新型制冷剂R1234ze(E)及其混合工质研究进展

低GWP值制冷剂R1234ze(E)(trans-1,3,3,3-tetrafluoropropene)作为R134a较为理想的替代品而被关注,但其单一成分的热力学性能和传输特性并不理想,在R1234ze(E)中混入R32成分可以有效改善其热力学性能。本文概述了低GWP值工质R1234ze(E)及其与R32混合物的热物性特征、传输特性及系统运行性能方面的研究现状,并与目前常用的制冷工质进行比较分析,指出R1234ze(E)与R32混合工质有望成为新型低GWP值替代工质。     

R1234ze/HCs非共沸混合工质热泵系统循环性能分析

在热泵热水器名义工况下,本文建立了热泵系统循环热力学模型,利用EES程序对混合工质R1234ze/HCs及对应的纯工质热泵系统循环性能进行了对比分析。结果表明:R1234ze/R600在质量分数(20/80)和R1234ze/R600a在质量分数(40/60)存在最优配比,对应的最大制热COP_h分别为3. 41和3. 32,而R1234ze/R290则呈现单调下降趋势。R1234ze/R600(20/80)系统的制热COP_h比R1234ze/R600a(40/60)、R1234ze、R290、R600、R600a系统分别高2. 7%、17%、0. 09%、16. 3%和17. 8%,排气温度为76. 9℃,冷凝压力为0. 711 MPa,压比为6. 32,有望成为新型替代工质。     

Condensation heat transfer and two-phase frictional pressure drop in a single minichannel with R1234ze(E) and other refrigerants

R1234ze(E), trans-1, 3, 3, 3-tetrafluoropropene, is a fluorinated propene isomer which may be a substitute of R134a for refrigeration applications. R1234ze(E) has a much lower GWP_100-years than that of R134a. In this paper, the local heat transfer coefficient during condensation of R1234ze(E) is investigated in a single minichannel, horizontally arranged, with hydraulic diameter equal to 0.96 mm. Since the saturation temperature drop directly affects the heat transfer rate, the pressure drop during adiabatic two phase flow of R1234ze(E) is also measured. Predictive models are assessed both for condensation heat transfer and pressure drop. A comparative analysis is carried out among several fluids (R1234ze(E), R32, R134a and R1234yf) starting from experimental data collected at the same conditions and using the Performance Evaluation Criteria (PEC) named Penalty Factor (PF) and Total Temperature Penalization (TTP) to rank the tested refrigerants in forced convective condensation.     

Isothermal vapor liquid equilibrium measurements for difluoromethane (R32) + fluoroethane (R161) + trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) ternary mixtures

Difluoromethane (R32) + fluoroethane (R161) + trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) ternary system could be a promising alternative refrigerant mixture. The vapor liquid equilibrium (VLE) data for this system are important for the evaluation of its performance. In this work, the VLE of R32 + R161 + R1234ze(E) were measured for the first time by a quasi-static analytical apparatus over the temperature range of 283.15 to 323.15 K. The ternary system of R32 + R161 + R1234ze(E) is a zeotropic system within the studied temperature range. The Peng–Robinson–Stryjek–Vera (PRSV) equation of state combined with the Wong–Sandler (WS) mixing rule and the non-random two-liquid (NRTL) activity coefficient model was used to predict the ternary VLE data by using the parameters of binary mixtures (R32 + R161, R32 + R1234ze(E) and R161 + R1234ze(E)). The calculated values show excellent agreement with the experimental results. The average absolute deviation (AAD) of pressure is 0.16%. The average absolute deviations of vapor phase mole fractions for R32 and R161 are 0.0021 and 0.0028, respectively.     

