Low gwp fluids for high temperature heat pump applications

Abstract

The present invention relates to refrigerants comprising HFO-1233zd, HFO-1234ze(E) and HFC-152a, and the use of such refrigerants in high temperature heat pumps.

Description

[0001] Cross-reference to related applications

[0002] This application relates to and claims priority to U.S. Application No. 19 / 054,549, filed February 14, 2025, and U.S. Provisional Application No. 63 / 558,088, filed February 26, 2024, each of which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention relates to compositions, methods and systems that are practical in heat transfer applications, with particular benefits in high-temperature heat pump applications; and in a particular aspect, to heat transfer and / or refrigerant compositions for replacing or substituting previously used refrigerants (including CFC-114, 1233zd(E) and 1234ze(Z)), particularly for providing heating in high-temperature heat pump systems. Background Technology

[0004] High-temperature heat pumps have been used to upgrade low-grade heat energy (such as from air, soil, surface water or groundwater, geothermal energy, solar energy, and industrial waste heat and process streams) into high-grade heat energy through thermodynamic cycles. Heat pump systems use a working fluid (i.e., a refrigerant) to facilitate the generation and transfer of heat in a vapor compression thermodynamic cycle. Heat pump systems have been used for both heating and cooling purposes.

[0005] Historically, certain chlorofluorocarbons (CFCs) have been used as working fluids in heat pumps, refrigerators, and other heating / cooling devices and machines. For high-temperature heat pumps, 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114) has been widely used. However, CFC-114 has a very high Global Warming Potential (GMP) value exceeding 10,000. While CFC-114 has been replaced in some applications by refrigerants such as R-134a, R-227ea, R-236fa, or R-245fa, the use of such materials has significant drawbacks. For example, all of the aforementioned refrigerants have relatively high GMP values, and R-134a and R-227ea have relatively low critical point temperatures, limiting their applicability to lower-temperature applications. Therefore, there remains a continued need for a more acceptable alternative to CFC-114 in high-temperature heat pumps.

[0006] U.S. Patent Publication 2016 / 0178255 discloses that heat transfer compositions containing the cis isomer of 1,3,3,3-tetrafluoropropylene (HFO-1234ze(Z)) can be used in a variety of heat transfer applications, including high-temperature heat pump applications. While HFO-1234ze(Z) may possess certain properties that could exhibit advantages in high-temperature heat pump applications, information regarding HFO-1234ze(Z) has been confirmed to be relatively scarce. (See Brown et al., International Journal of Refrigeration, Vol. 32, No. 6, September 2009, pp. 1412-1422, “The fluorinated olefin R-1234ze(Z) as a high-temperature heat pumping refrigerant”). Specifically, the applicant has recognized that the lack of information regarding the toxicity and flammability of HFO-1234ze(Z), coupled with the fact that the compound has not yet been registered for use in any geographic region, makes its current use in high-temperature heat pump applications less than satisfactory.

[0007] U.S. Patent 9,850,414 (assigned to the assignee of this application) discloses the use of 1233zd(E) alone and in blends with other refrigerants including 1234ze(E) in high-temperature heat pump applications. U.S. Patent 10,101,065 also discloses the use of 1233zd(E) and 1233zd(Z) in high-temperature heat pumps. U.S. Patent 11,827,834 discloses a refrigerant blend comprising: (a) carbon dioxide; and (b) a non-flammable, low-volatility component selected from the group consisting of: HFO1224yd(Z), HFO1224yd(E), HFO1233zd(E), HFO1233zd(Z), HFO1233xf, HFO1336mzz(E), HFO1336mzz(E). (c) a moderately volatile component selected from the group consisting of HFO1234yf, HFO1234ze(E), HFO-1225ye(Z), and HFO1243zf, or mixtures thereof; and (d) an optional component selected from HFC-227ea, HFC-152a, HFC-32, or mixtures thereof. One use of the refrigerant blends disclosed in the '834 patent is in heat pump applications. While the use of 1233zd(E) as disclosed in the '414 patent has significant advantages, the applicant has recognized that improvements in cost and complexity of equipment (particularly compressors) used in conjunction with such systems can be achieved by selecting new and advantageous refrigerant blends.

[0008] Therefore, the applicant has recognized the need for and / or the significant advantages that can be achieved through such a working fluid in high-temperature heat pumps, which exhibits low ODP, low GWP, low flammability, acceptable toxicity, and excellent thermal properties over a high-temperature range (preferably with high capacity relative to pure 1233zd(E), particularly in systems using high radiator temperatures of about 60°C or higher to condense the refrigerant). The applicant has recognized the need for the use of such a working fluid in new systems, as well as the need for a working fluid that is advantageous as an alternative and / or substitute for CFC-114 and / or HFO-1234ze(Z) and / or 1233zd(E) in high-temperature heat pump systems.

[0009] This invention offers significant advantages for large-scale centralized heat pump systems, particularly for district heating. In such systems, a shared centralized system is used as the heat source, such as underground pipe borehole arrays, air source systems, and waste heat recovery from industrial processes. These systems typically provide heat to several residential blocks, townhouses, or one or more high-rise apartment buildings. Such arrangements are known in the prior art and herein as district heating applications, and relatively large compressor units are typically used in these systems. The applicant has recognized that unexpected advantages can be achieved by using the refrigerants, systems, and methods of this invention, because these refrigerants are not only environmentally friendly and A2L or A1 grade, but they also provide at least about 20% more capacity than currently used heat pump refrigerants (particularly 1233zd(E)). In this context, given the ability to purchase compressors with a total compressor displacement at least 15% smaller than those used in previous systems, the invention can be implemented with substantial and significant cost savings, resulting in substantial savings in installation and potential maintenance costs over the life of the device.

[0010] The refrigerants, heat transfer compositions, systems, and methods of the present invention described herein meet these and / or other needs. Summary of the Invention

[0011] The applicant has unexpectedly and advantageously discovered that, as described in detail herein, compositions based on carefully selected amounts of HFO-1233zd(E), HFO-1234ze(E), and HFC-152a can provide refrigerants that satisfy all and all of the many and preferred requirements discussed above, as well as the additional requirements and / or advantages described below.

[0012] The applicant has discovered refrigerants, heat transfer compositions, refrigeration methods and systems utilizing one or more compositions of the present invention as refrigerants, including, and in particular, applications in conjunction with high-temperature heat pumps.

[0013] This invention includes refrigerants, which comprise:

[0014] (1) 81% to 89% by weight of HFO-1233zd(E);

[0015] (2) 4% to 15% by weight of HFO-1234ze(E); and

[0016] (3) Approximately 2% to 9% by weight of HFC-152a,

[0017] The refrigerant described therein has: (i) a global warming potential (GWP) of 10 or lower; (ii) a flammability of 2 L; and (iii) a critical temperature greater than 150 °C.

[0018] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 1A.

[0019] This invention includes a refrigerant that is substantially composed of the following components:

[0020] (1) 81% by weight to about 89% by weight of HFO-1233zd(E);

[0021] (2) 4% to 15% by weight of HFO-1234ze(E); and

[0022] (3) 2% to 9% HFC-152a by weight.

[0023] For convenience, the refrigerant mentioned in this paragraph is sometimes referred to as refrigerant 1B.

[0024] This invention includes a refrigerant composed of the following components:

[0025] (4) 81% to 89% by weight of HFO-1233zd(E);

[0026] (5) 4% to 15% by weight of HFO-1234ze(E); and

[0027] (6) 2% to 9% HFC-152a by weight.

[0028] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 1C.

[0029] This invention includes refrigerants, which comprise:

[0030] (1) 83% to 89% by weight of HFO-1233zd(E);

[0031] (2) 7% to 11% by weight of HFO-1234ze(E); and

[0032] (3) 3% to 7% HFC-152a.

[0033] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 2A.

[0034] This invention includes a refrigerant that is substantially composed of the following components:

[0035] (1) 83% to 89% by weight of HFO-1233zd(E);

[0036] (2) 7% to 11% by weight of HFO-1234ze(E); and

[0037] (3) 3% to 11% HFC-152a by weight.

[0038] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 2B.

[0039] This invention includes a refrigerant composed of the following components:

[0040] (1) 83% to 89% by weight of HFO-1233zd(E);

[0041] (2) 7% to 11% by weight of HFO-1234ze(E); and

[0042] (3) 3% to 7% HFC-152a.

[0043] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 2C.

