Article(id=1239215310583157156, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, articleNumber=null, orderNo=null, doi=10.12465/j.issn.0253-4339.2025.04.022, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1711296000000, receivedDateStr=2024-03-25, revisedDate=1721232000000, revisedDateStr=2024-07-18, acceptedDate=1721664000000, acceptedDateStr=2024-07-23, onlineDate=1773381553550, onlineDateStr=2026-03-13, pubDate=1755273600000, pubDateStr=2025-08-16, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773381553550, onlineIssueDateStr=2026-03-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773381553550, creator=13701087609, updateTime=1773381553550, updator=13701087609, issue=Issue{id=1239215308985136031, tenantId=1146029695717560320, journalId=1238823019242635269, year='2025', volume='46', issue='4', pageStart='1', pageEnd='170', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773381553169, creator=13701087609, updateTime=1773381893131, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1239216734947824534, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1239216734947824535, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239215308985136031, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=22, endPage=28, ext={EN=ArticleExt(id=1239215310771900838, articleId=1239215310583157156, tenantId=1146029695717560320, journalId=1238823019242635269, language=EN, title=Research on the Flammability Limits of R1234yf/R290 and R1234ze(E)/R290 Mixtures, columnId=null, journalTitle=Journal of Refrigeration, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Propane (R290) is a potential refrigerant substitute for household air conditioners. However, its flammability limits its application. In this study, the flammability limits of R290, 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,3,3,3-tetrafluoropropene (R1234ze(E)), R1234ze(E)/R290, and R1234yf/R290 were determined according to the ASHRAE 34-2022 standard. The effects of R1234yf and R1234ze(E) on the flammability of R290 were analyzed, and the inhibiting abilities of R1234yf, R1234ze(E), R32, R13I1, and R134a on the flammability of R290 were compared. In addition, the refrigeration cycle performance of R290 mixtures with different compositions was simulated. The results showed that both R1234yf and R1234ze(E) exhibited limited flame inhibition capabilities for R290. When the mass fractions of R1234yf and R1234ze(E) reached 80%, the lower flammability limit of the mixture increased by approximately 1.0%. The experimental data were correlated using the Le Chatelier model, which resulted in an average absolute deviation of 0.57% between the calculated and experimental results. Compared with R290, the energy efficiency ratio of the two refrigerants and R290 mixture decreased by less than 1%, and the volumetric cooling capacity increased by less than 0.4%. The flame inhibition effect of the refrigerant on R290 decreased in the following order: R13I1>R134a>R32>R1234ze(E)/R1234yf.

