HCFC-22替代制冷剂研究进展及其相关问题讨论

简要介绍制冷剂的发展历史,详细介绍相关行业中制冷剂的应用现状及我国目前在替代HCFC-22方面的工作,重点介绍若干最新备受关注的制冷剂如HFO-1234yf及其混合物、HFC-161及其混合物、HFC-32和R290等。由于这些制冷剂普遍存在的可燃性问题,本文也将介绍一些描述可燃性的参数以及相关的国际标准,并提出一些选择可燃制冷剂的注意点。     

Thermodynamic performance of air conditioners working with R417A and R424A as alternatives to R22

The energy and exergy parameters of R417A and R424A gases which can be used instead of R22 were experimentally investigated for a split-type air conditioner. Although GWP amounts of the available alternative refrigerants are higher compared to R22, their ODP values are zero. The experiments were accomplished for three different ambient temperature values of 25 °C, 30 °C and 35 °C. The covered test conditions were carried out for steady-state case while keeping the inside medium temperature at constant temperature of 22 °C. The cooling capacity, COP, exergy destruction of components in the unit (i.e., compressor, condenser, evaporator, and expansion device), exergetic efficiency and some other parameters of the system were determined. COP values for the refrigerants of R417A and R424A were noted to be smaller compared to R22. Similarly, both isentropic efficiency of the compressor and exergetic efficiency of the system were higher for R22. The use of R424A will be more suitable rather than R417A since COP values of R417A are lower about 5–16% compared to R424A. The COP value of R22 is greater than that of R417A and R424A by amounts of 17–23% and 4–18%, respectively. At the greater evaporation temperatures (0 °C to +5 °C as in the air-conditioners) it can be stated that R424A is more preferable than R417A as an alternative refrigerant to R22.     

Vapor–liquid equilibrium measurements and assessments of fluoroethane + N,N-dimethylformamide and fluoroethane + dimethylether diethylene glycol systems for the hybrid refrigeration cycle

This study aimed to develop novel working pairs for the hybrid refrigeration cycle. To this end, the vapor–liquid equilibrium data of fluoroethane (R161) + N,N-dimethylformamide (DMF) and R161 + dimethylether diethylene glycol (DMEDEG) systems were obtained from 293.15 K to 353.15 K. Experimental data were correlated using the nonrandom two-liquid (NRTL) activity coefficient model. The average relative pressure deviations are 1.33% and 1.45%, and the maximum relative pressure deviations are 3.68% and 3.90%, respectively. Experimental results show that the two binary mixtures exhibit negative deviations from Raoult's law. Finally, the performance of R161 + DMF, R161 + DMEDEG, and R134a + DMF systems were simulated and evaluated based on the hybrid refrigeration cycle. Results show that both R161 + DMF and R161 + DMEDEG systems are potential working pairs for the hybrid refrigeration cycle, and the R161 + DMEDEG system is better.     

低温室效应HCFCs替代物性能分析

在阐述目前国内外HCFCs替代形势的基础上,对热泵空调及冷冻冷藏系统典型HCFCs制冷剂R22和其传统替代制冷剂(R410A,R407C,R404A,R507A),以及低温室效应R22替代物(R161,R290,RTJU4,R32,R717及R1234yf)的热力性能、循环性能及其可燃特性进行对比与分析.结果表明,R161,R290,RTJU4,R717,R32不仅具有零ODP较低GWP值的优势,其热力学及传热学特性也优于传统的HCFCs替代物,其中部分工质在一定的应用条件下具有较好的循环性能.R32,R1234yf和RTJU4的可燃性较小;RTJU4在系统循环性能上具有较明显的优势;R717具有较好热力学、传热学和循环特性,经进一步的系统和部件改进也具有较强的替代潜力.     

制冷剂R161燃烧抑制试验研究

采用球形瓶法和柱形管法进行R161的燃烧极限和燃烧速度研究,并分别以R22,R134a和R125等不燃制冷剂为阻燃剂,研究其对R161的燃烧抑制情况。一方面,考查R22／R161,R134a／R161和R125／R161混合工质不同摩尔比、不同空气含量下的燃烧极限,获得各体系的燃烧范围和临界抑爆比;另一方面,考查各混合工质不同摩尔比、不同化学当量比下的燃烧速度,获得各体系的2L燃烧等级临界配比。从而为开发零ODP,低GWP的新型环保制冷剂提供重要的燃烧安全特性数据。     

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%.     

