基于多参数评估原则筛选高温热泵用三元非共沸混合工质

doi:10.11949/0438-1157.20230844

摘要/Abstract

摘要：

高温热泵因其能将低温废热转化为高温热能，成为低温废热再利用的一项关键节能技术。其中，针对高温热泵的混合工质筛选问题是当前研究焦点之一。基于由低沸点工质CO₂和中高沸点工质HC类、HFO类组成的低GWP三元非共沸混合工质，提出了一种广泛适用的基于工作压力、温度滑移、可燃性和能效等关键因素的热泵用非共沸混合工质筛选方法，并对高温热泵系统进行了能效评估。结果表明，当混合工质CO₂/R600a/R1234ze（Z）的质量分数为0.1/0.1/0.8时，设定工况下的热泵系统最大热力性能系数（COP_h）为4.31，对应的单位容积热容量（VHC）为2766 kJ/m³，㶲效率（η_ex）为0.50。

关键词: 非共沸混合工质, 余热回收, 高温热泵, 温度滑移, 热力学

Abstract:

High-temperature heat pumps have become a key energy-saving technology for low-temperature waste heat reuse because they can convert low-temperature waste heat into high-temperature thermal energy. To find a ternary zeotropic mixture suitable for the high-temperature heat pump, this paper proposes a comprehensive selected method that integrates considerations, including operating pressure, glide temperature, flammability, and energy efficiency. The results revealed that, with the optimal refrigerant selection, a ternary zeotropic mixture of CO₂/R600a/R1234ze(Z) with mass fraction of 0.1/0.1/0.8 is selected as the working medium for the high-temperature heat pump, resulting in a significant enhancement in performance. Under the specified conditions, the high-temperature heat pump system attains impressive performance metrics, including maximum coefficient of performance (COP_h) of 4.31, volumetric heat capacity (VHC) of 2766 kJ/m³, and exergy efficiency (η_ex) of 0.50. This study strongly advocates for the implementation of the high-temperature heat pump technology within the domain of low-grade industrial waste heat utilization. Through refrigerant selection, the high-temperature heat pump can effectively reclaim waste heat generated during industrial production processes, and making substantial contributions to the dual-carbon target.

Key words: zeotropic mixture, waste heat recovery, high-temperature heat pump, glide temperature, thermodynamics

中图分类号:

TB 61⁺1

周昉, 刘剑, 张小松. 基于多参数评估原则筛选高温热泵用三元非共沸混合工质[J]. 化工学报, 2023, 74(11): 4487-4500.

Fang ZHOU, Jian LIU, Xiaosong ZHANG. Selection of ternary zeotropic mixtures for high-temperature heat pumps on multiparameter evaluation principles[J]. CIESC Journal, 2023, 74(11): 4487-4500.

图/表 17

图1 单温工质(a)与非共沸混合工质(b)的换热过程不可逆损失对比

Fig.1 Comparison of irreversible losses during heat transfer between single-temperature refrigerant (a) and zeotropic mixture (b)

表1 高温热泵用混合工质研究现状

Table 1 Summary of zeotropic mixtures for high-temperature heat pump

年份	工质	出水温度/冷凝温度	COP	热泵类型	文献
2023	R1234ze(Z)/acetone R1234ze(Z)/isohexane	200℃	4.5	带中间换热器的高温热泵	[19]
2023	CO₂/R600 CO₂/R601	115℃	3.6	级联蒸汽压缩式	[20]
2023	R600a/R601a	80℃	4.82	单级蒸汽压缩式	[21]
2023	CO₂/acetone	200℃	5.15	带中间换热器的高温热泵	[22]
2022	CO₂/R134a	50℃	3.07	级联蒸汽压缩式	[23]
2020	R290/R600a/R13I1	90℃	3.8	两级压缩高温热泵	[24]
2019	CO₂/R32 CO₂/R41	99℃	5.28	带中间换热器的高温热泵	[25]
2010	R152a/R245fa	90℃	3.4	单级蒸汽压缩式	[26]