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Zhong Quan, male, senior engineer, Gree Electric Appliances Inc. of Zhuhai, 86-756-8587826, E-mail: . Research fields: environmentally friendly refrigerant.
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丙烷(R290)是一种极具潜力的家用空调替代制冷剂,但可燃性限制了其应用。根据ASHRAE 34-2022标准测试了R290、2,3,3,3-四氟丙烯(R1234yf)、反式-1,3,3,3-四氟丙烯(R1234ze(E))和二元混合物R1234ze(E)/R290、R1234yf/R290的可燃极限。分析了R1234yf和R1234ze(E)对R290可燃性的影响,并对比了R1234yf、R1234ze(E)、R32、R13I1和R134a对R290可燃性抑制能力。通过模拟计算了不同组分下R290混合物的制冷循环性能。结果表明:R1234yf和R1234ze(E)对R290可燃性的抑制能力相近且效果较差,当R1234yf和R1234ze(E)的质量分数达到80%时,混合物的可燃下限仅增加约1.0%。使用Le Chatelier模型对实验数据进行关联,计算结果与实验结果平均绝对偏差为0.57%。相比R290纯质,R1234ze(E)/R290与R1234yf/R290在共沸点附近的能效比衰减小于1%,单位容积制冷量增加小于0.4%。制冷剂对R290的燃烧抑制能力由大到小排序为:R13I1>R134a>R32>R1234ze(E)/R1234yf。

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钟权,男,高级工程师,珠海格力电器股份有限公司,0756-8587826,E-mail:。研究方向:环保制冷剂。
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Energy, 2023, 263: 126149., articleTitle=Experimental investigation on the inhibition of flame retardants on the flammability of R1234ze(E), refAbstract=null), Reference(id=1239232349595038702, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, doi=null, pmid=null, pmcid=null, year=2015, volume=35, issue=3, pageStart=2741, pageEnd=2748, url=null, language=null, rfNumber=[27], rfOrder=33, authorNames=TAKAHASHI F, KATTA V R, LINTERIS G T, journalName=Proceedings of the Combustion Institute, refType=null, unstructuredReference=TAKAHASHI F, KATTA V R, LINTERIS G T, et al. Combustion inhibition and enhancement of cup-burner flames by CF3Br, C2HF5, C2HF3Cl2, and C3H2F3Br[J]. Proceedings of the Combustion Institute, 2015, 35(3): 2741-2748., articleTitle=Combustion inhibition and enhancement of cup-burner flames by CF3Br, C2HF5, C2HF3Cl2, and C3H2F3Br, refAbstract=null), Reference(id=1239232349704090610, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, doi=null, pmid=null, pmcid=null, year=2001, volume=82, issue=2, pageStart=113, pageEnd=128, url=null, language=null, rfNumber=[28], rfOrder=34, authorNames=KONDO S, URANO Y, TOKUHASHI K, journalName=Journal of Hazardous Materials, refType=null, unstructuredReference=KONDO S, URANO Y, TOKUHASHI K, et al. Prediction of flammability of gases by using F-number analysis[J]. 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1进样口;2阀;3空气进口;4压力传感器;5真空泵;6恒温防爆箱;7 12 L球形烧瓶;8铂电阻温度计;9点火电极;10磁力搅拌器。