[0044] This invention includes refrigerants comprising at least about 95% by weight of the following three components in relative concentrations based on the total amount of all refrigerants:

[0045] (1) 81% to 86% by weight of HFO-1233zd(E);

[0046] (2) 10% to 13% by weight of HFO-1234ze(E); and

[0047] (3) 3% to 7% by weight of HFC-152a,

[0048] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 3A.

[0049] This invention includes a refrigerant that is substantially composed of the following components:

[0050] (1) 81% to 86% by weight of HFO-1233zd(E);

[0051] (2) 10% to 13% by weight of HFO-1234ze(E); and

[0052] (3) 4% to 7% HFC-152a.

[0053] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 3B.

[0054] This invention includes a refrigerant composed of the following components:

[0055] (1) 81% to 86% by weight of HFO-1233zd(E);

[0056] (2) 10% to 13% by weight of HFO-1234ze(E); and

[0057] 4% to 7% by weight of HFC-152a. For convenience, the refrigerant referred to in this article is sometimes referred to as refrigerant 3C.

[0058] This invention includes refrigerants that are essentially composed of the following three components in relative concentrations:

[0059] (1) 86.2 wt% + / - 2 wt% HFO-1233zd(E);

[0060] (2) 8.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0061] (3) 5% by weight + / - 1% by weight of HFC-152a.

[0062] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 4A.

[0063] This invention includes a refrigerant composed of the following components:

[0064] (1) 86.2 wt% + / - 2 wt% HFO-1233zd(E);

[0065] (2) 8.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0066] (3) 5% by weight + / - 1% by weight of HFC-152a.

[0067] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 4B.

[0068] This invention includes refrigerants that are essentially composed of the following three components in relative concentrations:

[0069] (1) 83.2% by weight + / - 2% by weight of HFO-1233zd(E);

[0070] (2) 11.8 wt% + / - 1 wt% of HFO-1234ze(E); and

[0071] (3) 5% by weight + / - 1% by weight of HFC-152a.

[0072] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 5A.

[0073] This invention includes a refrigerant composed of the following components:

[0074] (1) 83.2% by weight + / - 2% by weight of HFO-1233zd(E);

[0075] (2) 11.8 wt% + / - 1 wt% of HFO-1234ze(E); and

[0076] (3) 5% by weight + / - 1% by weight of HFC-152a.

[0077] For convenience, the refrigerant mentioned in this paragraph will sometimes be referred to as refrigerant 5B.

[0078] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0079] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 70°C to about 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0080] a. HFO-1233zd(E) of about 83% to about 89% by weight;

[0081] b. HFO-1234ze(E) of about 4 wt% to about 15 wt%; and

[0082] c. From about 2 wt% to about 8 wt% of HFC-152a, wherein the refrigerant has: (i) a global warming potential (GWP) of 10 or lower; (ii) a flammability of 2 L; and (iii) a critical temperature greater than 150 °C; and

[0083] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the volumetric volume of the refrigerant in the system is at least about 120% of the volumetric volume of R-1233zd(E) in the system.

[0084] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 1A in this paper.

[0085] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0086] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 70°C to about 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0087] a. HFO-1233zd(E) of about 81% to about 89% by weight;

[0088] b. HFO-1234ze(E) of about 4 wt% to about 15 wt%; and

[0089] c. From about 2% to about 9% by weight of HFC-152a, wherein the refrigerant has: (i) a global warming potential (GWP) of 10 or lower; (ii) a flammability of 2 L; and (iii) a critical temperature greater than 150°C; and

[0090] (2) Evaporate the refrigerant in the direct expansion evaporator, wherein the COP of the refrigerant in the system is at least 96% of the COP of R-1233zd(E) in the system.

[0091] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 1B in this paper.

[0092] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0093] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 70°C to about 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0094] (1) HFO-1233zd(E) of about 81% to about 89% by weight;

[0095] (2) HFO-1234ze(E) of about 4 wt% to about 15 wt%; and

[0096] (3) From about 2% to about 9% by weight of HFC-152a, wherein the refrigerant has: (i) a global warming potential (GWP) of 10 or lower; (ii) a flammability of 2 L; and (iii) a critical temperature greater than 150 °C; and

[0097] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant (i) has a volumetric capacity in the system that is at least about 120% of the volumetric capacity of R-1233zd(E) in the system, and (ii) has a COP in the system that is at least 96% of the COP of R-1233zd(E) in the system.

[0098] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 1C in this paper.

[0099] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0100] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0101] (a) HFO-1233zd(E) of about 83% to about 89% by weight;

[0102] (b) HFO-1234ze(E) of about 4 wt% to about 15 wt%; and

[0103] (c) about 2% to about 8% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0104] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the volumetric volume of the refrigerant in the system is at least about 120% of the volumetric volume of R-1233zd(E) in the system.

[0105] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 2A in this paper.

[0106] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0107] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0108] (a) HFO-1233zd(E) of about 83% to about 89% by weight;

[0109] (b) HFO-1234ze(E) of about 4 wt% to about 15 wt%; and

[0110] (c) about 2% to about 8% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0111] (2) Evaporate the refrigerant in the direct expansion evaporator, wherein the COP of the refrigerant in the system is at least 96% of the COP of R-1233zd(E) in the system.

[0112] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 2B in this article.

[0113] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0114] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0115] (a) HFO-1233zd(E) of about 83% to about 89% by weight;

[0116] (b) HFO-1234ze(E) of about 4 wt% to about 15 wt%; and

[0117] (c) about 2% to about 8% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0118] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric capacity in the system of at least about 120% of the volumetric capacity of R-1233zd(E) in the system; and (ii) has a COP in the system of at least 96% of the COP of R-1233zd(E) in the system.

[0119] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 2C in this article.

[0120] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0121] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0122] (a) HFO-1233zd(E) of about 83% to about 89% by weight;

[0123] (b) HFO-1234ze(E) of about 4 wt% to about 15 wt%; and

[0124] (c) about 2% to about 8% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0125] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric ...

[0126] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 2D in this article.

[0127] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0128] (1) A vapor compression refrigeration system is provided, comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant is substantially composed of the following three components in relative concentrations:

[0129] a. 86.2 wt% + / - 2 wt% of HFO-1233zd(E);

[0130] b.8.8% by weight + / -1% by weight of HFO-1234ze(E); and

[0131] c. 5% by weight + / - 1% by weight of HFC-152a; and

[0132] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the volumetric volume of the refrigerant in the system is at least about 120% of the volumetric volume of R-1233zd(E) in the system.

[0133] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 3A in this article.

[0134] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0135] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0136] (a) 86.2 wt% + / - 2 wt% HFO-1233zd(E);

[0137] (b) 8.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0138] (c) 5% by weight + / - 1% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0139] (2) Evaporate the refrigerant in the direct expansion evaporator, wherein the COP of the refrigerant in the system is at least 96% of the COP of R-1233zd(E) in the system.

[0140] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 3B in this article.

[0141] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0142] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0143] (a) 86.2 wt% + / - 2 wt% HFO-1233zd(E);

[0144] (b) 8.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0145] (c) 5% by weight + / - 1% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0146] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric capacity in the system of at least about 120% of the volumetric capacity of R-1233zd(E) in the system; and (ii) has a COP in the system of at least 96% of the COP of R-1233zd(E) in the system.

[0147] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 3C in this article.

[0148] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0149] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0150] (a) 86.2 wt% + / - 2 wt% HFO-1233zd(E);

[0151] (b) 8.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0152] (c) 5% by weight + / - 1% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0153] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric ...

[0154] For convenience, the method described in this paragraph is sometimes referred to as the 3D heat transfer method in this article.

[0155] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0156] (1) A vapor compression refrigeration system is provided, comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant is substantially composed of the following three components in relative concentrations:

[0157] a. 83.2 wt% + / - 2 wt% of HFO-1233zd(E);

[0158] b. 11.8 wt% + / - 1 wt% of HFO-1234ze(E); and

[0159] c. 5% by weight + / - 1% by weight of HFC-152a; and

[0160] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the volumetric volume of the refrigerant in the system is at least about 120% of the volumetric volume of R-1233zd(E) in the system.

[0161] For convenience, the method described in this section is sometimes referred to as heat transfer method 4A in this article.

[0162] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0163] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0164] (a) 83.2 wt% + / - 2 wt% HFO-1233zd(E);

[0165] (b) 11.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0166] (c) 5% by weight + / - 1% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0167] (2) Evaporate the refrigerant in the direct expansion evaporator, wherein the COP of the refrigerant in the system is at least 96% of the COP of R-1233zd(E) in the system.

[0168] For convenience, the method described in this section is sometimes referred to as heat transfer method 4B in this article.