全卤代烃CF3I和CF4的阻燃能力实验

实验测量了多组含CF3I或CF4的制冷剂混合物的爆炸极限,绘制了爆炸极限数据曲线和数据表格,确定了不同摩尔比例制冷剂混合物的爆炸三角区和临界爆炸比.参照文献中已得出的部分实验结论,通过分析比较得出全卤代烃CF3I和CF4比N2、CO2等"惰性气体"以及含氢卤代烃R134、R134a、R125等更能有效抑制可燃制冷剂的燃...     

R1234ze(E) flow boiling inside a 3.4 mm ID microfin tube

R1234ze(E) has a GWP<1 and a normal boiling temperature approximately 7.3 °C lower than that of R134a; it represents an interesting candidate for its replacement as working fluid in refrigerating machines. The refrigerant charge minimization in refrigerating and air conditioning equipment is a key issue for the new environmental challenges. Mini microfin tubes represent an optimal solution for both heat transfer enhancement and charge minimization tasks. This paper presents an experimental study of R1234ze(E) flow boiling inside a mini microfin tube with internal diameter at the fin tip of 3.4 mm. The experimental measurements were carried out at constant saturation temperature of 30 °C, by varying the refrigerant mass velocity between 190 kg m⁻² s⁻¹ and 940 kg m⁻² s⁻¹, the vapour quality from 0.2 to 0.99 at three different heat fluxes: 10, 25, and 50 kW m⁻². The experimental results are then compared with those obtained for the more traditional R134a.     

可燃制冷剂R32室内空调器泄漏扩散特性的实验研究

制冷剂R32具有良好的环保特性和热工性能,但其可燃性限制了它的应用推广,因此需要对R32的安全性进行分析。实验研究了分体壁挂式空调用制冷剂R32在空调运行时,蒸发器不同泄漏位置和不同泄漏速度对室内R32浓度分布的影响,得出R32在空调运行时的泄漏扩散特性。研究表明:可燃性制冷剂R32在室内机蒸发器处发生泄漏时,泄漏过程可分为快速泄漏阶段和低速泄漏阶段;蒸发器出口泄漏比蒸发器入口泄漏危险性高;仅在蒸发器出口大流量泄漏时,室内机附近区域R32浓度最大值为16.79%,超过可燃下限(14.4%)16.6%。可燃浓度持续了22 s,存在着火的可能性,但概率较低;排风作用对各测点的浓度衰减影响强烈,可有效降低室内R32的浓度。     

Condensation heat transfer coefficients of flammable refrigerants

In this study, external condensation heat transfer coefficients (HTCs) of six flammable refrigerants of propylene (R1270), propane (R290), isobutane (R600a), butane (R600), dimethylether (RE170), and HFC32 were measured at the vapor temperature of 39 °C on a plain tube of 19.0 mm outside diameter with a wall subcooling of 3–8 °C under a heat flux of 7–23 kW m⁻². Test results showed a typical trend that external condensation HTCs decrease with the wall subcooling. No unusual behavior or phenomenon was observed for these flammable refrigerants during experiments. HFC32 and DME showed 28–44% higher HTCs than those of HCFC22 due to their excellent thermophysical properties. Propylene and butane showed the similar HTCs as those of HCFC22 while propane and isobutane showed 9% lower HTCs than those of HCFC22. Finally, a general correlation was made by modifying Nusselt's equation based upon the measured data of eleven fluids of various vapor pressures including halogenated refrigerants. The general equation showed an excellent agreement with all data exhibiting a deviation of less than 3%.     

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.     

A Regional Comparison of Calibration Results for Type K Thermocouple Wire from (100 to 1,100) °C

Under the auspices of the Inter-American Metrology System (SIM), the National Institute of Standards and Technology (NIST) initiated a regional comparison for type K thermocouples from (100 to 1,100) °C with 11 participating countries. The use of type K material above approximately 200 °C is considered destructive. Therefore, each participating laboratory was sent new, unused wire from a lot of material characterized by NIST. The uniformity of the lot was remarkable, especially at temperatures above 500 °C; the standard deviation of the thermocouple emf values of multiple cuts tested at NIST was 2.7 μV or less over the full temperature range. The high uniformity eliminated any need to correct for variations of the transfer standard among the laboratories, greatly simplifying the analysis. The level of agreement among the laboratories’ results was quite good. Even though test procedures and equipment varied significantly among the participants, the standard deviation of all emf values at each test temperature was less than the equivalent of 0.20 °C at 200 °C and below, and less than 0.60 °C from (400 to 1,100) °C. Of the 380 total bilateral combinations of the data at the eight test temperatures, only 13 (i.e., 3.4% of all combinations) are outside the k = 2 limits, and of these 13, only 3 are outside k = 3 limits. All the outliers occur at temperatures of 800 °C and below, which suggests that drift of the type K wire due to high-temperature oxidation did not cause changes in the thermocouple emf comparable to or larger than the claimed uncertainties.     