, figureFileSmall=P3/OmtWzoNJkpKc3O8nP8w==, figureFileBig=onglK2lMjkgevbkv5WfQKA==, tableContent=null), ArticleFig(id=1239232343530074923, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, language=EN, label=Fig.2, caption=Experimental flammability limits, figureFileSmall=rmxpXPsL1WrJK2Rd6GQrfA==, figureFileBig=YiVScnIx2zOnKs2crslcJw==, tableContent=null), ArticleFig(id=1239232343643321137, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, language=CN, label=图2, caption=可燃极限实验值, figureFileSmall=rmxpXPsL1WrJK2Rd6GQrfA==, figureFileBig=YiVScnIx2zOnKs2crslcJw==, tableContent=null), ArticleFig(id=1239232343739790135, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, language=EN, label=Fig.3, caption=F-number of R290 mixtures, figureFileSmall=Ak68WlbWyY4P+oH1wX2G/w==, figureFileBig=iRSb6WOY+rNNp9RaYQ4Kqg==, tableContent=null), ArticleFig(id=1239232343823676218, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, language=CN, label=图3, caption=R290混合物的F, figureFileSmall=Ak68WlbWyY4P+oH1wX2G/w==, figureFileBig=iRSb6WOY+rNNp9RaYQ4Kqg==, tableContent=null), ArticleFig(id=1239232343924339521, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, language=EN, label=Fig.4, caption=Variation of refrigeration performance of R290 mixed with R1234yf and R1234ze(E), figureFileSmall=mzrPo22mLR63GC1+qL0DNQ==, figureFileBig=uVgcPPeg07hKAIiQuhGebw==, tableContent=null), ArticleFig(id=1239232344020808516, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, language=CN, label=图4, caption=R290/R1234yf和R290/R1234ze(E)的制冷性能变化, figureFileSmall=mzrPo22mLR63GC1+qL0DNQ==, figureFileBig=uVgcPPeg07hKAIiQuhGebw==, tableContent=null), ArticleFig(id=1239232344100500290, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239215310583157156, language=EN, label=Tab.1, caption=Information of sample materials, figureFileSmall=null, figureFileBig=null, tableContent=
制冷剂名称来源纯度
R290丙烷山东粤安≥0.995
R1234ze(E)反式-1,3,3,3-四氟丙烯霍尼韦尔≥0.998
R1234yf2,3,3,3-四氟丙烯霍尼韦尔≥0.998
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制冷剂名称来源纯度
R290丙烷山东粤安≥0.995
R1234ze(E)反式-1,3,3,3-四氟丙烯霍尼韦尔≥0.998
R1234yf2,3,3,3-四氟丙烯霍尼韦尔≥0.998
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参数R290R1234ze(E)R1234yf
LFL/%UFL/%LFL/%UFL/%LFL/%UFL/%
实验值2.19.96.512.75.913.5
参考值2.0[13]9.9[13]6.4[26]12.2[26]5.5[13]13.0[13]
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参数R290R1234ze(E)R1234yf
LFL/%UFL/%LFL/%UFL/%LFL/%UFL/%
实验值2.19.96.512.75.913.5
参考值2.0[13]9.9[13]6.4[26]12.2[26]5.5[13]13.0[13]
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质量分数/%R1234yf/R290R1234ze(E)/R290
LFLexp/%LFLcal/%UFLexp/%UFLcal/%LFLexp/%LFLcal/%UFLexp/%UFLcal/%