[0169] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0170] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0171] (a) 83.2 wt% + / - 2 wt% HFO-1233zd(E);

[0172] (b) 11.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0173] (c) 5% by weight + / - 1% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0174] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric capacity in the system of at least about 120% of the volumetric capacity of R-1233zd(E) in the system; and (ii) has a COP in the system of at least 96% of the COP of R-1233zd(E) in the system.

[0175] For convenience, the method described in this section is sometimes referred to as heat transfer method 4C in this article.

[0176] This invention includes a method for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0177] (1) Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 90°C to 130°C, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 30°C to about 90°C to the liquid phase of the refrigerant, wherein the refrigerant comprises:

[0178] (a) 83.2 wt% + / - 2 wt% HFO-1233zd(E);

[0179] (b) 11.8 wt% + / - 1 wt% HFO-1234ze(E); and

[0180] (c) 5% by weight + / - 1% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0181] (2) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric ...

[0182] For convenience, the method described in this section is sometimes referred to as heat transfer method 4D in this article.

[0183] This invention includes a method for providing district heating to multiple residential spaces, the method comprising:

[0184] (1) A vapor compression refrigeration system comprising: one or more compressors receiving refrigerant vapor from one or more direct expansion evaporators; and one or more condensers receiving compressed refrigerant vapor from the one or more compressors and producing condensed liquid refrigerant for supply to the one or more expanders, the one or more expanders producing liquid refrigerant for supply to the one or more direct expansion evaporators.

[0185] (2) A heat source with a temperature of about 30°C to about 90°C is provided, which directly or indirectly evaporates the liquid refrigerant in the one or more evaporators.

[0186] (3) Providing a radiator that directly or indirectly condenses the vapor refrigerant in the condenser, wherein at least one or more compressors are not located in the residence, and wherein the radiator comprises air and / or water circulating in the residence at a temperature of about 90°C to about 130°C, and wherein the refrigerant comprises:

[0187] (a) 83% to 89% by weight of HFO-1233zd(E);

[0188] (b) 4% to 15% by weight of HFO-1234ze(E); and

[0189] (c) 2% to 9% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0190] (4) Evaporating the refrigerant in the direct expansion evaporator, wherein the volumetric volume of the refrigerant in the system is at least about 120% of the volumetric volume of R-1233zd(E) in the system.

[0191] For convenience, the method described in this section is sometimes referred to as heat transfer method 5A in this article.

[0192] This invention includes a method for providing district heating to multiple residential spaces, the method comprising:

[0193] (1) A vapor compression refrigeration system comprising: one or more compressors receiving refrigerant vapor from one or more direct expansion evaporators; and one or more condensers receiving compressed refrigerant vapor from the one or more compressors and producing condensed liquid refrigerant for supply to the one or more expanders, the one or more expanders producing liquid refrigerant for supply to the one or more direct expansion evaporators.

[0194] (2) A heat source with a temperature of about 30°C to about 90°C is provided, which directly or indirectly evaporates the liquid refrigerant in the one or more evaporators.

[0195] (3) Providing a radiator that directly or indirectly condenses the vapor refrigerant in the condenser, wherein at least one or more compressors are not located in the residence, wherein the radiator comprises air and / or water circulating in the residence at a temperature of about 90°C to about 130°C, and wherein the refrigerant comprises:

[0196] (a) 81% to 89% by weight of HFO-1233zd(E);

[0197] (b) 4% to 15% by weight of HFO-1234ze(E); and

[0198] (c) 2% to 9% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0199] (4) Evaporating the refrigerant in the direct expansion evaporator, wherein the COP of the refrigerant in the system is at least 96% of the COP of R-1233zd(E) in the system.

[0200] For convenience, the method described in this paragraph is sometimes referred to as heat transfer method 5B in this article.

[0201] This invention includes a method for providing district heating to multiple residential spaces, the method comprising:

[0202] (1) A vapor compression refrigeration system comprising: one or more compressors receiving refrigerant vapor from one or more direct expansion evaporators; and one or more condensers receiving compressed refrigerant vapor from the one or more compressors and producing condensed liquid refrigerant for supply to the one or more expanders, the one or more expanders producing liquid refrigerant for supply to the one or more direct expansion evaporators.

[0203] (2) A heat source with a temperature of about 30°C to about 90°C is provided, which directly or indirectly evaporates the liquid refrigerant in the one or more evaporators.

[0204] (3) Providing a radiator that directly or indirectly condenses the vapor refrigerant in the condenser, wherein at least one or more compressors are not located in the residence, wherein the radiator comprises air and / or water circulating in the residence at a temperature of about 90°C to about 130°C, and wherein the refrigerant comprises:

[0205] (a) 81% to 89% by weight of HFO-1233zd(E);

[0206] (b) 4% to 15% by weight of HFO-1234ze(E); and

[0207] (c) 2% to 9% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0208] (4) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric capacity in the system of at least about 120% of the volumetric capacity of R-1233zd(E) in the system; and (ii) has a COP in the system of at least 96% of the COP of R-1233zd(E) in the system.

[0209] For convenience, the method described in this section is sometimes referred to as heat transfer method 5C in this article.

[0210] This invention includes a method for providing district heating to multiple residential spaces, the method comprising:

[0211] (1) A vapor compression refrigeration system comprising: one or more compressors receiving refrigerant vapor from one or more direct expansion evaporators; and one or more condensers receiving compressed refrigerant vapor from the one or more compressors and producing condensed liquid refrigerant for supply to the one or more expanders, the one or more expanders producing liquid refrigerant for supply to the one or more direct expansion evaporators.

[0212] (2) A heat source with a temperature of about 30°C to about 90°C is provided, which directly or indirectly evaporates the liquid refrigerant in the one or more evaporators.

[0213] (3) Providing a radiator that directly or indirectly condenses the vapor refrigerant in the condenser, wherein at least one or more compressors are not located in the residence, wherein the radiator comprises air and / or water circulating in the residence at a temperature of about 90°C to about 130°C, and wherein the refrigerant comprises:

[0214] (a) 81% to 89% by weight of HFO-1233zd(E);

[0215] (b) 4% to 15% by weight of HFO-1234ze(E); and

[0216] (c) 2% to 9% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0217] (4) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric capacity in the system of at least about 120% of the volumetric capacity of R-1233zd(E) in the system; (ii) has a COP in the system of at least 96% of the COP of R-1233zd(E) in the system; and (iii) has an evaporator glide temperature of about 2°C to less than about 10°C.

[0218] For convenience, the method described in this section is sometimes referred to as heat transfer method 5D in this article.

[0219] This invention includes a method for providing district heating to multiple residential spaces, the method comprising:

[0220] (1) A vapor compression refrigeration system comprising: one or more compressors receiving refrigerant vapor from one or more direct expansion evaporators; and one or more condensers receiving compressed refrigerant vapor from the one or more compressors and producing condensed liquid refrigerant for supply to the one or more expanders, the one or more expanders producing liquid refrigerant for supply to the one or more direct expansion evaporators.

[0221] (2) A heat source with a temperature of about 30°C to about 90°C is provided, which directly or indirectly evaporates the liquid refrigerant in the one or more evaporators.

[0222] (3) Providing a radiator that directly or indirectly condenses the vapor refrigerant in the condenser, wherein the radiator comprises air and / or water circulating in each of the plurality of residences, wherein at least one or more compressors are not located in the residences, wherein the radiator comprises air and / or water circulating in the residences at a temperature of about 90°C to about 130°C, and wherein the refrigerant comprises:

[0223] (a) 81% to 89% by weight of HFO-1233zd(E);

[0224] (b) 4% to 15% by weight of HFO-1234ze(E); and

[0225] (c) 2% to 8% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0226] (4) Evaporating the refrigerant in the direct expansion evaporator, wherein the refrigerant: (i) has a volumetric capacity in the system of at least about 120% of the volumetric capacity of R-1233zd(E) in the system; (ii) has a COP in the system of at least 96% of the COP of R-1233zd(E) in the system; and (iii) has an evaporator glide temperature of about 2°C to less than about 10°C.

[0227] For convenience, the method described in this section is sometimes referred to as heat transfer method 5D in this article.