Flexural behaviour of CNT-filled glass/epoxy composites in an in-situ environment emphasizing temperature variation

The paucity of structural defects in carbon nanotube (CNT) with unrivalled mechanical properties has always posed an interest to material scientists for its potential incorporation in soft polymer resins to achieve superior mechanical stability. Present investigation focuses on the assessment of flexural behaviour of glass/epoxy (GE) and multiwalled carbon nanotubes (MWCNT) embedded glass/epoxy (0.3 wt. % of epoxy) (CNT-GE) composites at different in-service environmental temperatures. In-situ 3-point bend tests were performed on GE and CNT-GE composites at −80 °C, −40 °C, room temperature (20 °C), 70 °C and 110 °C temperatures at 1 mm/min crosshead speed. The results revealed that at 110 °C temperature, the flexural strength of GE and CNT-GE composites was significantly decreased by 67% and 81% respectively in comparison to their strength at −80 °C temperature. Similarly, 38% and 77% decrement in modulus was noted for GE and CNT-GE composites respectively. Dynamic mechanical thermal analysis (DMTA) was carried out in the temperature range of −100 °C to 200 °C to correlate the mechanical and thermo-mechanical response of both the material systems. Addition of 0.3 wt. % MWCNT in GE composite resulted in lowering of glass transition temperature (T_g) by 12 °C. Furthermore, to understand various possible deformation and failure mechanisms, the post failure analysis of the fractured specimens, tested at different temperatures, was carried out using scanning electron microscope (SEM). The critical parameters needed during designing composite structures were calculated and modelled using Weibull constitutive model.     

Retrofitting of R404a commercial refrigeration systems using R410a and R407f refrigerants

This paper presents an experimental analysis about the retrofitting of two commercial stationary refrigeration systems marketed by an Italian leading company. Such systems operate both at medium temperature (MT), i.e. [−5; 10]°C, and low temperature (LT), i.e. [−25; −15]°C, and they are originally designed to work with hydrofluorocarbon (HFC) R404a, known as a high global warming potential (GWP) fluid (GWP = 3922). The goal is to investigate the performances of HFC R410a (GWP = 2088) and R407f (GWP = 1825), chosen as effective alternatives to HFC R404a. Such fluids are compatible with the refrigeration systems, non-flammable and easy-available. Furthermore, they meet the European Union (EU) restrictions in force in the next future, so that they are suitable to start the transition toward efficient and eco-friendly refrigeration systems. The experimental campaign shows the feasibility of adopting R407f and R410a for the MT refrigeration system and R407f fluid for the system operating at LT.     

Tensile properties and fracture behaviour of an ultrafine grained Ti–47Al–2Cr (at.%) alloy at room and elevated temperatures

An ultrafine grained (UFG) Ti–47Al–2Cr (at.%) alloy has been synthesized using a combination of high energy mechanical milling and hot isostatic pressing (HIP) of a Ti/Al/Cr composite powder compact. The material produced has been tensile tested at room temperature, 700 and 800 °C, respectively, and the microstructure of the as-HIPed material and the microstructure and fracture surfaces of the tensile tested specimens have been examined using X-ray diffractometry, optical microscopy, scanning electron microscopy and transmission electron microscopy. The alloy shows no ductility during tensile testing at room temperature and 700 °C, respectively, but very high ductility (elongation to fracture 70–100%) when tensile tested 800 °C, indicating that its brittle to ductile transition temperature (BDTT) falls within the temperature range of 700–800 °C. The retaining of ultrafine fine equiaxed grain morphology after the large amount of plastic deformation of the specimens tensile tested at 800 °C and the clear morphology of individual grains in the fractured surface indicate that grain boundary sliding is the predominant deformation mechanism of plastic deformation of the UFG TiAl based alloy at 800 °C. Cavitation occurs at locations fairly uniformly distributed throughout the gauge length sections of the specimens tensile tested at 800 °C, again supporting the postulation that grain boundary sliding is the dominant mechanism of the plastic deformation of the UFG TiAl alloys at temperatures above their BDTT. The high ductility of the UFG alloy at 800 °C and its fairly low BDTT indicates that the material a highly favourable precursor for secondary thermomechanical processing.     