图2 非共沸混合工质高温热泵循环图

Fig.2 Diagram of high-temperature heat pump with zeotropic mixture

表2 高温热泵系统运行参数

Table 2 Operating parameters of high-temperature heat pump system

参数	数值	参数	数值
废水入口温度（T₅）	30℃	蒸发器中露点温度（T_evap,dew）	T₅-5℃
废水出口温度（T₆）	5℃	冷凝器中露点温度（T_cond,dew）	T₈+5℃
热水进口温度（T₇）	30℃	蒸发器中过热度（T_sh）	5℃
热水出口温度（T₈）	85℃	冷凝器中过冷度（T_sc）	3℃

表3 系统各部件能量平衡和㶲平衡

Table 3 Energy and exergy balance of each component

部件	能量平衡	㶲平衡^②
压缩机	$W c o m p = m r (h 2 - h 1) = m r (h 2, s - h 1) / η s ①$	$E x d, c o m p = W c o m p + m r (e x 1 - e x 2)$
冷凝器	$Q c o n d = m r (h 2 - h 3) = m h w (h 8 - h 7)$	$E x d, c o n d = m r (e x 2 - e x 3) + m h w (e x 7 - e x 8)$
膨胀阀	$h 3 = h 4$	$E x d, v a = m r (e x 3 - e x 4)$
蒸发器	$Q e v a p = m r (h 1 - h 4) = m w (h 5 - h 6)$	$E x d, e v a p = m r (e x 4 - e x 1) + m w (e x 5 - e x 6)$

表3 系统各部件能量平衡和㶲平衡

Table 3 Energy and exergy balance of each component

部件	能量平衡	㶲平衡^②
压缩机	$W c o m p = m r (h 2 - h 1) = m r (h 2, s - h 1) / η s ①$	$E x d, c o m p = W c o m p + m r (e x 1 - e x 2)$
冷凝器	$Q c o n d = m r (h 2 - h 3) = m h w (h 8 - h 7)$	$E x d, c o n d = m r (e x 2 - e x 3) + m h w (e x 7 - e x 8)$
膨胀阀	$h 3 = h 4$	$E x d, v a = m r (e x 3 - e x 4)$
蒸发器	$Q e v a p = m r (h 1 - h 4) = m w (h 5 - h 6)$	$E x d, e v a p = m r (e x 4 - e x 1) + m w (e x 5 - e x 6)$

表4 所选工质的物性参数及其环境性能［34］

Table 4 Physical parameters and environmental performance of common pure refrigerants［34］

工质	标准沸点/℃	临界温度/℃	临界压力/MPa	GWP₁₀₀	可燃性	LFL/%（体积分数）	UFL/%（体积分数）
CO₂	-78.46	30.98	7.38	1	A1	—	—
R600a	-11.75	134.66	3.63	约20	A3	1.8	8.4
R290	-42.11	96.74	4.25	5	A3	2.1	9.5
R1270	-47.62	91.06	4.56	1.8	A3	2	11.1
RE170	-24.78	127.23	5.34	1	A3	3.4	27
R1336mzz(Z)	33.45	171.35	2.90	2	A1	—	—
R1234ze(Z)	9.75	150.12	3.53	＜1	A2L	7.5	16.4

图3 不同三元非共沸混合工质的高温热泵特性筛选流程图

Fig.3 Selection flow chart of proposed high-temperature heat pump using various ternary zeotropic mixtures

表5 纯工质的生成焓（298 K）［34］

Table 5 Enthalpy of formation of various pure refrigerants （298 K）［34］

反应物		生成物
工质	生成焓/(kJ/mol)	工质	生成焓/(kJ/mol)
CO₂	-393.51	CO₂	-393.51
R600a	-134.20	COF₂	-638.90
R290	-104.70	H₂O	-241.83
R1270	20.41	HF	-273.30
RE170	-184.10
R1336mzz(Z)	—
R1234ze(Z)	-781.82