[0228] The present invention also includes a method for reducing the cost of forming a high-temperature heat pump system for providing heat to a radiator containing a fluid or object to be heated, the method comprising:

[0229] (1) A vapor compression refrigeration system is provided, the vapor compression refrigeration system comprising:

[0230] a. A compressor for compressing a gaseous refrigerant, wherein the displacement of the compressor is at least about 15% smaller than that required to achieve the same capacity using a refrigerant composed of 1233zd(E) in the system;

[0231] b. A condenser that transfers heat directly or indirectly from the gaseous refrigerant to a radiator, wherein the temperature of the radiator is from about 90°C to about 130°C; and a direct expansion evaporator that transfers heat directly or indirectly from a heat source to the liquid phase of the refrigerant, wherein the temperature of the heat source is from about 30°C to about 90°C, wherein the refrigerant comprises:

[0232] i. 81% to 89% by weight of HFO-1233zd(E);

[0233] ii. 4% to 15% by weight of HFO-1234ze(E); and

[0234] iii. 2% to 9% by weight of HFC-152a, wherein the refrigerant is 2L; and

[0235] (2) Evaporate the refrigerant in the direct expansion evaporator, wherein the COP of the refrigerant in the system is at least 96% of the capacity of R-1233zd(E) in the system.

[0236] For convenience, the method described in this paragraph is sometimes referred to as heat pump cost reduction method 1 in this article.

[0237] The present invention includes a vapor compression heat pump that provides heat to a radiator containing a fluid or object to be heated, the vapor compression heat pump comprising:

[0238] (1) Refrigerant;

[0239] (2) A compressor for compressing the gaseous phase of the refrigerant;

[0240] (3) A condenser that transfers heat directly or indirectly from the gaseous refrigerant to a radiator at a temperature of about 90°C to about 130°C; and

[0241] (4) A direct expansion evaporator that transfers heat from a heat source at a temperature of about 30°C to about 90°C to the refrigerant in the liquid phase.

[0242] (5) The refrigerant comprises:

[0243] i. 81% to 89% by weight of HFO-1233zd(E);

[0244] ii. 4% to 15% by weight of HFO-1234ze(E); and

[0245] iii. 2% to 9% by weight of HFC-152a,

[0246] The refrigerant: (a) is 2L; and (b) its capacity in the system is at least about 120% of the capacity of R-1233zd(E) in the system.

[0247] For convenience, the heat pump mentioned in this paragraph is sometimes referred to as heat pump 1A.

[0248] The present invention includes a vapor compression heat pump that provides heat to a radiator containing a fluid or object to be heated, the vapor compression heat pump comprising:

[0249] (1) Refrigerant;

[0250] (2) A compressor for compressing the gaseous phase of the refrigerant;

[0251] (3) A condenser that transfers heat directly or indirectly from the gaseous refrigerant to a radiator at a temperature of about 90°C to about 130°C; and

[0252] (4) A direct expansion evaporator that transfers heat from a heat source at a temperature of about 30°C to about 90°C to the refrigerant in the liquid phase.

[0253] (5) The refrigerant comprises:

[0254] i. 81% to 89% by weight of HFO-1233zd(E);

[0255] ii. 4% to 15% by weight of HFO-1234ze(E); and

[0256] iii. 2% to 9% by weight of HFC-152a,

[0257] The refrigerant therein: (a) is 2L; and (b) has a COP of at least about 96% of the COP of R-1233zd(E) in the system.

[0258] For convenience, the heat pump mentioned in this paragraph is sometimes referred to as heat pump 1B.

[0259] The present invention includes a vapor compression heat pump that provides heat to a radiator containing a fluid or object to be heated, the vapor compression heat pump comprising:

[0260] (1) Refrigerant;

[0261] (2) A compressor for compressing the gaseous phase of the refrigerant;

[0262] (3) A condenser that transfers heat directly or indirectly from the gaseous refrigerant to a radiator at a temperature of about 90°C to about 130°C; and

[0263] (4) A direct expansion evaporator that transfers heat from a heat source at a temperature of about 30°C to about 90°C to the refrigerant in the liquid phase.

[0264] The refrigerant comprises:

[0265] i. 81% to 89% by weight of HFO-1233zd(E);

[0266] ii. 4% to 15% by weight of HFO-1234ze(E); and

[0267] iii. 2% to 8% by weight of HFC-152a,

[0268] The refrigerant: (a) is 2L; (b) has a capacity in the system that is at least about 120% of the capacity of R-1233zd(E) in the system; and (c) has a COP that is at least about 96% of the COP of R-1233zd(E) in the system.

[0269] For convenience, the heat pump mentioned in this paragraph is sometimes referred to as heat pump 1C. Attached Figure Description

[0270] Figure 1 This is a schematic diagram of an exemplary heat transfer system that can use the refrigerant of the present invention and can be used in the systems and methods of the present invention, including high-temperature heat pump systems and methods. Detailed Implementation

[0271] definition :

[0272] The phrase “coefficient of performance” (abbreviated as “COP” in this paper) is a universally accepted metric for refrigerant performance, particularly useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving refrigerant evaporation or condensation. In refrigeration engineering, the term represents the ratio of useful cooling, refrigeration, or heating capacity to the energy consumed by the compressor in compressing vapor, and thus indicates the ability of a given compressor to pump heat for a given volumetric flow rate of a heat transfer fluid, such as a refrigerant. In other words, for a given compressor, a refrigerant with a higher COP will provide more cooling or heating power. One approach to estimating the refrigerant COP under specific operating conditions is to start with the thermodynamic properties of the refrigerant and use standard refrigeration cycle analysis techniques (see, for example, RC Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, the full text of which is incorporated herein by reference).

[0273] The phrase “Global Warming Potential” (abbreviated as “GWP” in this paper) is used to allow for comparisons of the effects of different gases on global warming. It compares the heat captured by a given mass of a particular gas to the heat captured by a similar mass of carbon dioxide over a specific time period. The Intergovernmental Panel on Climate Change (IPCC) chose carbon dioxide as the reference gas, with a GWP of 1. The higher the GWP, the greater the warming effect of the given gas compared to CO2 over that time period. As used herein, the term GWP refers to the amount of heat captured by the gas as determined by the IPCC Fourth Assessment Report (2014). 1The GWP values ​​were measured using AR4 (referred to as AR4 in this document), but for components for which GWP values ​​were not measured in AR4 (such as R1233zd(E) and R1234ze(E)), the values ​​used were based on the fifth evaluation report.

[0274] 1 Myhre, G., D. Shindell, F.‐M. Bréon, W. Collins, J. Fuglestvedt, J.Huang, D. Koch, J.‐F. Lamarque, D. Lee, B. Mendoza, T. Nakajima, A. Robock, G.Stephens, T. Takemura, and H. Zhang, 2013: Anthropogenic and Natural Radiative Forcing.

[0275] In: Climate Change 2013: The Physical Science Basis.

[0276] Working Group 1's contribution to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change [Stocker, TF, D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen, J. Boschung, A. Nauels, Y. Xia, V. Bex and PM. Midgley (eds.)]. Cambridge University Press, Cambridge, United Kingdom

[0277] And New York, NY, USA.

[0278] https: / / www.ipcc.ch / pdf / assessmentreport / ar5 / wg1 / WG1AR5_Chapter08_FINAL.pdf (Pages 73-79)

[0279] As used herein, the term “non-flammable” refers to a compound or composition that is classified as Class 1 or 2L according to ASHRAE 34-2016 (which specifies the conditions and equipment) and using the current method ASTM E681-09 Appendix A1. Therefore, refrigerants not classified as Class 1 or 2L according to ASHRAE 34-2016 (which specifies the conditions and equipment) and using the current method ASTM E681-09 Appendix A1 will be considered flammable herein. ASTM Standard E-681-2009, “Standard Test Method for Flammability Concentration Limits of Chemicals (Vapor and Gas),” described in ASHRAE Standard 34-2016, “Refrigerant Nomenclature and Safety Classification,” and in ASHRAE Standard 34-2016 Appendix B1 (whichever is more current as of the date of this application), are incorporated herein by reference in their entirety.

[0280] As used herein, the phrase "acceptable toxicity" means that the composition is classified as "A" according to ASHRAE Standard 34-2016, "Nomenclature and Safety Classification of Refrigerants," and its description conforms to Annex B1 of ASHRAE Standard 34-2016 (as of the date of this application). A non-flammable substance with acceptable toxicity or a slightly flammable substance with acceptable toxicity will be classified as "A1" or "A2L" according to ASHRAE Standard 34-2016, and its description conforms to Annex B1 of ASHRAE Standard 34-2016 (as of the date of this application).

[0281] When used herein, the term "substitute" for a particular heat transfer composition or refrigerant of the present invention as a "substitute" for a particular existing refrigerant means the use of the specified composition of the present invention in heat transfer systems that have historically been used with that existing refrigerant. For example, when the refrigerant or heat transfer composition of the present invention is used in heat transfer systems (such as residential and commercial air conditioning systems, including rooftop systems, variable refrigerant flow (VRF) systems, and cooler systems) designed to date for use with R410A, the refrigerant of the present invention is a substitute for R410A in such systems.