02.12.19.99.92.12.19.99.9
202.12.310.110.22.22.310.110.1
402.42.510.810.52.42.510.810.4
602.52.811.211.02.72.811.210.8
803.13.513.311.83.23.613.311.4
1005.95.913.513.56.56.512.712.7
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质量分数/%R1234yf/R290R1234ze(E)/R290
LFLexp/%LFLcal/%UFLexp/%UFLcal/%LFLexp/%LFLcal/%UFLexp/%UFLcal/%
02.12.19.99.92.12.19.99.9
202.12.310.110.22.22.310.110.1
402.42.510.810.52.42.510.810.4
602.52.811.211.02.72.811.210.8
803.13.513.311.83.23.613.311.4
1005.95.913.513.56.56.512.712.7
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蒸发温度/℃冷凝温度/℃过热度/℃过冷度/℃等熵效率
1040550.75
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蒸发温度/℃冷凝温度/℃过热度/℃过冷度/℃等熵效率
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混合物R1234yf/R290和R1234ze(E)/R290的可燃极限研究
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沈军 , 黄宇杰 , 钟权 , 史贺纯 , 李华杰 , 赵桓
制冷学报 | 2025,46(4): 22-28
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制冷学报 | 2025, 46(4): 22-28
混合物R1234yf/R290和R1234ze(E)/R290的可燃极限研究
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沈军, 黄宇杰, 钟权 , 史贺纯, 李华杰, 赵桓
作者信息
  • 珠海格力电器股份有限公司 珠海 519070

通讯作者:

钟权,男,高级工程师,珠海格力电器股份有限公司,0756-8587826,E-mail:。研究方向:环保制冷剂。
Research on the Flammability Limits of R1234yf/R290 and R1234ze(E)/R290 Mixtures
Jun Shen, Yujie Huang, Quan Zhong , Hechun Shi, Huajie Li, Huan Zhao
Affiliations
  • Gree Electric Appliances Inc of Zhuhai, Zhuhai, 519070, China
出版时间: 2025-08-16 doi: 10.12465/j.issn.0253-4339.2025.04.022
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丙烷(R290)是一种极具潜力的家用空调替代制冷剂,但可燃性限制了其应用。根据ASHRAE 34-2022标准测试了R290、2,3,3,3-四氟丙烯(R1234yf)、反式-1,3,3,3-四氟丙烯(R1234ze(E))和二元混合物R1234ze(E)/R290、R1234yf/R290的可燃极限。分析了R1234yf和R1234ze(E)对R290可燃性的影响,并对比了R1234yf、R1234ze(E)、R32、R13I1和R134a对R290可燃性抑制能力。通过模拟计算了不同组分下R290混合物的制冷循环性能。结果表明:R1234yf和R1234ze(E)对R290可燃性的抑制能力相近且效果较差,当R1234yf和R1234ze(E)的质量分数达到80%时,混合物的可燃下限仅增加约1.0%。使用Le Chatelier模型对实验数据进行关联,计算结果与实验结果平均绝对偏差为0.57%。相比R290纯质,R1234ze(E)/R290与R1234yf/R290在共沸点附近的能效比衰减小于1%,单位容积制冷量增加小于0.4%。制冷剂对R290的燃烧抑制能力由大到小排序为:R13I1>R134a>R32>R1234ze(E)/R1234yf。

制冷剂  /  可燃极限  /  丙烷  /  2,3,3,3-四氟丙烯  /  反式-1,3,3,3-四氟丙烯

Propane (R290) is a potential refrigerant substitute for household air conditioners. However, its flammability limits its application. In this study, the flammability limits of R290, 2,3,3,3-tetrafluoropropene (R1234yf), trans-1,3,3,3-tetrafluoropropene (R1234ze(E)), R1234ze(E)/R290, and R1234yf/R290 were determined according to the ASHRAE 34-2022 standard. The effects of R1234yf and R1234ze(E) on the flammability of R290 were analyzed, and the inhibiting abilities of R1234yf, R1234ze(E), R32, R13I1, and R134a on the flammability of R290 were compared. In addition, the