1. Introduction
Rising levels of GHG in the atmosphere cause changes that permeate in the ecosystem, due to the delicate interconnectedness of animate and inanimate subjects or objects. While the focus and conversations gravitate around atmospheric GHG levels, the dire effects of GHG on the oceans and cryosphere are equally important. Oceans cover 71% of the Earth’s surface and contain about 97% of the Earth’s water. Of the frozen parts of the Earth (cryosphere), approximately 10% of the Earth’s landmass is covered by glaciers or ice sheets [
1]. Between 2006 and 2015, the Greenland ice sheet lost ice mass at an average rate of 278 ± 11 Gt y
−1, mostly due to surface melting; the Antarctic ice sheet lost mass at an average rate of 155 ± 19 Gt y
−1, and glaciers outside Greenland and Antarctica lost mass at an even higher average rate of 220 ± 30 Gt y
−1 [
1]. The year 2016 was ranked as the warmest on record. The global phasedown of hydrofluorocarbons (HFCs) is estimated to reduce warming by 0.5 °C by 2100. Challenges to global warming require the reduction of GHG emissions, and the increased use of renewable energy. Heat pumps extract energy from renewable sources and convert it to more useable forms for space conditioning and for water heating. They can be powered by renewable sources of electricity and must be engineered to use low-GWP refrigerants for a sustainable economy.
Early refrigerants up until 1930 included air, water, carbon dioxide, and ammonia, which today are classified as low-GWP natural refrigerants. However, some early refrigerants also included sulfur dioxide (toxic, corrosive), ethers (toxic) and hydrocarbons such as propane and butane (flammable). In 1930, chlorofluorocarbons (CFCs) were introduced as an “ideal” refrigerant for refrigerators because of their properties and chemical stability. CFCs were also used as a solvent, propellant, and blowing agent. The 1930s to 1960s saw even more CFCs entering the economy. By 1963, these refrigerants represented 98% of the organic fluorine industry. Following Molina and Rowland’s pioneering work on ozone depletion [
2], concerns regarding the role of CFCs in the thinning of the earth’s ozone layer began to grow. These concerns led to the ratification of the Montreal Protocol in 1987 that required the phasing out of CFCs and hydrochlorofluorocarbons (HCFCs). Hydrofluorocarbons (HFCs) emerged as a replacement for CFCs and HCFCs because of their lower first cost. Among the HFC and HFC blends used are R-134A, R-410A, R-407C, etc. However, although their ODP is negligible, their GWPs are 1300, 1924, and 1732, respectively. The Kigali amendment to the Montreal Protocol further emphasized HFC phase-down, allowing the transition to hydrofluoroolefins (HFOs) as alternate refrigerants. HFOs have an ODP = 0 and low-GWP. However, HFOs are not drop-in refrigerants. They require substantial hardware modifications and changes in compressor design because of the lack of compatibility issues with lubricants. Hence, their replacement in retrofit is not possible. In order to cope with this issue, the Environmental Protection Agency (EPA) in the United States, under Section 612 of the amended Clean Air Act (CAA) off 1990, introduced the significant new alternatives policy (SNAP) program to evaluate the use of low-GWP fluids as a direct, drop-in substitute for refrigerants such as R-410A, which this work addresses for application to heat pumps that may be used in cold climates. McLinden and Huber [
3] elegantly describe the evolution of refrigerants, from the 1920s to the 2010s, and the search for new refrigerants.
Currently, R-410A is the refrigerant used almost exclusively in residential heat pumps, and research has focused on finding low-GWP alternatives to R-410A. Lower-GWP replacements for R-410A should possess the following key characteristics: (1) similar volumetric capacity, to enable available compressors to provide a similar cooling capacity; (2) equal or higher energy efficiency; (3) accommodate the same or a wider working envelope, i.e., an adequately high refrigerant critical temperature for high ambient operation; and (4) possess similar or moderately higher compressor discharge temperature levels, to prevent the need to change the compressor lubricant and maintain the same level of reliability.