[0282] The term "superheat" or simply "superheat" refers to the temperature rise of the refrigerant at the evaporator outlet above its saturated vapor temperature (or dew point temperature).

[0283] As used herein, the term "evaporator slip temperature" refers to the difference between the refrigerant saturation temperature at the evaporator inlet and the refrigerant dew point at the evaporator outlet, assuming the evaporator outlet pressure is the same as the inlet pressure. As used herein, the phrase "saturation temperature" refers to the temperature at which a liquid refrigerant boils into vapor at a given pressure.

[0284] As used herein, the term "condenser glide temperature" refers to the difference between the dew point temperature of the refrigerant at or near the condenser inlet and the saturation temperature of the refrigerant at or near the condenser outlet, assuming the pressure at the condenser outlet is the same as the pressure at the inlet. As used herein, the phrase "saturation temperature" refers to the temperature at which a liquid refrigerant boils into vapor at a given pressure.

[0285] As used herein, the terms “direct expansion evaporator” and “Dx evaporator” mean a heat exchanger that receives a non-azeotropic liquid refrigerant blend and produces unfractionated superheated vapors of the non-azeotropic refrigerant blend.

[0286] As used in this article, the term "flooded evaporator" refers to a heat exchanger that transfers heat to a boiling liquid refrigerant reservoir.

[0287] As used herein, the term “district heating” means a system or method for heating multiple adjacent residential spaces, such as residential spaces in a high-rise apartment building, using a single or series of shared heat source loops (such as a single or series of geothermal underground pipe loops).

[0288] As used in this article, the term "shallow geothermal source" refers to heat extracted from depths of 2 to 500 meters underground.

[0289] As used herein, the terms “1234ze”, “HFO-1234ze” and “R1234ze” each refer to 1,1,1,3-tetrafluoropropylene, with no restriction on the isomer form.

[0290] As used herein, the terms trans1234ze, 1234ze(E) and R-1234ze(E) each refer to trans-1,3,3,3-tetrafluoropropylene.

[0291] As used herein, the terms cis1234ze and 1234ze(Z) respectively refer to cis1,3,3,3-tetrafluoropropylene.

[0292] As used herein, the term 1233zd refers to 1-chloro-3,3,3-trifluoropropene, with no restriction on the isomer form.

[0293] As used herein, the terms trans-1233zd and 1233zd(E) respectively refer to trans-1-chloro-3,3,3-trifluoropropene.

[0294] As used herein, the terms “R-152a” and “HFC-152a” each refer to 1,1-difluoroethane.

[0295] As used herein, the terms “R-134a” and “HFC-134a” each refer to 1,1,1,2-tetrafluoroethane.

[0296] As used herein, the terms “high-temperature heat pump system” and “high-temperature heat pump” refer to a vapor compression system that can operate in a heating mode at a refrigerant condensation temperature of about 70°C or higher.

[0297] As used herein, references to defined groups, such as “refrigerants 1-5”, refer to each composition within that group, including cases where the definition number has a suffix. For example, a reference to refrigerants 1-2 includes a reference to each of refrigerants 1A, 1B, 1C, 2A, 2B, and 2C.

[0298] As used herein, the term “about” refers to a quantity expressed as a weight percentage, meaning that the amount of a component may vary by + / - 10 wt% on a relative weight basis. Thus, if a quantity is described as “about 10 wt%”, it is intended to cover a quantity of 10 wt% + / - 1 wt%; and if a quantity is described as “about 20 wt%”, it is intended to cover a quantity of 20 wt% + / - 2 wt%, and so on.

[0299] heat pump

[0300] A high-temperature heat pump (sometimes referred to herein as "HTHP" for convenience) includes a fluid loop in its basic configuration that utilizes a circulating refrigerant to draw or absorb heat from at least one heat storage tank at a relatively low temperature (sometimes referred to herein as a "heat source") (sometimes referred to herein as a "low-temperature heat source"), and then releases or transfers the heat to at least one second storage tank at a relatively high temperature (sometimes referred to herein as a "radiator") (sometimes referred to herein as a "high-temperature radiator" for convenience). In a preferred configuration, the low-temperature heat source is a sufficient heat source at a relatively low temperature, such as that available from low-temperature industrial waste heat, geothermal energy from the ground and / or groundwater, etc., and the high-temperature radiator is a fluid, such as hot water or steam or hot air, that is desired to be maintained in a relatively high temperature range.

[0301] The temperature of the cryogenic heat source used in conjunction with the refrigerant, system, and method of the present invention can vary over a wide range, but in a preferred embodiment, the temperature of the heat provided is about 5°C to about 90°C, or about 25°C to about 90°C, or about 40°C to about 90°C, or about 50°C to about 90°C, or about 40°C to about 80°C, or about 30°C to about 80°C, or about 5°C to about 20°C, or about 5°C to about 15°C. Examples of cryogenic heat sources that can be used in conjunction with the present invention include low-grade industrial heat, air from the environment, water from the environment, brine, and, in the case of geothermal energy, heat from the earth (including groundwater).

[0302] Regarding high-temperature radiators that can absorb heat according to the invention, it is believed that the invention can be used in a variety of such radiators, including hot air, hot water (i.e., hot water at a temperature of at least about 55°C), and steam.

[0303] Figure 1 This is a generalized schematic diagram of a basic high-temperature heat pump device that includes and operates using the refrigerant of the present invention (including each of refrigerants 1-5).

[0304] Figure 1 The HTHP 100 according to the invention is illustrated in block diagram form. The HTHP includes an evaporator 50 that receives heat from a low-temperature heat source (schematically represented by ellipse 60), including undergoing a phase change from liquid to gaseous state while absorbing heat from the low-temperature heat source. However, it should be understood that a certain degree of sensible heat may also be transferred from the low-temperature heat source to the refrigerant of the invention (including each of refrigerants 1-5). The gaseous refrigerant leaving the evaporator 50 via line 51 is introduced to the suction side of a compressor 10, which performs work on the refrigerant and increases the temperature and pressure of the refrigerant vapor. This high-temperature vapor from the compressor 10 is conveyed via line 11 to a condenser 20, in which the refrigerant of the invention (including each of refrigerants 1-5) supplies heat at a relatively high temperature to a high-temperature radiator, schematically represented by a fan 30 (but not limited thereto). Subsequently, the condensing refrigerant of the present invention is delivered via line 21 to a pressure reducing device (such as expansion valve 40), where the pressure of the liquid refrigerant is reduced, thereby producing a relatively low-temperature liquid refrigerant, which is then introduced via line 21 into evaporator 50, and the cycle begins again.

[0305] The specific type of equipment used in the heat pump system of this invention can vary considerably within the scope of this invention. For example, the compressor can be centrifugal, screw, or positive displacement type.

[0306] Regarding heat exchangers 50 and 20, the applicant notes that the preferred refrigerants of the present invention have condenser glide temperatures of about 4°C to less than about 15°C, and for the use of the refrigerants of the present invention (including each of refrigerants 1-5), counter-flow and / or cross-flow heat exchangers are preferably used for the evaporator and condenser. The applicant recognizes that the use of such heat exchangers in the systems and methods described herein advantageously achieves glide temperature matching with the radiator or heat source. Furthermore, heat exchangers that do not allow fractionation during evaporation or condensation are preferred; therefore, flooded heat exchangers are not preferred on the refrigerant side, but rather brazed plate heat exchangers and similar heat exchangers that do not allow refrigerant fractionation are preferred. For example, if a shell-and-tube heat exchanger is used for the condenser or evaporator, it is highly preferred that the refrigerant flows on the tube side of the heat exchanger rather than the shell side. Therefore, the heat exchangers 20 and 50 in the system and method of the present invention are preferably of the dry expansion or direct expansion type (rather than the flooded type), and in the case of the evaporator 50, vapor with a superheat of at least about 5°C is generated, while in the case of the condenser 20, liquid with a supercool of at least about 5°C is generated.

[0307] The type of expansion device used can vary. The expansion device can be an expansion valve, which can be electronic or thermostatic, depending on specific design requirements. This description does not limit any possible additional variations in specific equipment, nor does it limit anything not specified herein. Figure 1 The use of additional components shown (such as intake line heat exchangers, steam ejectors, etc.)