Numerical research on R32/R1234ze(E) air source heat pump under variable mass concentration

R32/R1234ze(E) mixtures are potentially low-GWP alternative refrigerants for air conditioning and heat pumps while the rare pure refrigerants can totally meet the requirements of new international protocols on environmental conservation, thermodynamic performance, and safety. The system performance under different concentrations is important for selection of working concentration for the new R32/R1234ze(E) refrigeration or heat pump. In this paper, the thermodynamic model of an ASHP with R32/R1234ze(E) mixtures is built and used to investigate the influence of the refrigerant composition on the performance of the system. The results show that when the mass fraction of R1234ze(E) changes from 0% to 100%, the heating capacity of the ASHP decreases by 67.2%, while the COP continuously increases by 70.3%, which means the changing tendency of system COP is quite different from previous research under fixed evaporating and condensing temperature. Adjusting the refrigerant concentration will be a good system modulation method for ASHPs with R32/R1234ze(E) to meet both the heating capacity and energy efficiency requirements. Furthermore, temperature matching degree is an important factor that affects the energy efficiency of ASHPs with non-azeotropes, which can guide the circuitry optimization of evaporator and condenser in ASHPs with non-azeotropes.     

Flow boiling of non-azeotropic mixture R32/R1234ze(E) in horizontal microfin tubes

Flow boiling of a potential refrigerant R32/R1234ze(E) in a horizontal microfin tube of 5.21 mm inner diameter is experimentally investigated. The heat transfer coefficient (HTC) and pressure drop are measured at a saturation temperature of 10 °C, heat fluxes of 10 and 15 kW m^?2, and mass velocities from 150 to 400 kg m^?2 s^?1. The HTC of R1234ze(E) is lower than that of R32. Degradation in the HTC of the R32/R1234ze(E) mixture is significant; the HTC is even lower than that of R1234ze(E). The HTC is minimized at the composition 0.2/0.8 by mass, where the temperature glide and the mass fraction distribution are maximized. A predicting correlation based on Momoki et al. (1995) associated with the correction methods of Thome (1981) to consider the mass transfer resistance and Stephan (1992) to consider the additionally required sensible heat is proposed and validated with the experimental results.     

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%.     

Correlations for the viscosity of 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) and trans-1,3,3,3-tetrafluoropropene (R1234ze(E))

Due to concerns about global warming, there is interest in 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) and trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) as potential replacements for refrigerants with high global warming potential (GWP). In this paper we survey available data and provide viscosity correlations that cover the entire fluid range including vapor, liquid, and supercritical regions. The correlation for R1234yf is valid from the triple point (220 K) to 410 K at pressures up to 30 MPa, and the correlation for R1234ze(E) is valid from the triple point (169 K) to 420 K at pressures up to 100 MPa. The estimated uncertainty for both correlations at a 95% confidence level is 2% for the liquid phase over the temperature range 243 K to 363 K at pressures to 30 MPa, and 3% for the gas phase at atmospheric pressure.     

R1234ze(E)在多元醇脂油中溶解度的实验研究

R1234ze(E)（1,1,1,3-四氟丙烯）是当下具有较强替代潜能的环保制冷剂之一,本文搭建了溶解度测试实验系统,对R1234ze(E)在两种多元醇脂油中的溶解度进行测试,测试的温度范围为40~80 ℃,压力范围为0.123~0.360 MPa。采用PR状态方程和MHV2混合规则及NRTL活度系数模型对实验结果进行关联计算,得到不同温度下的交互系数及计算值与实验值的平均相对误差。结果表明,R1234ze(E)在两种多元醇脂油中的溶解度均随着温度的升高而降低,且R1234ze(E)在两种多元醇脂油中的平衡压力与溶解度之间存在立方函数关系。在两种多元醇酯油中,计算值与实验值的平均相对误差分别为1.68%和1.11%,可较好的描述R1234ze(E)在两种多元醇酯油中的相平衡行为。     

Energy performance evaluation of R1234yf,R1234ze(E), R600a,R290 and R152a as low-GWP R134a alternatives

In 2014, the Directive 517/2014 was introduced by European Parliament to reduce the use of high-GWP greenhouse gases in the European area in order to limit global climate change in accordance with the objectives marked by the EU Research and Innovation programme Horizon 2020. These restrictions affect the large majority of artificial refrigerants among which R134a is included due to its relatively high GWP₁₀₀ (1301). The widely used of R134a in the refrigeration and air conditioning fields reveals the need to identify new low-GWP alternatives. Accordingly, in this work five low-GWP R134a possible choices have been tested and compared in an identical refrigerating facility equipped with a hermetic compressor, under the same operating conditions.The refrigerants used in this analysis are: R290 and R600a (HCs); R134a and R152a (HFCs), and finally, R1234yf and R1234ze(E) (HFOs). All of them have been assayed without changes in the facility, that is, as direct drop-ins. The results obtained from the experimental tests are presented and commented in this work from the energetic point of view.     