Among efforts to meet the Kigali Agreement, there is a worldwide effort to find alternate low- or lower-GWP refrigerants. The American Heating and Refrigeration Institute (AHRI) launched an industry-wide cooperative program known as the low-GWP alternate refrigerants evaluation program (Low-GWP AREP) [
4] to evaluate refrigerants for major product categories, identifying thirty-eight alternate refrigerant candidates for further evaluation. The American Society for Heating Refrigeration and Air-conditioning (ASHRAE) published a report in 2019 [
5], describing industry efforts to identify lower-GWP replacement refrigerants to replace R-410A in ducted residential and light commercial packaged units. The viewpoint of the experts in the industry is to look for options among lower-GWP refrigerants with clear advantages in total equivalent warming index (TEWI) and life-cycle cost performance (LCCP), relative to existing high-GWP refrigerants. Tightening European F-gas regulations have suggested myriad alternative refrigerant replacements containing HFC/HFO/HC/R744 mixtures. R-430A (GWP of 107) presents the closest values to R-134a, exceeding the COP values for all working conditions in room air conditioners [
6]. Replacements for R-410A include R-446A, R-447A, R-447B, R-452B, R-459B. Pham and Rajendran [
7] reviewed the technical and policy search for next-generation refrigerants with both low-GWP and LCCP factors, with a focus on replacing R-410A in unitary air conditioning and heat pumps. They concluded that R-32 (GWP of 675) offers an attractive lower-GWP solution for mainstream air-conditioning and heat pump applications, especially in new equipment re-designed to optimize performance. They further argue that the GWPs of HFOs are constrained to less than 500, not much lower than the GWP of 675 for R-32. Furthermore, HFOs remain very expensive. A theoretical screening of refrigerant mixtures by Yu [
8] came up with thirty-four mixtures with a GWP < 150 that matched the volumetric capacity and COP of R-410A, of which a smaller subset of four refrigerants also offered almost the same pressure as that of R-410. The four refrigerants are: R32/R1123/R161/R1131 (20/40/10/30), R1123/R161/R1131 (65/5/30), R1123/R152a/R1311 (65/5/30), and R1123/R1234ze(E)/R1311 (65/5/30). Issues pertaining to lubricant compatibility/miscibility, etc., are yet to be determined and confirmed experimentally. Yang [
9] evaluated blends of HFC32/HFO1234yf and HFC32/HFO1234ze(E), with a GWP of about 300 for domestic heat pumps with reduced life cycle environmental impact, as promising substitutes for R-410A. Sieres [
10] investigated R-452B and R-454B as drop-in replacements for R-410A in liquid-to-water heat pumps, with the caveat that there is an optimum refrigerant charge that maximizes the COP, to be determined experientially.
Potential lower-GWP refrigerants for R-410A used in this study are indicated in
Table 1. The R-410A replacements are mostly blends containing R-32 with HFCs (R-125) and HFOs (R-1234yf) (see footnotes to
Table 1). Candidate refrigerants have approximately 70% lower GWPs than R-410A. Some compositions of R-32 and R-1234yf are mildly flammable and are classified as A2L. R-466A is an A1 refrigerant, i.e., non-flammable. These refrigerant blends have negligible temperature glides. All the listed alternatives have higher critical temperatures than R-410A, making them more suitable for high condensing temperature operation, enabling them to be used in integrated heat pumps with water heating capability while simultaneously providing space cooling.