[0308] Table 1 below identifies the preferred high-temperature heat pump method of the present invention (identified by the HTHP method number in column 1) using the refrigerant of the present invention (identified by the number corresponding to the refrigerant number defined above in column 2), using a direct expansion evaporator, and having the operating parameters specified in the table.

[0309] High-temperature heat pump method conditions

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322] The applicant has discovered that the refrigerant compositions of the present invention (including each of refrigerants 1-5) can meet the requirements of HTHP systems for excellent performance in terms of environmental impact in a superior and unexpected manner, while providing other important performance characteristics, such as, but not limited to, high capacity and high efficiency, Class 1 or 2L flammability, and acceptable toxicity.

[0323] In a preferred embodiment, the compositions of the present invention (including each of refrigerants 1-5) provide alternatives and / or substitutes for the working fluids currently used in high-temperature heat pump applications, particularly and preferably as alternatives and / or substitutes for CFC-114 and R-1233zd(E).

[0324] In a preferred embodiment, each of the methods of the present invention (including heat transfer method 1 and HTHP methods 1-64) uses the refrigerant of the present invention (including each of refrigerants 1-5), wherein the critical temperature of the refrigerant is higher than the temperature of the high-temperature radiator.

[0325] In a preferred embodiment, each of the methods of the present invention (including heat transfer method 1 and HTHP methods 1-64) uses the refrigerant of the present invention (including each of refrigerants 1-5), wherein the critical temperature of the refrigerant is higher than the temperature of the high-temperature radiator, and wherein the critical temperature of the refrigerant is about 160°C or lower.

[0326] heat transfer composition

[0327] The compositions of the present invention are those compositions comprising the refrigerants of the present invention (including each of refrigerants 1-5). The applicant has found that the use of the components of the present invention within the stated scope is essential for achieving the important but difficult-to-achieve combination of performance characteristics exhibited by the compositions of the present invention, particularly in preferred HTHP systems and methods.

[0328] The compositions of the present invention are those compositions containing the refrigerants of the present invention (including each of refrigerants 1-5) with a critical temperature of 160°C or lower.

[0329] In addition to the refrigerants of the present invention, the heat transfer compositions of the present invention may also contain other components for the purpose of enhancing or providing certain functions to the heat transfer composition, or in some cases reducing the cost of the composition. For example, heat transfer compositions containing the refrigerants of the present invention (including refrigerants 1-5), when used in preferred vapor compression HTHP systems, typically also contain one or more lubricants. The amount of lubricant in the heat transfer composition can vary even within an HTHP system, typically ranging from as little as 0.1% by weight to as much as about 20% by weight. For a given system, the percentage of the relative amount of lubricant present in the system relative to the total amount of lubricant and refrigerant in the system can also vary considerably, such as from about 30% by weight to about 50% by weight.

[0330] The applicant has discovered that, in certain embodiments, polyol esters (POE) and polyvinyl ethers (PVE), PAG oils, silicone oils, and lubricants previously used in refrigeration machinery with hydrofluorocarbon (HFC) refrigerants can be advantageously used in the heat transfer compositions of the present invention, as well as in HTHP systems and methods. Commercially available esters include neopentyl glycol dinonanoate, obtained under the names Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark). Other available esters include phosphate esters, diesters, and fluorinated esters. Preferred lubricants include POE and PVE. Of course, different mixtures of different types of lubricants can be used.

[0331] Heat transfer methods and systems

[0332] Therefore, the methods, systems, and compositions of the present invention are suitable for use in conjunction with a variety of heat transfer systems, and particularly HTHP systems. Preferred high-temperature heat pump systems include those in which the refrigerant of the present invention condenses at temperatures above 90°C and even more preferably above about 100°C. Examples of such systems include, but are not limited to, systems used industrially as boiler replacements, district heating heat pumps (including shallow geothermal district heating systems), and commercial heat pumps. Examples include water-to-water heat pumps for shopping malls. They can also be used in the oil or mining industries where heat sources are readily available. Compressors are typically centrifugal and screw compressors, but other types, such as scroll compressors, can also be used. Heat exchangers can be direct expansion shell-and-tube (preferably with refrigerant on the tube side) and brazed plate heat exchangers. In a preferred embodiment, the heat pump system of the present invention may also include an economizer with vapor injection enthalpy enhancement and a suction line heat exchanger.

[0333] As described above, the present invention offers significant advantages when combined with heat pump systems, including particularly and preferred high-temperature heat pump systems. Non-limiting examples of such systems are provided in the embodiments below. The following embodiments provide typical conditions and parameters for certain high-temperature heat pumps but do not limit the broad scope of operation of the systems and methods of the present invention. Therefore, the conditions used in the examples are generally representative but should not be considered as limitations on the invention, as those skilled in the art will understand that they can vary based on one or more of a variety of factors, including but not limited to environmental conditions, intended application, time of year, etc. Such examples also do not necessarily limit the definition of the term "high-temperature heat pump system".

[0334] It is conceivable that, in some embodiments, the present invention provides a method for reducing the cost of providing high-temperature heat pumps by replacing at least a majority of the heat transfer fluids (including refrigerants and optional lubricants) in existing systems with the refrigerants of the present invention (including each of refrigerants 1-5). One advantage of the replacement method of the present invention is that, compared to previously used refrigerants (particularly including 1233zd(E)), a compressor with a significantly reduced displacement can be used in the same application, thereby achieving a reduction in system cost. In some preferred embodiments, the compressor displacement is about 90% or less of the displacement required to achieve the same capacity in the system using 1233zd(E), preferably 85% or less of the displacement required to achieve the same capacity in the system using 1233zd(E), and even more preferably at least about 80% or less of the displacement required to achieve the same capacity in the system using 1233zd(E).

[0335] Example

[0336] The following embodiments are provided to illustrate the present invention, but do not limit the scope of the invention.

[0337] Comparative Example 1

[0338] Under the following operating conditions, a high-temperature heat pump (HTHP) system is operated using a refrigerant consisting of 1233zd(E):

[0339] 1. Radiator temperature = 100℃

[0340] 2. Heat source temperature = 25℃

[0341] 3. Refrigerant condensation temperature = 130℃

[0342] 4. Condenser subcooling = 5.0℃

[0343] 5. Refrigerant evaporation temperature = 60℃

[0344] 6. Evaporator superheat = 5.0℃

[0345] 7. Isoentropy efficiency = 65%

[0346] 8. Volumetric efficiency = 95%

[0347] Run the HTHP system and determine the system's coefficient of performance (COP) and capacity (based on pressure drops and heat transfer in the connecting lines (suction and liquid lines) considered negligible, and heat leakage through the compressor housing being ignored). COP is a universally accepted metric for refrigerant performance, particularly useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving refrigerant evaporation or condensation. In refrigeration engineering, the term represents the ratio of the usable cooling capacity to the energy exerted by the compressor when compressing vapor. The cooling capacity of a refrigerant represents the amount of cooling or heating it provides and provides some measure of the compressor's ability to pump heat under given refrigerant volume flow rate and other operating conditions. In other words, for a given compressor and a set of operating conditions, a refrigerant with a higher cooling capacity will provide more cooling or heating power. One way to estimate the COP capacity of a refrigerant under specific operating conditions is to start from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, RC Downing, FLUOROCARBONREFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988).

[0348] For comparison, the COP and capacity of the HTHP using a refrigerant composed of 1233zd(E) and operated according to Comparative Example 1 were set as baselines and referred to in the following examples as the baseline having a COP and volumetric capacity value of 100%.

[0349] Examples 1A1-1A12

[0350] According to the present invention, twelve refrigerants are formed according to blends identified as A1-A12 in Table Ex1A below, and each refrigerant is found to have a combustion rate (“BV”) and a global warming potential (“GWP”) determined according to the above definition and reported in the table below:

[0351] Table Ex1A

[0352]

[0353] As can be seen from the table above, the applicant has found that each of the refrigerants A1-A13 not only has a GWP of less than 15, but also a combustion rate of 10 cm / s (3.94 in / s) or lower, and is therefore a 2L class refrigerant.

