperature and critical volume of the pure substances, which can be used to quickly calculate critical temperature of CO₂+HFC and CO₂+HFO. For the CO₂+HC, the RK method showed the lowest deviations when predicting the critical pressure. Due to the completeness on experimental data points and sets of critical properties, the correlation can be directly obtained through RK method for application.

Key words: critical property, binary mixture, supercritical fluid, carbon dioxide, model

摘要：

二氧化碳（CO₂）混合工质是具有应用潜力的动力循环工质，临界参数作为CO₂混合工质的关键基础热物性，对其进行准确地计算和预测具有重要意义。采用4种不同类型的计算模型，分别针对CO₂+HFC、CO₂+HFO和CO₂+HC三类二元混合工质的临界温度和临界压力进行了推算，并与公开发表的实验数据和REFPROP数据库计算结果进行对比，分析讨论了各种计算方法对各类CO₂混合工质的适用性。结果表明，Li方法形式简单，混合物临界温度的计算式仅与纯质组分的临界温度及临界体积有关，可用于CO₂+HFC和CO₂+HFO混合工质临界温度的快速推算。对于CO₂+HC混合工质，RK方法计算偏差最小，该类混合物临界参数实验数据点数和套数较多，因此可直接通过RK方法回归得到关联式进行应用。

关键词: 临界参数, 二元混合物, 超临界流体, 二氧化碳, 模型

CLC Number:

TK 123

Rui SUN, Hua TIAN, Zirui WU, Xiaocun SUN, Gequn SHU. Study on the critical properties calculation models of CO₂-based binary mixture working fluid[J]. CIESC Journal, 2024, 75(2): 439-449.

孙瑞, 田华, 吴子睿, 孙孝存, 舒歌群. 二氧化碳混合工质临界参数计算模型对比研究[J]. 化工学报, 2024, 75(2): 439-449.

Figures/Tables 12

References 48

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混合工质	CO₂摩尔分数	点数	文献
CO₂+HFC-32	0.18~0.84	25	[19]
	0~1		[20]
	0~1		[21]
CO₂+HFC-134a	0~1	10	[22]
CO₂+HFC-152a^①	0~1	11	[23]
CO₂+HFO-1234yf	0~1	11	[24]
	0~1	9	[25]
CO₂+HFO-1234ze(E)	0~1	11	[24]
	0~1	9	[26]
CO₂+HFO-1243zf	0~1	11	[27]
CO₂+丙烷	0.152~0.939	38	[28]
	0.407~0.795		[29]
	0.13~0.92		[30]
	0.9015~1		[31]
	0.1394~0.78		[32]
	0~1		[33]
CO₂+正丁烷	0.139~0.861	40	[28]
	0.188~0.831		[34]
	0.914~1		[31]
	0.51~0.875		[35]
	0.088~0.839		[36]
	0~1		[33]
CO₂+异丁烷	0~1	8	[37]

混合工质	CO₂摩尔分数	点数	文献
CO₂+HFC-32	0.18~0.84	25	[19]
	0~1		[20]
	0~1		[21]
CO₂+HFC-134a	0~1	10	[22]
CO₂+HFC-152a^①	0~1	11	[23]
CO₂+HFO-1234yf	0~1	11	[24]
	0~1	9	[25]
CO₂+HFO-1234ze(E)	0~1	11	[24]
	0~1	9	[26]
CO₂+HFO-1243zf	0~1	11	[27]
CO₂+丙烷	0.152~0.939	38	[28]
	0.407~0.795		[29]
	0.13~0.92		[30]
	0.9015~1		[31]
	0.1394~0.78		[32]
	0~1		[33]
CO₂+正丁烷	0.139~0.861	40	[28]
	0.188~0.831		[34]
	0.914~1		[31]
	0.51~0.875		[35]
	0.088~0.839		[36]
	0~1		[33]
CO₂+异丁烷	0~1	8	[37]

工质	名称	T_c/K	p_c/MPa	V_c/(cm³·mol^-1)	ω
CO₂	二氧化碳	304.13	7.377	94.118	0.224
HFC-32	二氟甲烷	351.26	5.782	122.698	0.277
HFC-134a	1,1,1,2-四氟乙烷	374.21	4.059	199.320	0.327
HFC-152a	1,1-二氟乙烷	386.41	4.517	179.486	0.275
HFO-1234yf	2,3,3,3-四氟丙烯	367.85	3.382	239.808	0.276
HFO-1234ze(E)	反式-1,3,3,3-四氟丙烯	382.51	3.635	233.100	0.313
HFO-1243zf	3,3,3-三氟丙烯	376.93	3.518	232.558	0.260
丙烷	丙烷	369.89	4.251	200.000	0.152
丁烷	正丁烷	425.13	3.796	254.922	0.201
异丁烷	2-甲基丙烷	407.81	3.629	257.748	0.184

