适配环保制冷剂R290的阻燃剂性能研究

doi:10.11949/0438-1157.20241289

摘要/Abstract

摘要：

目前国际社会对环保工质的需求越来越大，但由于环保工质往往具有一定的可燃性，其使用受到限制。实验测试了R227ea对环保工质R290可燃性的抑制效果，发现随着R227ea比例的增加，混合物的可燃下限逐渐上升，可燃上限先上升后下降，R227ea对R290可燃性的临界抑制比为3.35。提出在R227ea中加入R1216组成新型混合阻燃剂，以达到性能“优势互补”的目的。混合阻燃剂相比R227ea具有更大的单位容积制冷量，相比R1216具有更高的制冷系数和热导率，更低的黏度。比较三元混合工质R290/R227ea/R1216与纯工质R290的性能发现，当R290/R227ea/R1216的比例为21%/6%/73%时，其制冷系数和单位容积制冷量分别为R290的103.8%和94.2%，并且环保性和可燃性满足要求。研究结果对环保工质R290的安全应用及新型混合阻燃剂的研究具有参考意义。

关键词: 制冷剂, R290, 阻燃剂, 可燃性, 二元混合物, 爆炸, 有机化合物

Abstract:

At present, the international community demand for environmentally friendly working fluids is more and more big, but their use is limited due to their flammability. This study experimentally tested the inhibition effect of R227ea on the flammability of environmentally friendly working fluid R290. It was found that as the proportion of R227ea increased, the lower flammability limit of the mixture gradually increased, and the upper flammability limit first increased and then decreased. The critical inhibitory ratio of R227ea on the flammability of R290 was 3.35. Considering the strong greenhouse effect of R227ea, this study proposed to add environmentally friendly R1216 to R227ea to form a new hybrid flame retardant, thereby achieving“complementary advantages”in their performance. The new mixed flame retardant has a large unit volume cooling capacity compared to R227ea, higher cooling coefficient and thermal conductivity compared to R1216, and lower viscosity. By comparing the performance of ternary mixed refrigerant R290/R227ea/R1216 with pure refrigerant R290, it was found that when the composition ratio of R290/R227ea/R1216 is 21%/6%/73%, its coefficient of performance and unit volume cooling capacity were 103.8% and 94.2% of pure R290, respectively, and its environmental friendliness and flammability meet the requirements. The research results have reference significance for the safe application of R290 and the study of new hybrid flame retardant.

Key words: refrigerant, R290, flame retardant, flammability, binary mixture, explosions, organic compounds

中图分类号:

TB 64

冯彪, 张昭, 李思琪, 王秉睿, 吴红颖, 史淼, 王丹, 马素霞. 适配环保制冷剂R290的阻燃剂性能研究[J]. 化工学报, 2025, 76(S1): 462-468.

Biao FENG, Zhao ZHANG, Siqi LI, Bingrui WANG, Hongying WU, Miao SHI, Dan WANG, Suxia MA. Performance of flame retardant for environmentally friendly refrigerant R290[J]. CIESC Journal, 2025, 76(S1): 462-468.

图/表 8

图1 实验装置示意图

Fig.1 Schematic diagram of experimental setup

表1 验证实验装置精度

Table 1 Verify accuracy of experimental setup

工质	可烯极限	文献值/%	测试值/%	相对误差/%
R290	LFL	2.1^{[10, 25]}	2.13	+1.43
R290	UFL	9.5^[10]	9.6	+1.05

图2 可燃下限（LFL）火焰现象

Fig.2 Flame phenomenon of lower flammability limit

图3 可燃上限（UFL）火焰现象

Fig.3 Flame phenomenon of upper flammability limit

图4 R227ea/R290可燃极限

Fig.4 Flammability limit of R227ea/R290

表2 可燃极限拟合的多项式参数

Table 2 Polynomial parameters of flammability limit

项目	k_a	k_b	k_c	k_d	R²
LFL	0.13357	-0.26246	1.7975	2.14464	0.986
UFL	-0.22987	-0.30369	4.10417	8.92672	0.978