[0354] Each of refrigerants A1-A13 was then used in the same high-temperature heat pump as described in Comparative Example 1 and under the same operating conditions. The following results regarding COP and capacity were determined for the above conditions and are reported in Table Ex1B below:

[0355] Table Ex1B

[0356]

[0357] As can be seen from the table above, each of the refrigerants A1-A12 of the present invention can unexpectedly achieve a GWP of less than 15, a flammability classification of 2L, and a COP of more than 96% when operating in HTHP, and a capacity of 120% or higher of the 1233z(E) capacity under the same specified operating conditions in the same HTHP system. Preferred compositions are A5, A7, A9, and A11 because each of these refrigerants has a combustion rate of less than 10 cm / s and simultaneously achieves a COP of more than 96% or a capacity of 120% or higher. Particularly preferred compositions are A7, A9, and A11 because each of these refrigerants has a combustion rate of less than 10 cm / s and simultaneously achieves a COP of more than 96% and a capacity of more than 120%. Refrigerant composition A6 is preferred because it can achieve a combustion rate of less than 8 cm / s while simultaneously achieving a capacity of more than 122%; and refrigerant composition A7 is preferred because it can achieve a combustion rate of less than 8 cm / s while simultaneously achieving a COP of more than 96%.

[0358] Examples 2A1-2A3

[0359] The HTHP system of Comparative Example 1 was operated in the same manner as that of Comparative Example 1, except that it used the three refrigerant blends indicated in Table Ex2A below.

[0360] Table Ex2

[0361]

[0362] As shown in the results of Example 2, the applicant unexpectedly found that while refrigerants containing 2% by weight or less of HFC-152a could achieve a COP of 96%, the tested refrigerants were found to have failed to achieve a preferred capacity of 120% or higher.

[0363] Examples 3A, 3B and 3C

[0364] The HTHP system of Comparative Example 1 was operated in the same manner as in Comparative Example 1, except that it used the refrigerant blends indicated in Table Ex3 below. Flammability and performance tests were performed on these refrigerants, and the results are reported in Table Ex3 below.

[0365] Table Ex3

[0366]

[0367] As shown in the results of Examples 3A-3C, the applicant unexpectedly discovered that although each of the refrigerant blends Ex3A, Ex3B and Ex3C could achieve the desired COP and capacity performance of the optimal refrigerant of the present invention, the applicant found that none of these refrigerants could be classified as 2L class because each of them had a combustion rate higher than 10.

[0368] Comparative Example 2—R-1233ZD(E) in industrial high-temperature environments where the heat source temperature is above 60°C and the refrigerant condensation temperature is 130°C Applications of heat pumps

[0369] Provides a feature such as Figure 1 The industrial heat pump system shown has a basic structure and is used to provide heat for industrial processes in the form of direct heating, heating of auxiliary fluids, or steam generation. The system uses waste heat from another process or waste heat at temperatures above 60°C as the heat source for its evaporator and provides heat to a radiator at temperatures of approximately 90°C–135°C. The system operates using R-1233zd(E) as the refrigerant under the following conditions:

[0370] 1. Refrigerant condensation temperature = 130℃

[0371] 2. Condenser subcooling = 5℃

[0372] 3. Refrigerant evaporation temperature = 60℃

[0373] 4. Evaporator superheat = 5℃

[0374] 5. Isoentropy efficiency = 65%

[0375] 6. Volumetric efficiency = 100%

[0376] The system performance under these conditions was used as a baseline for the following Examples 4A and 4B (i.e., the values ​​of heating capacity, compressor pressure ratio, compressor displacement and discharge pressure were set to 100% baseline for comparison purposes, and the discharge temperature difference was reported relative to the discharge temperature of this Comparative Example 2).

[0377] Examples 4A and 4B: Refrigerant A14 of the present invention containing R-152a, R-11233zd(E) and R-1234ze(E) A15 is used in industrial high-temperature heat pumps with a heat source temperature of 60°C and a refrigerant condensation temperature of 130°C.

[0378] Comparative Example 2 was repeated, except that refrigerants A14 and A15, as identified in Table E4A below, were used to produce the results reported in Table E4B. These results are listed together with those from Comparative Example 1 for comparison:

[0379] Table E4A

[0380]

[0381] Table E4B

[0382]

[0383] As can be seen from the results in Tables E4A and E4B, the refrigerants A14 and A15 of the present invention provide 20%-23% higher heating capacity than R-1233zd(E), while exhibiting minimal efficiency loss of only 3%-4%. This allows for the use of compressor displacements of only about 80%-85% of those required in Comparative Example 2, thus providing the possibility of significant savings in system costs and / or its ongoing maintenance expenses. The discharge pressure and pressure ratio of both refrigerants also show a slight increase, which may allow for the use of the same compressor design as R-1233zd(E). The discharge pressure is 26%-30% higher than R-1233zd(E); however, since R-1233zd(E) is already a low-pressure refrigerant, and the boiling points of A14 and A15 are much lower than those of R-1233zd(E), the refrigerants of the present invention will operate at pressures above atmospheric pressure at these temperatures.

[0384] Comparative Example 3—r-1233ZD(E) in industrial high-temperature environments where the heat source temperature is above 30°C and the refrigerant condensation temperature is 130°C Applications of heat pumps

[0385] Comparative Example 2 was repeated, except that the heat source temperature was approximately 30 °C, and the following system conditions were changed as follows:

[0386] a. Refrigerant evaporation temperature = 30℃

[0387] b. Isoentropy efficiency = 60%

[0388] The system performance under these conditions was used as a baseline for the following Examples 5A and 5B (i.e., the values ​​of heating capacity, compressor pressure ratio, compressor displacement and discharge pressure were set to 100% baseline for comparison purposes, and the discharge temperature difference was reported relative to the discharge temperature of this Comparative Example 3).

[0389] Examples 5A-5B: Refrigerants containing R-152a, R-1233zd(E) and R-1234ze(E) are used for high heat source temperatures. Applications of industrial high-temperature heat pumps with a refrigerant condensation temperature of 130°C and a temperature of 30°C.

[0390] Comparative Example 3 was repeated, except that the refrigerant identified in Table E4A above was used to produce the results reported in Table E5 below. These results are listed together with the results from Comparative Example 3 for comparison:

[0391] Table E5

[0392]

[0393] As can be seen from the results in Table E5, the refrigerants A14 and A15 of the present invention provide 20%-23% higher heating capacity than R-1233zd(E), while exhibiting minimal efficiency loss of only 3%. This allows for the use of compressor displacements of only about 80%-85% of those required in Comparative Example 2, thus providing the possibility of significant savings in system costs and / or its ongoing maintenance expenses. The discharge pressure and pressure ratio of both refrigerants also show a slight increase, which may allow for the use of the same compressor design as R-1233zd(E). The discharge pressure is 26%-30% higher than R-1233zd(E); however, since R-1233zd(E) is already a low-pressure refrigerant, and the boiling points of A14 and A15 are much lower than those of R-1233zd(E), the refrigerants of the present invention will operate at pressures above atmospheric pressure at these temperatures.

[0394] Comparative Example 4—R-1233ZD(E) in industrial high-temperature environments where the heat source temperature is above 60°C and the refrigerant condensation temperature is 90°C Applications of heat pumps

[0395] Provides a feature such as Figure 1 The industrial heat pump system shown has a basic structure and is used to provide heat for industrial processes in the form of direct heating, heating auxiliary fluids, or generating steam. The system uses waste heat from another process or waste heat at temperatures above 60°C as the heat source for its evaporator. The system operates using R-1233zd(E) as the refrigerant under the following conditions:

[0396] a. Refrigerant condensation temperature = 90℃

[0397] b. Condenser subcooling = 5℃

[0398] c. Refrigerant evaporation temperature = 60℃

[0399] d. Evaporator superheat = 5℃

[0400] e. Isoentropy efficiency = 70%

[0401] f. Volumetric efficiency = 100%

[0402] The system performance under these conditions was used as a baseline for the following Examples 6A and 6B (i.e., the values ​​of heating capacity, compressor pressure ratio, compressor displacement and discharge pressure were set to 100% baseline for comparison purposes, and the discharge temperature difference was reported relative to the discharge temperature of this Comparative Example 4).

[0403] Examples 6A and 6B: Refrigerant A13 of the present invention containing R-152a, R-11233zd(E) and R-1234ze(E) A14 is used in industrial high-temperature heat pumps with a heat source temperature of 60°C and a refrigerant condensation temperature of 90°C.

[0404] Comparative Example 4 was repeated, except that refrigerants A14 and A15, identified in Table E4A above, were used to produce the results reported in Table E6 below. These results are listed together with those from Comparative Example 4 for comparison purposes:

[0405] Table E6

[0406]

[0407] As can be seen from the results in Table E6, the refrigerants A14 and A15 of the present invention provide 29%-33% higher heating capacity than R-1233zd(E), while exhibiting minimal efficiency loss of only 1%. This allows for the use of compressor displacements of only about 75%-80% of those required in Comparative Example 4, thus providing the possibility of significant savings in system costs and / or its ongoing maintenance expenses. The discharge pressure and pressure ratio of both refrigerants also show a slight increase, which may allow for the use of the same compressor design as R-1233zd(E). The discharge pressure is 30%-35% higher than R-1233zd(E); however, since R-1233zd(E) is already a low-pressure refrigerant, and the boiling points of A14 and A15 are much lower than those of R-1233zd(E), the refrigerants of the present invention will operate at pressures above atmospheric pressure at these temperatures.