Thermodynamic assessment of high-temperature heat pumps using Low-GWP HFO refrigerants for heat recovery

Reducing energy consumption by utilizing heat recovery systems has become increasingly important in industry. This paper presents an exploratory assessment of heat pump type heat recovery systems using environmentally friendly refrigerants. The coefficient of performance (COP) of 4 cycle configurations used to raise the temperature of heat media to 160 °C with a waste heat at 80 °C is calculated and compared for refrigerants R717, R365mfc, R1234ze(E), and R1234ze(Z). A multiple-stage “extraction” cycle drastically reduces the throttling loss and exergy loss in the condensers, resulting in the highest COP for R1234ze(Z). A cascade cycle using R1234ze(Z) and R365mfc has a relatively high COP and provides practical benefits. Even under adverse conditions, the primary energy efficiency is greater than 1.3 when the transmission end efficiency of the electric power generation is 0.37. The assessment demonstrated that high-temperature heat pumps are a promising approach for reducing primary energy consumption for industrial applications.     

Measurements of PρT properties,vapor pressures,saturated densities,and critical parameters for R 1234ze(Z) and R 245fa

Pressure-density-temperature (PρT) properties, vapor pressures, and saturated liquid and vapor densities for refrigerants R 1234ze(Z) (cis-1,3,3,3-tetrafluoroprop-1-ene; CF₃CHCHF) and R 245fa (1,1,1,3,3-pentafluoropropane; C₃H₃F₅) were measured with two types of isochoric methods. Pressure was measured with a digital quartz pressure transducer. Temperature was measured with 25 Ω standard platinum resistance thermometer on the ITS-90 temperature scale. Density was calculated from the mass of sample and the inner volume of pressure vessel. By using the present vapor pressure data, new vapor pressure correlations for R 1234ze(Z) and R 245fa have been formulated. In addition, the critical temperature T_c, critical density ρ_c, and critical pressure P_c were directly determined on the basis of direct observation of the meniscus disappearance.     

尼龙11/POE共混物的形态与力学性能

采用动态力学分析(DMTA)和扫描电镜(SEM)等方法研究了相容剂乙烯辛烯共聚物接枝马来酸酐聚合物(POE-g-MAH)对尼龙11(PA11)共混体系力学性能及共混物形态的影响。结果表明,混合弹性体中m(POE-g-MAH)/m(POE)=2∶1时,PA11共混物的缺口冲击强度达到81.2 kJ/m2;共混物缺口冲击强度对MAH接枝率敏感;加入混合弹性体,共混体系分子间的作用力增大,损耗峰向高温方向移动,Tg升高;PA11与POE各个共混体系的β松弛峰高显著低于纯PA11的,加入POE和POE-g-MAH可有效降低PA11的吸水性;POE-g-MAH可显著改善PA11/POE共混材料的相容性,使分散相尺寸减小,分布均匀,且材料缺口冲击强度显著增大。     

Drop-in replacement in a R134 ejector refrigeration cycle by HFO refrigerants

The present work reports a numerical analysis of a single-phase supersonic ejector working with R134a as well as hydrofluoroolefin (HFO) refrigerants R1234yf and R1234ze(E). Comparisons were made regarding the ejector performances under varying operating conditions and refrigerant mixture proportions. The calculations have been then extended to an existing ejector heat driven refrigeration cycle (EHDRC). R1234yf appears to be a good candidate for drop-in replacement of R134a in a real EHDRC, while using R1234ze(E) would induce some modifications due to its thermodynamic properties. Maintaining the same pressure ratio for the ejector would lead on one hand to better entrainment ratio using R1234ze(E) and on the other hand to reduced coefficient of performance (COP) and cooling power by 4.2% and 26.6% in average, respectively. Using R1234yf under the same conditions induces a decrease of 5.2% for the entrainment ratio, 9.6% for the COP and 19.8% for the cooling power in average.     