图5 混合阻燃剂R1216/R227ea的相对性能参数

Fig.5 Relative performance parameters of mixed flame retardant R1216/R227ea

图6 性能分析

Fig.6 Performance analysis

参考文献 30

1	Official Journal of the European Union. Regulation(EU) No. 517/2014 of the European parliament and of the council of 16 April 2014 on fluorinated greenhouse gases and repealing regulation (EC) No. 842/2006 [R]. European Union: OJ, 2014.
2	Papasavva S, Andersen S O. Green‐MAC‐LCCP^©: life‐cycle climate performance metric for mobile air conditioning technology choice[J]. Environmental Progress & Sustainable Energy, 2011, 30(2): 234-247.
3	Mota-Babiloni A, Makhnatch P, Khodabandeh R, et al. Experimental assessment of R134a and its lower GWP alternative R513A[J]. International Journal of Refrigeration, 2017, 74: 682-688.
4	肖学智, 周晓芳, 徐浩阳, 等. 低GWP制冷剂研究现状综述[J]. 制冷技术, 2014, 34(6): 37-42.
	Xiao X Z, Zhou X F, Xu H Y, et al. An overview on the research progress of low GWP alternatives to HCFCs[J]. Chinese Journal of Refrigeration Technology, 2014, 34(6): 37-42.
5	吴曦, 区祖迪, 张鑫杰, 等. HFO-1243zf 爆燃特性实验研究[J]. 化工学报, 2023, 74(S1): 346-352.
	Wu X, Ou Z D, Zhang X J, et al. Experimental study on the flammability of HFO-1243zf[J]. CIESC Journal, 2023, 74(S1): 346-352.
6	周培旭, 李亚伦, 叶恭然, 等. 有限空间内工质物性对制冷剂泄漏扩散特性的影响[J]. 化工学报, 2023, 74(2): 953-967.
	Zhou P X, Li Y L, Ye G R, et al. Influence of physical properties of working fluids on leakage and diffusion characteristics of refrigerant in limited space[J]. CIESC Journal, 2023, 74(2): 953-967.
7	刘敬辉, 陈江平, 陈芝久. 碳氢制冷剂用于汽车空调的理论分析和实验研究[J]. 化工学报, 2006, 57(9): 2048-2052.
	Liu J H, Chen J P, Chen Z J. Theoretical analysis and experimental study on hydrocarbons to replace R134a in car air conditioners[J]. CIESC Journal, 2006, 57(9): 2048-2052.
8	Zhong Q, Huang Y J, Zhao H, et al. Experimental study on the influence of trifluoroiodomethane on the flammability of difluoromethane and propane[J]. International Journal of Refrigeration, 2022, 135: 14-19.
9	Fan X Y, Liu Y F, Li X X, et al. Experimental study on the influence of flame retardants under high-temperature conditions on the flammability of R1234ze(E) and R290[J]. Energy, 2024, 293: 130569.
10	Cai D H, Hao Z A, Xu H, et al. Research on flammability of R290/R134a, R600a/R134a and R600a/R290 refrigerant mixtures[J]. International Journal of Refrigeration, 2022, 137: 53-61.
11	Zhong L, Zhang W, Li X, et al. Effects of trifluoroiodomethane and pentafluoroethane on combustion characteristics of flammable refrigerant propane[J]. International Journal of Refrigeration, 2023, 148: 25-34.
12	杨昭, 彭继军, 黄海涛. R245fa阻燃特性理论与试验研究[J]. 燃烧科学与技术, 2006, 12(4): 358-361.
	Yang Z, Peng J J, Huang H T. Theoretical and experimental study on flame-retarding characteristics of R245fa[J]. Journal of Combustion Science and Technology, 2006, 12(4): 358-361.
13	Feng B, Zhang Z, Jian L R, et al. Effect of two halogenated olefins on combustion characteristics of Isobutane[J]. Fuel, 2024, 360: 130545.
14	冯彪, 张昭, 简琳睿, 等. 新型高温热泵混合工质替代R245fa的性能研究[J]. 太原理工大学学报, 2023, 54(5): 941-949.
	Feng B, Zhang Z, Jian L R, et al. Study on the performance of new high temperature heat pump mixtures as alternatives to R245fa[J]. Journal of Taiyuan University of Technology, 2023, 54(5): 941-949.
15	钟志锋, 张子琦, 李小燕, 等. 可燃制冷剂的风险评估和降低风险措施[J]. 制冷技术, 2013, 33(1): 45-47.