This study compares short-term replacements of R-410A, i.e., direct drop-in without modifying the existing hardware and manufacturing lines. These replacements require comparable volumetric capacity and energy efficiency to R-410A and have negligible temperature glides. The industry has selected those refrigerants having lower GWPs of around 700 as short-term options, as shown in
Table 1. Refrigerants having GWPs < 150 will be long-term replacements, which tend to have significant temperature glides, and need a re-design of the system and components. To do this, the performance of a heat pump is simulated with R-410A and then with each of the alternatives. The results of the simulations are used to compare the performance of the heat pump with each alternative to its performance relative to R-410A. The simulations are performed using the DOE/ORNL heat pump design model (HPDM) [
11], a research tool developed by the U.S Department of Energy for industry and academics. In addition to an online version, the HPDM is also provided in a free, downloadable desktop version. More than three major US manufacturers have adopted HPDM as their in-house product design tool. In particular, the Emerson Company has integrated HPDM into their compressor selection and system simulation software, and they developed their own interface and have distributed it to over 80 worldwide equipment manufacturers. In a report published by RTI International [
12], the DOE/ORNL heat pump design model was acknowledged as one of the five most rewarding investments made by the U.S. Department of Energy in HVAC, water heating, and appliance technologies since 1976. The model has been used worldwide over 350,000 times, with extensive scientific and technical literature validating the simulations [
1,
12,
13,
14,
15,
16].
4. Model Description, Features, and Assumptions
The DOE/ORNL heat pump design model (HPDM) with a two-speed compressor simulated the performances for all refrigerants. The two-speed heat pump has a rated cooling capacity of 5-ton/17.6 kW at 35 °C ambient temperature/26.7 °C indoor dry-bulb (DB) temperature, and 19.4 °C indoor wet-bulb temperature (WB). The high and low speeds of the scroll compressor provide 100% and 67% of the rated capacity, respectively. The indoor and outdoor heat exchangers are described in
Table 2. To model the system, the evaporator exit was assumed to have a constant superheat degree of 10 R (5.6 K).
This study is based on the AHRI 210/240 standard (AHRI, 2008) rating conditions for 2-speed heat pumps. In cooling mode, the heat pump should provide performance metrics at 35 °C and 27.8 °C ambient temperature, and an indoor condition of 26.7 °C DB/19.4 °C WB.
Table 3 below presents the predicted cooling performances of the heat pump using R-410A at the low- (_L) and high-speed (_H) levels, including cooling capacities (kW), cooling COPs (W/W), compressor discharge temperature (C/F) and compressor efficiency, as defined by Equation (2).
The two-speed scroll compressor uses the full displacement volume at 100% capacity. At 67% capacity, only part of the scroll is utilized, which causes more loss factors. As a result, the compressor efficiency of the low speed is roughly 7% lower than the high speed. The shell loss ratio, relative to the compressor power, is 10% for all the cooling conditions.
Figure 2 shows cooling capacity variations of the drop-in alternative refrigerant compared to R-410A. R-32 and R-466A result in 4% to 6% higher cooling capacities in all conditions, whereas R-452B and R-454B lead to approximately 2% smaller capacities.
Figure 3 shows increments in cooling COPs. With the same heat exchangers, larger cooling capacity tends to cause higher condensing temperatures and lower evaporating temperatures, degrading the efficiency because the temperature lift is higher. Consequently, R-32 and R-466A have larger volumetric capacities at the expense of reduced COPs. R-452B and R-454B result in higher COPs.
Figure 4 presents the compressor discharge temperatures. R-32 has significantly higher discharge temperatures, up to 16.67 K (30R). The other alternative refrigerants show slightly higher temperatures, up to 5.56 K (10R). At the low speed, the discharge temperatures are lower than those at the high speed, because the condensing temperature is reduced at the part-load operation.
Figure 5 compares the seasonal cooling COPs, calculated from AHRI 210/240. They differ slightly, ranging from 4.45 to 4.58. R-454B results in the highest COP, and R-466A results in the lowest COP.
The systemic COPs based on the first law present an adumbrate view of energy efficiency. To investigate systemic inefficiency and where the opportunity for further efficiency improvements may be found, an exergy analysis is imperative, utilizing both the first and second law of thermodynamics.
5. General Mass, Energy, and Exergy Balances
Cycle analyses are based on the values of stated variables at stated points corresponding to
Figure 1, obtained from the HPDM simulations, and thermodynamic properties from REFPROP 10.0 [
27].