Comparative experimental study of low GWP alternative for R134a in a walk-in cold room

The environmental problems induced by the ongoing increase in the global worming potential (GWP) pose a significant interest among researchers. It was found that, the currently used refrigerants are with high GWP (National Refrigerants Inc., 2004), so that it becomes necessary to search for alternatives to these refrigerants that can properly operate on the same systems but with low GWP. Therefore a walk-in cold room working with vapor compression cycle is constructed and tested in this paper. The performance of R134a refrigerant with high GWP is compared to another low GWP refrigerant R1234ze in a trail to provide a solution of the problem of high GWP of refrigerants currently used in cold rooms. The results obtained in this study have shown that, the cooling capacity of R1234ze was lower than that of R134a by 2% to 13%. The lowest evaporating temperature that could be reached for R1234ze is −13 °C while the lowest temperature of R134a is −30 °C. Regarding the power consumption, R1234ze has lower power consumption than R134a by about 9% to 15% therefore it can be concluded that R 1234ze can be recommended to be used at high and medium evaporating temperature after carrying out the suitable modifications on the refrigeration cycle.     

Relative permittivity of mixtures of R-134a and R-1234yf and a polyol ester lubricating oil

The relative permittivity (dielectric constant) of mixtures of a polyol ester (POE) ISO VG 10 lubricating oil and refrigerants R-134a and R-1234yf was evaluated experimentally for temperatures ranging from 298 to 328 K. The experimental apparatus was designed and built specifically for determining the dielectric properties of mixtures of lubricants and liquified gases (refrigerants) at high pressures. The mixture relative permittivity was inversely proportional to the temperature and directly proportional to the refrigerant concentration. The relative permittivity of the R-1234yf mixture was slightly lower than that of the R-134a mixture at identical conditions. The Böttcher mixing rule for the relative permittivity and the Oster rule for the mixture polarity showed the best agreement with the experimental data, with root-mean square (RMS) deviations smaller than 1%.     

R32及其常用两种润滑油POE和PVE物性计算模型

准确计算制冷剂和润滑油的物性是压缩机优化设计的基础。本文根据已知数据,通过显式拟合法,给出了在常见范围内制冷剂R32饱和液体、饱和气体、过热气体及POE和PVE润滑油的热物性计算模型,并比较分析了这些物质的物性的特点。模型对物性参数的计算值与已知数据的偏差均在5%以内,为R32与POE或PVE混合物物性计算奠定了基础。本文提出的计算模型简单、可靠,可使模拟计算时间更短、精度更高。     

Effect of blend composition on the rheology property of polypropylene/poly (ethylene-1-octene) blends

In the present study, the dynamic viscoelastic properties for binary blends consisting of polypropylene (PP) and poly (ethylene-1-octene) (POE) were investigated using a Stresstech Rheometer in molten states at 210 °C. The results show that the blends with different content of POE present diversified rheological behaviors. Meanwhile, the blends with 10 wt% and 20 wt% POE show especial rheological behaviors. The dynamic complex viscosity of the blends with 10 wt% and 20 wt% POE are higher than that of others. The storage modulus and loss modulus of the blends with 10–40 wt% POE are different from other blends, and the blends with 10 wt% POE present the largest relaxation time. This behavior is probably related to the miscibility and long chain branch of POE in the PP/POE blends.     

Experimental study of R450A drop-in performance in an R134a small capacity refrigeration unit

The Kigali amendment to the Montreal Protocol has highlighted the hydrofluorocarbons (HFCs) phase out as a priority to reduce the future global mean temperature increase. R134a is the most abundant HFC in the atmosphere and therefore it must be substituted using environmentally benign alternatives. In the short term, blends of HFCs and hydrofluoroolefins can replace R134a. This paper experimentally evaluates R450A (GWP of 547), a non-flammable mixture of R1234ze(E) and R134a, in an R134a small capacity refrigeration system. The controlled experimental conditions cover evaporating temperatures from −15 to 12.5 °C and condensing temperature of 25, 30 and 35 °C (36 tests in total for each refrigerant). The experimental results showed that with only a thermostatic expansion valve adjustment the average R450A cooling capacity and COP are 9.9% and 2.9% lower than those measured using R134a. Besides, the observed compressor discharge temperature values of R450A are not greater than that of R134a.