refrigeration cycle performance of R290 mixtures with different compositions was simulated. The results showed that both R1234yf and R1234ze(E) exhibited limited flame inhibition capabilities for R290. When the mass fractions of R1234yf and R1234ze(E) reached 80%, the lower flammability limit of the mixture increased by approximately 1.0%. The experimental data were correlated using the Le Chatelier model, which resulted in an average absolute deviation of 0.57% between the calculated and experimental results. Compared with R290, the energy efficiency ratio of the two refrigerants and R290 mixture decreased by less than 1%, and the volumetric cooling capacity increased by less than 0.4%. The flame inhibition effect of the refrigerant on R290 decreased in the following order: R13I1>R134a>R32>R1234ze(E)/R1234yf.

refrigerant  /  flammability limit  /  propane  /  2,3,3,3-tetrafluoropropene  /  trans-1,3,3,3-tetrafluoropropene
沈军, 黄宇杰, 钟权, 史贺纯, 李华杰, 赵桓. 混合物R1234yf/R290和R1234ze(E)/R290的可燃极限研究. 制冷学报, 2025 , 46 (4) : 22 -28 . DOI: 10.12465/j.issn.0253-4339.2025.04.022
Jun Shen, Yujie Huang, Quan Zhong, Hechun Shi, Huajie Li, Huan Zhao. Research on the Flammability Limits of R1234yf/R290 and R1234ze(E)/R290 Mixtures[J]. Journal of Refrigeration, 2025 , 46 (4) : 22 -28 . DOI: 10.12465/j.issn.0253-4339.2025.04.022
空调使用率和保有量随经济发展而稳步上升,据统计[1],2020年中国居民空调保有量达到了5.2亿台,碳排放量也随着空调使用量的增加而增加。空调碳排放包括直接排放和间接排放2部分,而直接排放为制冷剂的排放。当前空调主要使用R32和R410A制冷剂,碳排放当量是CO2的上千倍。2016年世界各国达成《<蒙特利尔议定书>基加利修正案》以减少温室气体氢氟烃(HFCs)的碳排放,R32、R134a、R125等18种HFCs被列入管控目录。为达成《基加利修正案》,各国制定一系列法规以限制高全球变暖潜值(Global Warming Potential,GWP)制冷剂使用,其中欧盟的要求最为严苛,2024年1月欧盟通过了最新的F-gas修订案,在2029年对于额定制冷量小于12 kW的分体式热泵或空调,禁止使用GWP>150的制冷剂,低GWP制冷剂的应用已成为家用空调发展面临的重要挑战。
R290的臭氧损耗潜值(ozone depletion potential,ODP)为0,GWP<1,可燃性类别为3类(高可燃性)[2],作为一种自然存在的物质,R290成本低廉且可持续,可以从生物气体或石油和天然气加工的副产品中获取。R290具有良好的环保性能和热物理特性[3-4],用于家用空调器的全生命周期碳排放量约为R32的85%[5],中国政府正积极推动R290家用空调产品的市场化,并纳入了《中国消耗臭氧层物质替代品推荐名录》中,但高可燃性限制了它的广泛使用[6]。一般认为,使用不可燃或弱可燃制冷剂与R290混合,可有效抑制R290的可燃性。Zhong Quan等[7]实验得出R13I1和R32均可抑制R290的可燃性。Cai Dehua等[8]研究了不同配比下R134a/R290和R134a/R600a的可燃极限,结果表明R134a对R290的可燃性抑制效果优于R600a。Zhong Li等[9]通过测试燃烧速度和可燃极限研究了制冷剂R125对R290的抑制效果。
作为第4代制冷剂,2,3,3,3-四氟丙烯(R1234yf)和反式-1,3,3,3-四氟丙烯(R1234ze(E)),不仅ODP=0,GWP=1,且可燃性分类均为2L类(弱可燃性)[2]。R1234ze(E)和R1234yf属于同分异构体,它们的可燃性已被广泛研究。B. Minor等[10]根据标准ASTM E681-04,测得R1234yf的可燃极限为3.83%~15.0%。S. Kondo等[11]根据标准ASHRAE 34-2007,在温度为35 ℃时,测得干空气中R1234yf的可燃极限为6.7%~11.7%,在相对湿度为50%的湿空气中R1234yf和R1234ze(E)的可燃极限分别为5.5%~13.0%和5.86%~12.8%。S. Kondo等[12-13]研究了环境温度和压力对R1234yf可燃极限的影响,环境温度从5 ℃增至100 ℃,R1234yf的可燃下限(lower flammability limit,LFL)减小,可燃上限(upper flammability limit,UFL)增加,环境压力从常压增至2 500 kPa,R1234yf的LFL减小,而UFL增加。Dong Hanhai等[14]测试了初始温度对R1234yf可燃极限和燃烧速度的影响。郭智恺等[15]根据GB/T 12474—2008标准测试了R1234ze(E)在不同湿度下的可燃极限。Lü Zijian等[16]的实验研究结果表明,随着R1234yf比例的增加,R1234yf/R32和R1234yf/R152a的燃烧速度减小和可燃极限范围收窄。Feng Biao等[17]的研究同样表明,R1234yf有抑制R152a可燃性的效果。因此,可以推断R1234ze(E)和R1234yf具有抑制R290可燃性的潜力。