工质	名称	T_c/K	p_c/MPa	V_c/(cm³·mol^-1)	ω
CO₂	二氧化碳	304.13	7.377	94.118	0.224
HFC-32	二氟甲烷	351.26	5.782	122.698	0.277
HFC-134a	1,1,1,2-四氟乙烷	374.21	4.059	199.320	0.327
HFC-152a	1,1-二氟乙烷	386.41	4.517	179.486	0.275
HFO-1234yf	2,3,3,3-四氟丙烯	367.85	3.382	239.808	0.276
HFO-1234ze(E)	反式-1,3,3,3-四氟丙烯	382.51	3.635	233.100	0.313
HFO-1243zf	3,3,3-三氟丙烯	376.93	3.518	232.558	0.260
丙烷	丙烷	369.89	4.251	200.000	0.152
丁烷	正丁烷	425.13	3.796	254.922	0.201
异丁烷	2-甲基丙烷	407.81	3.629	257.748	0.184

混合工质	k_ij
CO₂+HFC-32	-0.015
CO₂+HFC-134a	0.017
CO₂+HFC-152a	0.015
CO₂+HFO-1234yf	0.022
CO₂+HFO-1234ze(E)	0.035
CO₂+HFO-1243zf	0.020
CO₂+丙烷	0.100
CO₂+正丁烷	0.150
CO₂+异丁烷	0.125

Study on the critical properties calculation models of CO₂-based binary mixture working fluid

二氧化碳混合工质临界参数计算模型对比研究

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混合工质	参数	i
混合工质	参数	1	2	3	4	5	6
CO₂+HFC-32	c_i	19.992	11.564	-86.780	234.360	-284.363	131.804
CO₂+HFC-32	d_i	0.050	-0.213	0.302	0.316	-1.109	0.720
CO₂+HFC-134a	c_i	49.094	53.934	-250.929	683.153	-834.737	391.168
CO₂+HFC-134a	d_i	0.209	-1.360	4.016	-5.897	3.931	-0.837
CO₂+HFC-152a	c_i	48.274	93.808	-346.395	813.068	-960.045	440.489
CO₂+HFC-152a	d_i	0.135	-0.577	0.746	0.496	-2.034	1.298
CO₂+HFO-1234yf	c_i	100.092	-60.854	147.436	134.445	-586.749	390.412
CO₂+HFO-1234yf	d_i	0.243	-1.573	5.216	-9.177	7.703	-2.393
CO₂+HFO-1234ze(E)	c_i	77.751	-15.252	-39.746	517.360	-868.373	475.568
CO₂+HFO-1234ze(E)	d_i	0.277	-2.319	8.529	-15.494	13.353	-4.340
CO₂+HFO-1243zf	c_i	98.126	64.441	-299.780	906.444	-1253.048	614.351
CO₂+HFO-1243zf	d_i	-8.936	19.701	-28.049	-49.576	146.804	-91.540
CO₂+丙烷	c_i	48.580	-169.524	533.658	-1211.609	1045.265	-320.067
CO₂+丙烷	d_i	0.135	-1.066	3.737	-7.371	7.463	-2.816
CO₂+丁烷	c_i	69.746	-182.626	1168.023	-2414.712	1902.741	-543.175
CO₂+丁烷	d_i	0.236	-1.530	5.760	-11.550	10.599	-3.417
CO₂+异丁烷	c_i	96.779	-258.365	1051.786	-1945.810	1443.448	-386.902
CO₂+异丁烷	d_i	0.278	-2.431	9.252	-17.703	15.902	-5.222

二元系	混合工质	AAD(T_c)/%
二元系	混合工质	Li	CP	RK	REFPROP 10.0
CO₂+HFC/HFO	CO₂+HFC-32	0.15	0.15	0.08	0.40
	CO₂+HFC-134a	1.14	0.81	0.13	1.45
	CO₂+HFC-152a	0.09	0.19	0.06	0.57
	CO₂+HFO-1234yf	0.69	0.23	0.13	2.28
	CO₂+HFO-1234ze(E)	0.47	0.14	0.14	1.29
	CO₂+HFO-1243zf	0.76	0.44	0.19	2.63
	平均值	0.55	0.33	0.12	1.44
CO₂+HC	CO₂+丙烷	2.76	0.67	0.24	0.43
	CO₂+正丁烷	3.46	0.84	0.28	0.64
	CO₂+异丁烷	2.82	0.98	0.34	0.73
	平均值	3.01	0.83	0.29	0.60

二元系	混合工质	AAD(p_c)/%
二元系	混合工质	CP	CP (k_ij =0)	RK	Li+KK	CP+KK	REFPROP 10.0
CO₂+HFC/HFO	CO₂+HFC-32	0.56	3.16	0.47	2.64	2.30	0.57
	CO₂+HFC-134a	1.38	2.79	0.57	8.57	6.41	5.22
	CO₂+HFC-152a	0.69	2.07	0.25	3.47	1.81	3.19
	CO₂+HFO-1234yf	0.91	4.14	0.24	14.02	10.77	13.11
	CO₂+HFO-1234ze(E)	0.67	6.46	0.62	13.91	10.34	7.56
	CO₂+HFO-1243zf	1.29	3.99	0.74	12.22	9.09	13.12
	平均值	0.92	3.77	0.48	9.14	6.79	7.13
CO₂+HC	CO₂+丙烷	4.75	15.83	1.79	9.16	6.20	2.39
	CO₂+正丁烷	5.89	24.94	1.46	14.75	5.38	1.64
	CO₂+异丁烷	4.68	24.91	0.14	15.43	5.30	4.98
	平均值	5.10	21.89	1.13	13.11	5.63	3.00

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