The general mass and energy balance equations are given by Equations (3) and (4), respectively,
where
is the rate of thermal energy exchanged between the control volume (CV) around a specific component of the heat pump and the surroundings at
;
is the rate of work input to the compressor;
represent enthalpy, kinetic energy, and potential energy, respectively; and
is the refrigerant mass flow rate. Under a steady state, the steady flow assumption of the model, transient terms,
and
in Equations (3) and (4), respectively, reduce to zero.
The general exergy balance equation [
28], applied across each discrete component under evaluation, is:
where
is the sum of the entropy generation rates due to internal irreversibility and those from irreversible thermal energy transfer between the CV surrounding each component, and its surrounding. This method of exergy analysis of heat pumps has been validated and applied to low-GWP heat pumps, and in more complex cases (due to interaction with both the ground and the ambient air) for ground source heat pumps [
29,
30,
31] and for cold-climate heat pumps [
18].
Irreversibility, the thermodynamic measure of the lost opportunity to do useful work is related to the rate of entropy generation by:
The mass flow rate and values of state functions around the CV for each heat pump component are obtained from the HPDM model. The application of Equations (3)–(6) to the particular heat pump component and its corresponding state points (see
Figure 1) yield the component and systemic irreversibility and energy balances shown in
Table 4.
6. Energy, Entropy Generation, and Irreversibility
The work input to the compressor obtained from the HPDM model for each outdoor temperature is the algebraic sum of
and
, which equals
as shown in
Table 5. The negative sign for
is because heat is flowing out of the compressor CV, as per IUPAC convention (energy inflow is positive, outflow is negative). From entropy generation rate,
, the total compressor irreversibility is
, where
is the ambient temperature specified in the headings of
Table 5.
For a rigorous analysis, we must show consistency between the compressor work input (
) from the HPDM model and that calculated from irreversibility analysis. The total actual work input to the compressor must be the sum of the Carnot work and the irreversibility losses. The Carnot COP (cooling mode) for an ideal heat pump with no irreversibility is given by:
where
is the heat reject temperature, specified on the header of
Table 4, and
is the indoor set-point temperature (26.67 °C). The total cyclic irreversibility,
, is the sum of the irreversibility of each component: the compressor, condenser, EXV, and line loss between the evaporator and the compressor inlet
, and the line loss from the compressor outlet to the evaporator inlet
. The actual work input must be the sum of the ideal work (Carnot work) and the lost work due to irreversibility.
Thus, in
Table 5,
and is in reasonable agreement with the work input to the heat pump (HP),
derived from the model. This calculation is performed for each ambient temperature. We emphasize that the work computed from irreversibility analysis for the heat pump cycle and that obtained from the HPDM model are consistent, complementary, and therefore validate our analyses.
9. Conclusions
It is technically feasible to replace R-410A (GWP 1934) with lower-GWP refrigerants (
Table 2) without changing the heat-pump hardware. Cooling capacity increments of the drop-in alternative refrigerant compared to R-410A are 4% and 6% better for R-32 and R-466A, respectively, and 2% worse for R-452B and R-454B, respectively.
We conclude that seasonal cooling COPs, calculated using AHRI 210/240 specifications, show slight variation from 4.45 to 4.58. R-454B results in the highest COP, and R-466A results in the lowest COP (
Figure 5). Systemic irreversibility calculated from using both the first and the second laws of thermodynamics pointed toward slightly lower compressor irreversibility with R-452B and R-454B, relative to the other refrigerants, for high and low compressor speeds. Evaporator irreversibility exceeded compressor irreversibility, except for the 35 °C low-speed condition, where it was marginally less. The conclusion from the irreversibility analysis strongly suggests that to mitigate lost work, it is essential to focus on heat exchanger technology to reduce the condenser and evaporator irreversibility. The total systemic irreversibility is least significant for R-452B and for R-454B, for all conditions of temperature and compressor speed.
All the candidate low-GWP refrigerants have better efficiency and performance characteristics. The energy input to the compressor, systemic irreversibility, and condenser duty are important considerations before selecting a refrigerant. In particular, R-452B and R-454B have the lowest systemic irreversibility. Overall, any of the four alternative refrigerants are viable drop-in replacements.