已有学者对R1234yf/R290和R1234ze(E)/R290的气液相平衡特性[18-19]和系统循环性能[20-23]进行研究。Zhang Haiyang等[18]测量了R1234ze(E)/R290混合物在253.141~293.284 K的气液平衡数据。Zhong Quan等[19]测量了R1234yf/R290混合物在254.28~348.30 K的气液平衡数据。Zhang Nuochen等[21]通过仿真计算,得出在汽车空调上使用R1234yf/R290(摩尔比为0.3/0.7)的系统循环性能要优于R134a。Liang Youcai等[22]计算分析了余热回收系统,得出使用R1234ze(E)/R290工作流体的新型有机朗肯循环和喷射器膨胀制冷循环系统要优于传统的有机朗肯循环和蒸气压缩制冷循环系统。Wang Lele等[23]分析了不同组分的R290/R1234ze(E)混合物的制冷性能,发现可以用R1234ze(E)/R290(质量比为0.45/0.55)代替R22。王方等[24]分析了二元非共沸混合工质R1234ze(E)/碳氢化合物(HCs)热泵系统循环性能,发现R1234ze(E)/HCs有望成为新型替代工质。
可燃极限是确定制冷剂可燃等级分类的重要参数之一,若LFL≤3.5%,可燃等级分类为3类[2],标准法规对于使用3类制冷剂产品的系统设计、制造、储存和运输等过程的安全要求管控更加严格,使得推广困难。现有研究主要通过向R290添加R13I1、R134a、R32等物质以降低其可燃性,添加R1234ze(E)和R1234yf的报道较少,虽有R1234ze(E)/R290、R1234yf/R290混合物的物性和系统性能研究,但未考虑混合物的安全性能。本文在ASHRAE 34-2022标准[2]的条件下测试了R290、R1234yf、R1234ze(E)纯质和R1234ze(E)/R290、R1234yf/R290二元混合物的可燃极限。使用H. Le Chatelier公式[25]关联实验数据,并分析了R1234yf和R1234ze(E)对R290可燃性的影响。此外,模拟计算不同组分下R290混合物的制冷循环性能。研究结果可为R290混合制冷剂的安全应用提供参考。
使用根据标准ASHRAE 34—2022[2]搭建的可燃极限测试装置进行实验,如图1所示。实验容器为12 L单颈球形玻璃烧瓶。磁力搅拌器用于混合玻璃烧瓶中的气体(空气/制冷剂)。使用直径为1 mm、间距为6.4 mm的L形钨丝电极点燃气体混合物。将点火源放置在离测试容器底部1/3容器直径的高度处。测试在60 ℃和大气压下进行。烧瓶中的温度通过恒温防爆箱保持,波动在1 ℃以内。
测试前,首先对烧瓶和管道系统进行3次抽真空换气清洁。恒温防爆箱的温度设定为60 ℃,烧瓶再次抽空。将混合物加入烧瓶中,通过分压控制加入量,然后引入绝对湿度为0.008 8 g±0.000 5 g(每克干燥空气中水蒸气的克数)的空气,使烧瓶内压力恢复至大气压。开启搅拌器使瓶内物质完全混合并达到热平衡5 min。搅拌器停止工作60 s后,产生电火花(15 kV,30 mA,火花持续时间0.4 s)点燃烧瓶内的气体混合物。通过摄像头观察火焰,从电极顶端到容器壁若形成超过90°扇形的连续火焰传播,则认为混合物在该浓度下可燃。测试以约10%的体积分数增量进行,如2.0%、2.2%、2.4%。记录产生火焰传播和不产生火焰传播的体积分数,将其平均值作为实验可燃极限。本实验使用的样品信息如表1所示,所有样品均未经进一步纯化。
对于混合物,实验的不确定度主要来自混合物组分、分压和测试步长。采用重量法,测试混合物由高精度电子天平(梅特勒-托利多XPR5003S)配制,分辨率为1 mg,摩尔分数的不确定度小于0.002。压力由数字压力传感器测量,量程为101 kPa,额定精度为0.1%。本文中LFL的测量步长在0.1%~0.3%,UFL的测量步长在0.4%~1.0%。考虑以上因素,LFL和UFL的实验不确定度分别小于0.3%和小于0.6%。
为了验证测试装置的可靠性,在60 ℃和101 325 Pa下对纯R290和R1234yf、R1234ze(E)进行测量,实验数据如表2所示。
对于R290,LFL的测试值与文献值之间的偏差为0.1%,UFL的偏差为0,满足ASTM E681关于卤代烃的测试误差应不超过LFL的0.1%和UFL的0.9%的要求。对于R1234yf,LFL的测试值与文献值之间的偏差为0.4%,UFL的偏差为0.5%,满足LFL和UFL对大淬火距离材料的测试偏差应不超过0.9%和1.8%的要求。
在60 ℃、常压下测试了R1234yf/R290和R1234ze(E)/R290的可燃极限,如表3所示。
H. Le Chatelier模型通常用于预测可燃气体混合的可燃极限,二元混合物的可燃下限和上限可通过以下等式计算[25]
式中:LfUf分别为混合物的可燃下限和上限;LiUi分别为组分i的可燃下限和上限;xi为组分i的摩尔分数。通过H. Le Chatelier公式分别计算了R1234yf/R290和R1234ze(E)/R290的可燃极限数据,结果列于表3并绘制于图2。该关联模型计算的可燃下限和可燃上限与实验结果之间的平均绝对偏差分别为0.22%和0.57%。由图2表3可知,当R1234yf或R1234ze(E)的质量分数增至20%时,混合物的LFL并未明显变化,质量分数增至80%时,混合物的LFL仅增加约1.0%,且小于3.5%(LFL>3.5%是制冷剂可燃性为2类的必要条件之一[2])。随着R1234yf和R1234ze(E)的质量分数增加,混合物的LFL和UFL均呈现逐渐增大的趋势,R1234ze(E)/R290的可燃极限与R1234yf/R290基本相似。R1234yf或R1234ze(E)在R290混合制冷剂中的质量分数至少需要高于80%,才能使可燃等级由3类变为2类。
