新型低GWP高温热泵工质HFO-1234ze(Z)的研究进展

高温热泵可以有效回收工业余热，达到节能减排和保护环境的目的。目前，有关高温热泵技术的研究热点在于寻找一种全球变暖潜能值(GWP)低、使用性能良好的工质，以替代现有CFC-114、HFC-245fa工质。对新型环境友好型工质HFO-1234ze(Z)进行了综述，其GWP＜1，临界温度高于423 K，是一种潜在的高温热泵替代工质。总结了近年来国内外学者对HFO-1234ze(Z)的合成技术、热力学性质、输运性质、传热性能等方面的研究，并分析了HFO-1234ze(Z)在高温热泵系统中应用的可行性，认为HFO-1234ze(Z)在高温热泵中具有较好的工作性能和发展前景。     

Development and validation of a micro-fin tubes evaporator model using R134a and R1234yf as working fluids

This paper presents a model of shell and tube evaporator with micro-fin tubes using R1234yf and R134a. The model developed for this evaporator uses the ε-NTU method to predict the evaporating pressure, the refrigerant outlet enthalpy and the outlet temperature of the secondary fluid. The model accuracy is evaluated using different two-phase flow boiling correlations for micro-fin tubes and comparing predicted and experimental data. The experimental tests were carried out for a wide range of operating conditions using R134a and R1234yf as working fluids. The predicted parameter with maximum deviations, between the predicted and experimental data, is the evaporating pressure. The correlation of Akhavan– Behabadi et al. was used to predict flow boiling heat transfer, with an error on cooling capacity prediction below 5%. Simulations, carried out with this validated model, show that the overall heat transfer coefficient of R1234yf has a maximum decrease of 10% compared with R134a.     

Condensation in two phase and desuperheating zone for R1234ze(E), R134a and R32 in horizontal smooth tubes

Condensation is usually assumed to begin when the bulk enthalpy reaches the saturated vapor enthalpy, which leads to discontinuity of heat transfer coefficient calculation in modeling. This paper addresses the discontinuity by showing the presence of condensation in desuperheating region when the wall temperature decreases below the saturation temperature at any operating condition. The experiments have been conducted with R134a, R1234ze(E) and R32 for mass fluxes of 100–300 kgm⁻² s⁻¹, saturation temperatures of 30^°C–50 °C and from x = 0.05 to superheat of 50 °C in a horizontal smooth tube with 6.1 mm inner diameter. R134a is observed to have approximately 10% higher and 20% lower HTC compared to R1234ze(E) and R32 respectively. Cavallini correlation predicted the data within an accuracy of 12% while Kondo-Hrnjak correlation predicted HTC for condensation in de-superheating zone within accuracy of 23%.     

水平管内R1234yf的流动沸腾换热特性

通过实验研究了环境友好型制冷剂R1234yf在内径为0.5mm的水平圆形微通道内的流动沸腾换热特性,测量了不同工况下R1234yf的沸腾换热系数（HTC）,并与传统制冷剂R134a进行了对比,分析了质量流速、热流密度和干度对换热系数变化规律的影响。实验条件为：饱和温度(17±1)℃,质量流速1000~2500kg/(m²·s),热流密度25~143kW/m²。实验结果表明：R1234yf的换热系数随着热流密度的增大而显著增大,而质量流速和干度的影响较小,核态沸腾为其主导换热机制。对比R1234yf和R134a在相同工况下的换热特性,发现两种工质的平均换热系数差别较小,并均随着热流密度增大而逐渐增加,但是R1234yf发生干涸（Dryout）时的热流密度小于R134a。将实验数据与已有文献中的核沸腾主导的经验关联式的预测结果进行了对比,得到了较好的吻合。     

Nucleate boiling heat transfer coefficients of HFO1234yf on various enhanced surfaces

In this study, nucleate boiling heat transfer coefficients (HTCs) of HFO1234yf HFC134a are measured on a flat plain, Turbo-B, Turbo-C, and Thermoexcel-E surfaces. All data are taken at the liquid pool temperature of 7 °C on small flat horizontal square copper plates (9.53 mm × 9.53 mm) at heat fluxes from 10 kW m⁻² to 200 kW m⁻² with an interval of 10 kW m⁻². Test results show that nucleate boiling HTCs of HFO1234yf on all four surfaces are similar to those of HFC134a at all heat fluxes tested in this study. At heat fluxes below 150 kW m⁻², Thermoexcel-E surface shows the highest heat transfer performance and hence is the best surface for the manufacture of the evaporators in refrigeration and air-conditioning equipment. On the other hand, at high heat fluxes above 150 kW m⁻², Turbo-B and Turbo-C show better heat transfer performance than Thermoexcel-E and hence are good for electronic cooling applications. Overall, HFO1234yf is a good long term candidate with excellent environmental properties to replace successfully HFC134a from the view point of pool boiling heat transfer. Hence HFO1234yf can be readily applied to the conventional evaporators designed for HFC134a.     