	Zhong Z F, Zhang Z Q, Li X Y, et al. Study on risk assessment and safety measures of flammable refrigerants[J]. Chinese Journal of Refrigeration Technology, 2013, 33(1): 45-47.
16	吴俊峰, 金钊, 张秀平, 等. 可燃性制冷剂的制冷空调产品生产过程安全防护策略[J]. 制冷技术, 2020, 40(1): 42-47.
	Wu J F, Jin Z, Zhang X P, et al. Safety protection strategy in production process of refrigeration and air-conditioning products with flammable refrigerants[J]. Chinese Journal of Refrigeration Technology, 2020, 40(1): 42-47.
17	Feng B, Zhang Z, Wu H Y, et al. Research on flammability of 3,3,3-trifluoropropene and its binary mixtures with flame retardants[J]. Process Safety and Environmental Protection, 2024, 190: 1002-1010.
18	Wu X, Zhang X J, Tang F Y, et al. Flammability inhibition effects of R227ea, R125, R134a, and R744 on 3,3,3-trifluoropropene (R1243zf)[J]. International Journal of Refrigeration, 2022, 134: 55-63.
19	Feng B, Yang Z, Zhai R. Experimental study on the influence of the flame retardants on the flammability of R1234yf[J]. Energy, 2018, 143: 212-218.
20	Wallington T J, Sulbaek Andersen M P, Nielsen O J. Atmospheric chemistry of short-chain haloolefins: photochemical ozone creation potentials (POCPs), global warming potentials (GWPs), and ozone depletion potentials (ODPs) main[J]. Chemosphere, 2014, 129(6): 135-141.
21	王小虎. R227ea在高温行车空调上的应用及性能分析[J]. 低温与超导, 2017, 45(4): 60-65.
	Wang X H. Analysis of application of R227ea in bridge crane air-conditioners at high ambient temperature[J]. Cryogenics and Superconductivity, 2017, 45(4): 60-65.
22	Kumma N, Kruthiventi S S H. Effect of dilutant concentration on the performance of environment-friendly mixed refrigerants used in domestic refrigerators[J]. Environmental Science and Pollution Research, 2022, 29(47): 71988-72000.
23	吴晓伟, 翁平, 邹高万, 等. 舰船绿色环保灭火剂选型分析[J]. 船舶, 2011, 22(6): 29-35.
	Wu X W, Weng P, Zou G W, et al. Analysis and selection of clean extinguishing agents in naval ship[J]. Ship & Boat, 2011, 22(6): 29-35.
24	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 制冷剂编号方法和安全性分类: [S]. 北京: 中国标准出版社, 2017.
	General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, Standardization Administration of the People's Republic of China. Number designation and safety classification of refrigerants: [S]. Beijing: Standards Press of China, 2017.
25	ASHRAE. Designation and safety classification of refrigerants: ANSI/A Standard 34-2019[S]. America: ASHRAE, 2019.
26	Feng B, Jian L R, Wu H Y, et al. Effect of trans-1,3,3,3-tetrafluoropropene on flammability of difluoromethane[J]. Fuel, 2024, 367: 131517.
27	易勇. R1234ze/152a在家用空调蒸发器中的仿真研究[D]. 南昌: 南昌大学, 2017.
	Yi Y. Simulation of R1234ze/152a in evaporator of domestic air conditioner[D]. Nanchang: Nanchang University, 2017.
28	Zhao Z, Luo J L, Yang K Y, et al. Experimental study on the influence of flame retardants on the flammability of R1234yf[J]. Journal of Loss Prevention in the Process Industries, 2023, 81: 104945.
29	Stephen R. 燃烧学导论: 概念与应用[M]. 姚强, 李水清, 王宇, 译. 3版. 北京: 清华大学出版社, 2015: 93.
	Stephen R. An Introduction to Combustion: Concepts and Applications[M]. Yao Q, Li S Q, Wang Y, trans. 3rd ed. Beijing: Tsinghua University Press, 2015: 93.
30	田贯三. 可燃制冷剂爆炸理论与燃烧爆炸抑制机理的研究[D]. 天津: 天津大学, 2000.
	Tian G S. Study on explosion theory of flammable refrigerant and suppression mechanism of combustion explosion[D]. Tianjin: Tianjin University, 2000.