[0408] Comparative Example 5—R-1233ZD(E) in industrial high-temperature environments where the heat source temperature is above 30°C and the refrigerant condensation temperature is 90°C Applications of heat pumps

[0409] Comparative Example 4 is repeated, except that the heat source temperature is approximately 30°C, and the following system conditions are changed as follows:

[0410] a. Refrigerant evaporation temperature = 30℃

[0411] b. Isoentropy efficiency = 65%

[0412] The system performance under these conditions was used as a baseline for the following Examples 7A and 7B (i.e., the values ​​of heating capacity, compressor pressure ratio, compressor displacement and discharge pressure were set to 100% baseline for comparison purposes, and the discharge temperature difference was reported relative to the discharge temperature of this Comparative Example 5).

[0413] Examples 7A-7B: Refrigerants containing R-152a, R-11233zd(E) and R-1234ze(E) are used for heat source temperature Applications of industrial high-temperature heat pumps with temperatures above 30°C and refrigerant condensation temperatures of 90°C

[0414] Comparative Example 5 was repeated, except that the refrigerant identified in Table E4A above was used to produce the results reported in Table E7 below. These results are listed together with the results from Comparative Example 5 for comparison:

[0415] Table E7

[0416]

[0417] As can be seen from the results in Table E7, the refrigerants A14 and A15 of the present invention provide 28%-32% higher heating capacity than R-1233zd(E), while exhibiting minimal efficiency loss of only 1%. This allows for the use of compressor displacements of only about 80%-85% of those required in Comparative Example 2, thus providing the possibility of significant savings in system costs and / or its ongoing maintenance expenses. The discharge pressure and pressure ratio of both refrigerants also show a slight increase, which may allow for the use of the same compressor design as R-1233zd(E). The discharge pressure is 30%-35% higher than R-1233zd(E); however, since R-1233zd(E) is already a low-pressure refrigerant, and the boiling points of A14 and A15 are much lower than those of R-1233zd(E), the refrigerants of the present invention will operate at pressures above atmospheric pressure at these temperatures.

[0418] Comparative Example 6: Refrigerant R-1234ze(E) for comfort cooling or cooler applications

[0419] Provides a feature such as Figure 1 The illustrated basic structure of the cooler system is used to provide cooling water for comfort cooling. The system operates using R-1234ze(E) as the refrigerant under the following conditions:

[0420] 1. Refrigerant condensation temperature = 45℃

[0421] 2. Condenser subcooling = 5℃

[0422] 3. Refrigerant evaporation temperature = 10℃

[0423] 4. Evaporator superheat = 5℃

[0424] 5. Isoentropy efficiency = 75%

[0425] 6. Volumetric efficiency = 100%

[0426] The system performance under these conditions was used as a baseline for Examples 8A and 8B (i.e., the values ​​of cooling capacity, compressor pressure ratio, and exhaust pressure were set to 100% baseline for comparison purposes, and the exhaust temperature difference was reported relative to the exhaust temperature of this example).

[0427] Examples 8A-8B: Refrigerants containing R-152a, R-1233zd(E) and R-1234ze(E) for comfort cooling or Applications of refrigerants with a condensation temperature of 45℃ and an evaporation temperature of 10℃.

[0428] Comparative Example 6 was repeated, except that the refrigerant identified in Table E4A above was used to produce the results reported in Table E8 below. These results are listed together with the results from Comparative Example 6 for comparison:

[0429] Table E7

[0430]

[0431] As can be seen from the results in Table E8, the heating capacity provided by refrigerants A14 and A15 of the present invention is only 42%-44% of that of R-1234ze(E), but at the same time, the efficiency is 4%-5% higher than that of R-1234ze(E). When efficiency takes precedence over capacity, the use of refrigerants A14 and A15 of the present invention will be preferred in this application.

Claims

1. A refrigerant comprising, based on the total amount of all refrigerants, at a relative concentration of at least about 95% of the following three components: (1) HFO-1233zd(E) of about 83% to about 89% by weight; (2) 4.6 wt% to approximately 15 wt% of HFO-1234ze(E); and (3) Approximately 2% to 7.4% by weight of HFC-152a.

2. The refrigerant according to claim 1, wherein the refrigerant is substantially composed of the following components: (1) HFO-1233zd(E) of about 83% to about 89% by weight; (2) 4.6 wt% to approximately 15 wt% of HFO-1234ze(E); and (3) Approximately 2% to 7.4% by weight of HFC-152a.

3. The refrigerant according to claim 2, wherein the refrigerant is composed of the HFO-1233zd(E), the HFO-1234ze(E), and the HFC-152a.

4. The refrigerant of claim 1, wherein the refrigerant has a GWP of 10 or less.

5. The refrigerant according to claim 1, wherein the refrigerant has a critical temperature of 150°C or higher.

6. The refrigerant according to claim 1, wherein the refrigerant is substantially composed of the following three components in relative concentrations: (1) 83.2 wt% + / - 2 wt% HFO-1233zd(E); (2) 11.8 wt% + / - 1 wt% HFO-1234ze(E); and (3) 5% by weight + / - 1% by weight of HFC-152a.

7. A method for generating heat in a high-temperature heat pump, the method comprising compressing and evaporating the refrigerant according to claim 1 in a direct expansion evaporator.

8. The method of claim 7, wherein the volumetric volume of the refrigerant in the system is at least about 120% of the volumetric volume of R-1233zd(E) in the system, and wherein the COP of the refrigerant in the system is at least 96% of the COP of R-1233zd(E) in the system.

9. A method for heating a radiator containing a fluid or object to be heated, the method comprising: a. Providing a vapor compression refrigeration system, the vapor compression refrigeration system comprising a compressor for compressing a gaseous refrigerant, a condenser for transferring heat from the gaseous refrigerant to a radiator at a temperature of about 40°C or higher, and a direct expansion evaporator for transferring heat from a heat source at a temperature of about 80°C or lower to the liquid phase of the refrigerant, wherein the refrigerant comprises: at least about 95% by weight of the following three components in relative concentrations based on the total amount of all refrigerants: i. Approximately 83% to approximately 89% by weight of HFO-1233zd(E); ii. HFO-1234ze(E) of about 4 wt% to about 15 wt%; and iii. about 2% to about 8% by weight of HFC-152a, wherein the refrigerant is 2L; and b. Evaporating the refrigerant in the direct expansion evaporator, wherein the volumetric volume of the refrigerant in the system is at least about 120% of the volumetric volumetric volume of R-1233zd(E) in the system, and wherein the COP of the refrigerant in the system is at least 96% of the COP of R-1233zd(E) in the system.

10. A method for providing at least about 1 megawatt (1 MW) of district heating shared by multiple residential spaces or for one or more fluid flows in an industrial process, the method comprising: (1) A vapor compression refrigeration system comprising: (i) one or more scroll, screw, or centrifugal compressors receiving refrigerant vapor from one or more direct expansion evaporators; (2) one or more condensers receiving compressed refrigerant vapor from the one or more compressors; and (3) generating condensed liquid refrigerant for supply to one or more expanders, the one or more expanders generating liquid refrigerant for supply to the one or more direct expansion evaporators; (2) Providing a heat source that directly or indirectly evaporates the liquid refrigerant in the one or more direct expansion evaporators. (3) Providing a radiator that directly or indirectly condenses the vapor refrigerant in the condenser, wherein when the system is district heating, the radiator includes air and / or water circulating in each of the plurality of residences, wherein at least one or more compressors are not located in the residences, wherein the radiator includes air and / or water circulating at a temperature of about 40°C to about 130°C (preferably about 60°C to about 130°C), and wherein the refrigerant comprises: Based on the total amount of all refrigerants, the following three components shall have a relative concentration of at least approximately 95% by weight: (a) HFO-1233zd(E) of about 83% to about 89% by weight; (b) HFO-1234ze(E) of about 4 wt% to about 15 wt%; and (c) about 2% to about 8% by weight of HFC-152a, wherein the refrigerant is 2L; (4) Evaporate the refrigerant in the evaporator, wherein the refrigerant has an evaporator glide temperature greater than about 3°C ​​and less than 15°C.

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