The New KRISS Low Frost-Point Humidity Generator

A new low frost-point humidity generator (LFPG) has been designed, and its performance has been tested, in order to extend the calibration capabilities to the low frost-point range at KRISS. The water vapor–gas mixture is generated by saturating air with water vapor over a surface of an ice-coated saturator under the conditions of constant temperature and pressure. This LFPG covers a range of frost point from  − 99 °C to  − 40 °C. The temperature of the saturator, which is controlled by thermoelectric devices and a two-stage mechanical refrigeration system, is stable within 5 mK, and the difference between the saturator temperature and the frost point generated at the saturator outlet is less than 20 mK. This stability is achieved by using oxygen-free high-conductivity copper materials as the saturator body, and applying a precision PID temperature control system. The performance of this new LFPG system is compared with the KRISS standard two-temperature generator in the frost-point range ( − 80 to  − 40) °C, and its performance is tested with a quartz crystal microbalance (QCM), which was built at KRISS, to  − 91 °C.     

Condensation heat transfer coefficients of R22, R407C, and R410A on a horizontal plain, low fin, and turbo-C tubes

In this study, condensation heat transfer coefficients (HTCs) were measured on a horizontal plain tube, low fin tube, and Turbo-C tube at the saturated vapor temperature of 39 °C for R22, R407C, and R410A with the wall subcooling of 3–8 °C. R407C, a non-azeotropic refrigerant mixture, exhibited a quite different condensation phenomenon from those of R22 and R410A and its condensation HTCs were up to 50% lower than those of R22. For R407C, as the wall subcooling increased, condensation HTCs decreased on a plain tube while they increased on both low fin and turbo-C tubes. This was due to the lessening effect of the vapor diffusion film with a rapid increase in condensation rate on enhanced tubes. On the other hand, condensation HTCs of R410A, almost an azeotrope, were similar to those of R22. For all refrigerants tested, condensation HTCs of turbo-C tube were the highest among the tubes tested showing a 3–8 times increase as compared to those of a plain tube.     

High temperature mechanical properties of triple phase steels

A 0.15% C–1.2% Si–1.7% Mn steel was intercritically annealed at 780 °C for 5 min and then isothermally held at 400 °C for 4 min followed by oil quenching to room temperature and the annealed microstructure consist of 75% ferrite , 15% bainite and 10% retained austenite was produced. Samples of this steel with triple phase structure were tensile tested at temperature range of 25–450 °C. Stress–strain curves showed serration flow at temperature range of 120–400 °C and smooth flow at the other temperatures. All of the stress–strain curves showed discontinuous yielding at all testing temperatures. Both yield and ultimate tensile strength decreased with increasing temperature, but there exists a temperature region (120–400 °C) where a reduction of strength with increasing temperature is retarded or even slightly increased. The variation in the mechanical properties with temperature was related to the effects of dynamic strain aging, high temperature softening, bainite tempering and austenite to martensite transformation during deformation.     

A study of working fluids for heat driven ejector refrigeration using lumped parameter models

This paper studies the influence of working fluids over the performance of heat driven ejector refrigeration systems performance by using a lumped parameter model. The model used has been selected after a comparison of different models with a set of experimental data available in the literature. The effect of generator, evaporator and condenser temperature over the entrainment ratio and the COP has been investigated for different working fluids in the typical operating conditions of low grade energy sources. The results show a growth in performance (the entrainment ratio and the COP) with a rise in the generator and evaporator temperature and a decrease in the condenser temperature. The working fluids have a great impact on the ejector performance and each refrigerant has its own range of operating conditions. R134a is found to be suitable for low generator temperature (70–100 °C), whereas the hydrocarbons R600 is suitable for medium generator temperatures (100–130 °C) and R601 for high generator temperatures (130–180 °C).     

On the development of high temperature ammonia–water hybrid absorption–compression heat pumps

Ammonia–water hybrid absorption–compression heat pumps (HACHP) are a promising technology for development of efficient high temperature industrial heat pumps. Using 28 bar components HACHPs up to 100 °C are commercially available. Components developed for 50 bar and 140 bar show that these pressure limits may be possible to exceed if needed for actual applications. Feasible heat supply temperatures using these component limits are investigated. A feasible solution is defined as one that satisfies constraints on the COP, low and high pressure, compressor discharge temperature, vapour water content and volumetric heat capacity. The ammonia mass fraction and the liquid circulation ratio both influence these constraining parameters. The paper investigates feasible combinations of these parameters through the use of a numerical model. 28 bar components allow temperatures up to 111 °C, 50 bar up to 129 °C, and 140 bar up to 147 °C. If the compressor discharge temperature limit is increased to 250 °C and the vapour water content constraint is removed, this becomes: 182 °C, 193 °C and 223 °C.