[1]	朱腾飞, 刘晔. 低GWP制冷剂在新能源汽车空调应用性能分析[J]. 化工学报, 2025, 76(S1): 343-350.
[2]	杨语晴, 李银龙, 晏刚. 采用低GWP制冷剂的级联加热自复叠高温热泵循环热力学分析[J]. 化工学报, 2025, 76(S1): 43-53.
[3]	彭建斌, 李明, 谢军龙, 陈建业. 液氢接收终端液氢泄漏扩散及爆炸超压研究[J]. 化工学报, 2025, 76(S1): 453-461.
[4]	拓振光, 李荣亮, 康绍辉, 牛玉清, 周志全, 叶开凯, 马海桃, 刘顺, 李洪, 高鑫. 静态法测定WF₆-MoF₆体系汽液相平衡数据的误差分析与修正[J]. 化工学报, 2025, 76(5): 2270-2278.
[5]	苏彬, 董浩伟, 罗振敏, 邓军, 王涛, 程方明. 气粉两相体系爆炸动力学特性及机理研究进展[J]. 化工学报, 2024, 75(6): 2109-2122.
[6]	张帅, 喻健良, 丁建飞, 闫兴清. 气流输运工况玉米淀粉爆炸火焰传播与压力特性实验研究[J]. 化工学报, 2024, 75(5): 2072-2080.
[7]	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.
[8]	王迪, 崔颖晗, 孙灵芳, 周云龙. 超临界二氧化碳混合工质储能系统热力学分析[J]. 化工学报, 2024, 75(10): 3414-3423.
[9]	吴曦, 区祖迪, 张鑫杰, 徐士鸣, 朱晓静. HFO-1243zf爆燃特性实验研究[J]. 化工学报, 2023, 74(S1): 346-352.
[10]	高润淼, 宋孟杰, 高恩元, 张龙, 张旋, 邵苛苛, 甄泽康, 江正勇. 冷链装备制冷剂相关温室气体减排研究进展[J]. 化工学报, 2023, 74(S1): 1-7.
[11]	李珍宝, 李超, 王虎, 王绍瑞, 黎泉. MPP抑制铝镁合金粉尘爆炸微观机理研究[J]. 化工学报, 2023, 74(8): 3608-3614.
[12]	杨克, 贾岳, 纪虹, 邢志祥, 蒋军成. 垃圾焚烧飞灰对瓦斯爆炸压力及火焰传播的抑制作用及机理研究[J]. 化工学报, 2023, 74(8): 3597-3607.
[13]	朱理想, 罗默也, 张晓东, 龙涛, 余冉. 醌指纹法指示三氯乙烯污染土功能微生物活性应用研究[J]. 化工学报, 2023, 74(6): 2647-2654.
[14]	雷博雯, 吴建华, 吴启航. R290低压比热泵高补气过热度循环研究[J]. 化工学报, 2023, 74(5): 1875-1883.
[15]	武子超, 汪志雷, 李荣业, 李可昕, 华敏, 潘旭海, 王三明, 蒋军成. 点火方式对欠膨胀氢气射流爆炸超压影响规律研究[J]. 化工学报, 2023, 74(3): 1409-1418.