Boiling heat transfer of HFO-1234yf flowing in a smooth small-diameter horizontal tube

The flow boiling heat transfer coefficient of the low-GWP (global warming potential) refrigerant HFO-1234yf inside a smooth small-diameter horizontal tube (inner diameter: 2 mm) was experimentally investigated. The local heat transfer coefficient was measured at heat fluxes of 6-24 kW m⁻², mass fluxes of 100-400 kg m⁻² s⁻¹, an evaporating temperature of 288.15 K, and an inlet vapor quality of 0-0.25. The results show that the effect of heat flux on the heat transfer was large at low vapor quality, while the effect of mass flux was large at high vapor quality. The heat transfer coefficient of HFO-1234yf was almost the same as that of R-134a. The heat transfer coefficients calculated based on correlations with Saitoh et al. agreed well with the measured values compared to other correlations. The measured pressure drop agreed well with that predicted by the Lockhart-Martinelli correlation.     

制冷工质燃烧(分解)及生成有毒气体的探讨

2010年6月以来,德国联邦材料研究与测试所(BAM)声称R1234yf暴露于点火源后会生成有毒HF气体,危害人身健康.2010年末国内也有对R32表达同样疑虑的反映.为此,从化学反应动力学原理、从生成有毒气体的种类及其允许暴露极限、并参考SAE研究成果等几方面,对BAM报告进行了探讨和分析,得出了一些看法,其中特别是从它们试验结果发现,在相同背景下凡是R1234yf导致生成HF浓度超标的,R134a也超标,这就说明了这个问题不足以构成它们应用的障碍;并有理由认为:即使在极端恶劣条件下,R32的HF和可燃风险概率也将分别小于或等于R1234yf(R134a)的10-122和10-14量级,处于极低的风险水平.     

氢氟烯烃气相异构化催化剂研究进展

综述了含氟烯烃中两类典型的HFCs替代品HFO-1225ye和HFO-1234ze顺式异构体合成催化剂的研究进展,并展望了今后异构化催化剂可能的研究方向。     

R1234yf热泵技术综述与潜力分析

为了满足逐步严苛的环保法规要求,R1234yf成为车用热泵制冷剂R134a的热门替代制冷剂之一。本文对R1234yf热泵技术的研究进行了综述与分析,其GWP<1,各方面性质均符合车用热泵系统的工作需求。在传热效果上,R1234yf的沸腾传热性能略优于R134a,且冷凝过程压降比R134a低5%~10%,优于R134a系统。在诸多R1234yf和R134a系统的仿真和实验研究中,R1234yf热泵性能略低于R134a,但可以通过优化零部件、强化补气、改善工况等方式使其与R134a十分接近甚至超越。R1234yf低压饱和压力比R134a高约15%,可以适配更高的压缩机转速,低温下制热性能比R134a更好,且较低的压缩机排气温度使系统工作更为稳定,强化补气的效果也优于R134a。因此,R1234yf在车用热泵中具有较好的工作性能和发展前景,可以作为R134a的替代制冷剂。     

Research progress of low GWP working fluid HFO-1234ze(Z) for high temperature heat pumps

High temperature heat pump can effectively recover industrial waste heat to achieve the purpose of energy saving,emission reduction and environmental protection. At present, novel working fluids for the high temperature heat pumps are studied to replace CFC-114 and HFC-245fa. The alternative working fluid should have low global warming potential (GWP) and good working performance. The eco-friendly working fluid HFO-1234ze(Z), whose GWP < 1 and critical temperature above 423 K, is considered as a potential heat pump replacement working fluid. This paper summarizes the research of HFO-1234ze(Z) including the synthesis technology, thermophysical properties, transport properties, and heat transfer performance. The feasibility of application of HFO-1234ze(Z) in high temperature heat pump system is analyzed. It is considered that HFO-1234ze(Z) has good performance and development prospect in high temperature heat pump.