表6 数学模型验证条件和结果［43］

Table 6 Compared working conditions and results［43］

CO₂/R32/

R1234yf

图4 计算值与实验值比较

Fig.4 Comparison between calculated values and experimental values

表7 根据运行压力挑选出的混合工质组分比

Table 7 Selected results with the operated pressure

混合工质	质量分数比例			运行压力
CO₂/R600a/R1336mzz(Z)	CO₂	R600a	R1336mzz(Z)	P_evap/MPa	P_cond/MPa
	0.4	0.1~0	0.5~0.6	0.34~0.26	2.90~2.23
	0.3	0.3~0	0.4~0.7	0.41~0.19	2.88~1.57
	0.2	0.8~0.1	0~0.7	0.47~0.18	2.37~1.43
	0.1	0.9~0.2	0~0.7	0.41~0.17	1.96~1.28
	0	1~0.3	0~0.7	0.35~0.16	1.64~1.12
CO₂/R290/R1336mzz(Z)	CO₂	R290	R1336mzz(Z)	P_evap/MPa	P_cond/MPa
	0.3	0.1~0	0.6~0.7	0.26~0.19	2.19~1.57
	0.2	0.3~0.1	0.5~0.7	0.35~0.19	2.87~1.56
	0.1	0.4~0.2	0.5~0.7	0.35~0.19	2.63~1.54
	0	0.6~0.3	0.4~0.7	0.46~0.19	2.76~1.49
CO₂/R1270/R1336mzz(Z)	CO₂	R1270	R1336mzz(Z)	P_evap/MPa	P_cond/MPa
	0.3	0.1~0	0.6~0.7	0.26~0.19	2.22~1.57
	0.2	0.2~0.1	0.6~0.7	0.26~0.20	2.20~1.58
	0.1	0.4~0.2	0.5~0.7	0.36~0.20	2.84~1.59
	0	0.6~0.3	0.4~0.7	0.46~0.19	2.76~1.49
CO₂/RE170/R1336mzz(Z)	CO₂	RE170	R1336mzz(Z)	P_evap/MPa	P_cond/MPa
	0.4	0.1~0	0.5~0.6	0.33~0.26	2.75~2.23
	0.3	0.3~0	0.4~0.7	0.39~0.19	2.74~1.57
	0.2	0.6~0.1	0.2~0.7	0.53~0.18	2.97~1.43
	0.1	0.8~0.2	0.1~0.7	0.56~0.17	2.84~1.29
	0	1~0.3	0~0.7	0.59~0.17	2.72~1.17
CO₂/R600a/R1234ze(Z)	CO₂	R600a	R1234ze(Z)	P_evap/MPa	P_cond/MPa
	0.3	0.1~0	0.6~0.7	0.44~0.38	2.91~2.55
	0.2	0.8~0	0~0.8	0.47~0.30	2.37~1.92
	0.1	0.9~0	0~0.9	0.41~0.23	1.96~1.46
	0	1~0	0~1	0.35~0.18	1.64~1.08
CO₂/R290/R1234ze(Z)	CO₂	R290	R1234ze(Z)	P_evap/MPa	P_cond/MPa
	0.2	0.1~0	0.7~0.8	0.37~0.30	2.47~1.92
	0.1	0.3~0	0.6~0.9	0.47~0.23	2.86~1.46
	0	0.5~0	0.5~1	0.56~0.18	2.90~1.08
CO₂/R1270/R1234ze(Z)	CO₂	R1270	R1234ze(Z)	P_evap/MPa	P_cond/MPa
	0.2	0.1~0	0.7~0.8	0.38~0.30	2.50~1.92
	0.1	0.2~0.1	0.7~0.9	0.38~0.23	2.42~1.46
	0	0.5~0	0.5~1	0.56~0.18	2.90~1.08
CO₂/RE170/R1234ze(Z)	CO₂	RE170	R1234ze(Z)	P_evap/MPa	P_cond/MPa
	0.3	0.1~0	0.6~0.7	0.45~0.38	2.89~2.55
	0.2	0.4~0	0.4~0.8	0.52~0.30	2.91~1.92
	0.1	0.8~0	0.1~0.9	0.61~0.23	2.95~1.46
	0	1~0.3	0~0.7	0.59~0.18	2.72~1.08