抑制燃烧主要涉及物理和化学2个方面。物理抑制机制主要体现在稀释、隔离和冷却,而化学抑制机制主要体现在清除活性自由基上。对于R1234ze(E)和R1234yf,抑制R290火焰的机理主要体现在对活性自由基的清除上。R1234yf初始热分解的主要中间体是CF3和H自由基[26]。CF3自由基参与清除反应,途径如反应式(4)~式(8)所示[27]。燃烧过程中产生的高活性自由基:O、H和OH,会被氟化基捕获并转化为稳定的产物。
使用F数对比分析R1234yf、R1234ze(E)、R32、R13I1和R134a对R290可燃性抑制能力,F数是由S. Kondo等[28]提出以描述可燃物的燃烧特性,表达式如下:
式中:LU分别为可燃物的LFL和UFL。F数介于0~1,且F数越大,可燃物的可燃性越强。当F数为0时,该物质不可燃。
图3所示为混合物的F数随抑燃制冷剂体积分数的变化。将实验测得的R1234yf/R290、R1234ze(E)/R290的F数与Zhong Quan等[7]测得的R32/R290、R13I1/R290和Cai Dehua等[8]测得的R134a/R290的F数进行了对比。由图3可知,各制冷剂对R290的燃烧抑制能力由大到小排序为:R13I1>R134a>R32>R1234ze(E)/R1234yf,可燃物的可燃性同卤素原子与氢原子比值大小以及碳碳双键均有关,虽然R1234ze(E)和R1234yf中的卤素原子与氢原子比值较大,但由于碳碳双键的存在,它们对R290的可燃性抑制能力最弱。
基于REFPROP 10.0模拟不同组分的R290混合物的制冷循环。研究并对比了不同R290质量分数下能效比(energy efficiency ratio,EER)、单位容积制冷量、单位质量制冷量和温度滑移的变化。制冷循环计算工况如表4所示,结果如图4所示。混合物的EER比纯制冷剂的小。随着R290质量分数的增加,混合物的EER先减小后增大。当R290的质量分数在70%及以上时,混合物的EER衰减小于1%,单位容积制冷量增加小于0.4%。当R290的质量分数小于70%时,R1234yf/R290的EER和单位容积制冷量始终大于R1234ze(E)/R290,而温度滑移始终小于R1234ze(E)/R290。2种混合物的单位容积制冷量的局部最大值均出现在共沸点附近。
综上所述,相比R290纯质,2种制冷剂分别与R290的混合物在共沸点附近实现了相对较小的EER衰减和单位容积制冷量增加。R290和R1234yf或R1234ze(E)形成的共沸混合物虽然具有较好的综合性能,并能够提高R290的可燃下限,但同时也应考虑单位质量制冷量减小带来灌注量提升的变化。
本文测量了R1234yf/R290和R1234ze(E)/R290混合制冷剂的可燃极限,使用Le Chatelier模型对实验数据进行关联,并对比了R1234yf、R1234ze(E)、R32、R13I1和R134a对R290可燃性的抑制能力。此外,模拟研究了不同组分下R290混合物的制冷循环性能。得到结论如下:
1)在60 ℃和1个大气压下,R290的LFL和UFL分别为2.1%和9.9%;R1234ze(E)的LFL和UFL分别为5.9%和13.5%;R1234yf的LFL和UFL分别为6.5%和12.7%。
2)R1234yf和R1234ze(E)对R290可燃性抑制能力较差,R1234yf或R1234ze(E)的质量分数达到20%时,混合物的LFL并没有明显变化,当质量分数达到80%时,混合物的可燃下限仅增加约1.0%。
3)在R1234yf、R1234ze(E)、R32、R13I1和R134a中,R1234yf和R1234ze(E)对R290可燃性抑制能力最弱,R13I1对R290可燃性抑制能力最强。
4)相比R290纯质,R1234yf和R1234ze(E)分别与R290形成的混合物在共沸点附近的EER衰减小于1%,单位容积制冷量增加小于0.4%,单位质量制冷量明显减小。
作为制冷剂可燃性等级分类的关键参数,本文只测试研究了可燃极限,未进行燃烧速度实验研究以进一步确定混合制冷剂的可燃等级,此外对于混合物的热力循环性能也未进行整机实验验证,在未来可以进行进一步的实验分析,得到可燃性和整机循环性能均较优的混合比例。
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2025年第46卷第4期
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doi: 10.12465/j.issn.0253-4339.2025.04.022
  • 接收时间:2024-03-25
  • 首发时间:2026-03-13
  • 出版时间:2025-08-16
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  • 收稿日期:2024-03-25
  • 修回日期:2024-07-18
  • 录用日期:2024-07-23
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    珠海格力电器股份有限公司 珠海 519070

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钟权,男,高级工程师,珠海格力电器股份有限公司,0756-8587826,E-mail:。研究方向:环保制冷剂。
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2种不同金属材料的力学参数

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
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红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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