图5 三元非共沸混合工质的温度滑移（P=2 MPa）

Fig.5 The glide temperature of ternary zeotropic mixtures

表8 根据温度滑移挑选出的混合工质组分比

Table 8 Selected results with the glide temperature

混合工质	质量分数比例			温度滑移	混合工质	质量分数比例			温度滑移
CO₂/R600a/ R1336mzz(Z)	CO₂	R600a	R1336mzz(Z)	ΔT_glide/K	CO₂/R600a/ R1234ze(Z)	CO₂	R600a	R1234ze(Z)	ΔT_glide/K
	0.2	0.8~0.6	0~0.2	56.55~58.90		0.2	0.8~0.2	0~0.6	56.55~58.79
	0.1	0.6~0.3	0.3~0.6	40.22~58.57		0.1	0.2~0	0.7~0.9	42.62~53.44
CO₂/R290/ R1336mzz(Z)	CO₂	R290	R1336mzz(Z)	ΔT_glide/K	CO₂/R290/ R1234ze(Z)	CO₂	R290	R1234ze(Z)	ΔT_glide/K
CO₂/R290/ R1336mzz(Z)	0.1	0.4~0.3	0.5~0.6	48.76~59.95	CO₂/R290/ R1234ze(Z)	0.1	0.2~0	0.7~0.9	44.38~53.44
CO₂/R1270/ R1336mzz(Z)	CO₂	R1270	R1336mzz(Z)	ΔT_glide/K	CO₂/R1270/ R1234ze(Z)	CO₂	R1270	R1234ze(Z)	ΔT_glide/K
CO₂/R1270/ R1336mzz(Z)	0.1	0.4~0.3	0.5~0.6	45.59~56.39	CO₂/R1270/ R1234ze(Z)	0.1	0.2~0	0.7~0.9	42.83~53.44
CO₂/RE170/ R1336mzz(Z)	CO₂	RE170	R1336mzz(Z)	ΔT_glide/K	CO₂/RE170/ R1234ze(Z)	CO₂	RE170	R1234ze(Z)	ΔT_glide/K
	0.2	0.5~0.4	0.3~0.4	41.83~50.67		0.2	0.3~0.1	0.5~0.7	42.42~58.39
	0.1	0.4~0.3	0.5~0.6	40.38~49.63		0.1	0.1~0	0.8~0.9	43.09~53.44

图6 根据HOC、LFL和燃烧速度分类的ASHRAE安全等级

Fig.6 ASHRAE safety classifications according to HOC, LFL and burning velocity characteristics

表9 根据安全性和可燃性挑选出的混合工质组分比

Table 9 Selected results with the safety and flammability

混合工质	工质对	质量分数比例	可燃等级	混合工质	工质对	质量分数比例	可燃等级
CO₂/R600a/ R1336mzz(Z)	R1	0.1/0.6/0.3	≤A2	CO₂/R600a/ R1234ze(Z)	R13	0.2/0.3/0.5	≤A2
	R2	0.1/0.5/0.4	≤A2		R14	0.2/0.2/0.6	≤A2
	R3	0.1/0.4/0.5	≤A2		R15	0.1/0.2/0.7	≤A2
	R4	0.1/0.3/0.6	≤A2		R16	0.1/0.1/0.8	≤A2
CO₂/R290/ R1336mzz(Z)	R5	0.1/0.4/0.5	≤A2	CO₂/R290/ R1234ze(Z)	R17	0.1/0.2/0.7	≤A2
CO₂/R290/ R1336mzz(Z)	R6	0.1/0.3/0.6	≤A2	CO₂/R290/ R1234ze(Z)	R18	0.1/0.1/0.8	≤A2
CO₂/R1270/ R1336mzz(Z)	R7	0.1/0.4/0.5	≤A2	CO₂/R1270/ R1234ze(Z)	R19	0.1/0.2/0.7	≤A2
CO₂/R1270/ R1336mzz(Z)	R8	0.1/0.3/0.6	≤A2	CO₂/R1270/ R1234ze(Z)	R20	0.1/0.1/0.8	≤A2
CO₂/RE170/ R1336mzz(Z)	R9	0.2/0.5/0.3	≤A2	CO₂/RE170/ R1234ze(Z)	R21	0.2/0.3/0.5	≤A2
	R10	0.2/0.4/0.4	≤A2		R22	0.2/0.2/0.6	≤A2
	R11	0.1/0.4/0.5	≤A2		R23	0.2/0.1/0.7	≤A2
	R12	0.1/0.3/0.6	≤A2		R24	0.1/0.1/0.8	≤A2

图7 不同质量分数的混合工质的高温热泵性能

Fig.7 High temperature heat pump performance of mixtures with various mass fractions

图8 工质对CO2/R600a/R1234ze(Z)（0.1/0.1/0.8）的热泵循环T-s图

Fig.8 T-s diagram of heat pump cycle with CO2/R600a/R1234ze(Z)(0.1/0.1/0.8) as refrigerant

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