CN111925775A

CN111925775A - Low GWP fluids for high temperature heat pump applications

Info

Publication number: CN111925775A
Application number: CN202010818546.3A
Authority: CN
Inventors: S·F·亚纳莫塔; M·W·斯帕茨; A·塞蒂
Original assignee: Honeywell International Inc
Current assignee: Honeywell International Inc
Priority date: 2013-03-14
Filing date: 2014-03-14
Publication date: 2020-11-13
Also published as: CN104046331A

Abstract

The present application relates to low GWP fluids for high temperature heat pump applications. The present invention relates in part to heat transfer compositions and related systems and methods, the compositions comprising: a first composition selected from the group consisting of HFO-1233zd, HFC-245fa, and combinations of these; optionally also comprising: a second composition selected from the group consisting of HFO-1234ze, HFC-134a, and combinations of these.

Description

Low GWP fluids for high temperature heat pump applications

Cross Reference to Related Applications

This application is a divisional application of an invention patent application having an application date of 2014, 14/3, application number 201410094258.2, entitled "low GWP fluid for high temperature heat pump applications". Priority of U.S. provisional application serial No. 61/783,787, filed on 3, 14, 2013, the entire contents of which are incorporated herein by reference.

Technical Field

The present invention relates to compositions, methods and systems for heat transfer applications which are particularly beneficial in medium or high temperature heat pump applications, particularly in heat transfer and/or refrigerant compositions, replacing refrigerant CFC-114 for heating and cooling applications, and to retrofit medium or high temperature heat pump systems. The present invention also includes new systems designed for such new heat transfer and/or refrigerant fluids.

Background

High temperature heat pumps have been used to upgrade low grade heat energy, e.g., derived from air, soil, surface or ground water, geothermal energy, solar energy, and industrial waste heat and process streams, to high grade heat energy through thermodynamic cycles. Heat pump systems have compressors that transfer energy to a low grade heat stream. Heat pump systems utilize a working fluid, i.e., a refrigerant, to facilitate the generation and conduction of heat through a thermodynamic cycle. Heat pump systems have been used for heating and cooling purposes.

Historically, chlorofluorocarbons, such as trichlorofluoromethane (CFC-11), 1, 2-trichlorotrifluoroethane (CFC-113) and 1, 2-dichloro-1, 1,2, 2-tetrafluoroethane (CFC-114), have been used as working fluids for heat pumps, refrigerators and other heating/cooling devices and machinery. Such working fluids have largely been eliminated due to their elevated levels of Ozone Depletion Potential (ODP) and Global Warming Potential (GWP).

In heating and cooling applications, chlorofluorocarbons have been replaced by other working fluids exhibiting lower ODP and GWP, such as hydrochlorofluorocarbons and hydrofluorocarbons. Such working fluids include chlorodifluoromethane (R-22), R-407C, R-410A, R-245fa, and 1,1,1, 2-tetrafluoroethane (R-134 a). R-407C is a blend of difluoromethane (R-32), 2-chloro-1, 1,1, 2-tetrafluoroethane (R-124), R-134a, 1-chloro-1, 1-difluoroethane (R142 b). R-410A is a blend of R-22 and pentafluoroethane (R-125).

At moderate to high heating temperatures, this alternative working fluid does not provide the same operating range that chlorofluorocarbon working fluids can provide. Of particular interest are medium-high temperatures, i.e. condensation temperatures of 70 ℃ to 100 ℃, and high temperatures, i.e. condensation temperatures above 100 ℃. For example, the maximum condensation temperature is 65 ℃ for R22, R407c, and R410A. For R134a, the highest achievable condensation temperature is 73 ℃. When the condensation temperature exceeds this limit, the cycle performance deteriorates, and the risk of malfunction increases due to excessive discharge pressure and temperature (discharge from the compressor).

It would be desirable to have a working fluid that exhibits low ODP and GWP and provides excellent thermal performance in the medium and high temperature range, particularly in the medium-high condensation temperature range of 70 ℃ to 100 ℃, or in the high condensation temperature range above 100 ℃. It is further desirable to have a working fluid that can be used in heat pump systems and other heating/cooling machines, such as air conditioning systems and chillers.

Disclosure of Invention

In certain aspects, the present invention relates to compositions, methods, uses, and systems comprising or using a multi-component mixture comprising a heat transfer composition, wherein the heat transfer composition comprises: (1) from about 60% to less than about 100% by weight of a first composition selected from the group consisting of HFO-1233zd, HFC-245fa, and combinations of these; and (2) from greater than about 0% to about 40% by weight of a second composition selected from the group consisting of HFO-1234ze, HFC-134a, and combinations of these; with the proviso that the amounts of components (a) and (b) are effective to improve one or more of the slip properties of the composition, the capacity of the composition and the efficiency of the composition.

In certain non-limiting aspects, the first component comprises HFO-1233zd, and in certain embodiments, HFO-1233zd may comprise, consist essentially of, or consist of HFO-1233zd (E). In certain aspects of this embodiment, HFO-1233zd may be provided together with HFO-1234 ze. To this end, in certain embodiments, such compositions comprise from about 60 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 40 wt.% HFO-1234 ze. In a further aspect, such compositions comprise from about 65 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 35 wt.% HFO-1234 ze. In a further aspect, such compositions comprise from about 70 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 30 wt.% HFO-1234 ze. In a further aspect, such compositions comprise from about 85 wt.% to less than about 100 wt.% HFO-1233zd and from greater than about 0 wt.% to about 15 wt.% HFO-1234 ze.

In a further aspect of the present invention, HFO-1233zd may be provided with HFC-134 a. To this end, in certain embodiments, such compositions comprise from about 60 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 40 wt.% HFC-134 a. In a further aspect, such compositions comprise from about 65 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 35 wt.% HFC-134 a. In a further aspect, such compositions comprise from about 70 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 30 wt.% HFC-134 a. In a further aspect, such compositions comprise from about 85 wt.% to less than about 100 wt.% HFO-1233zd and from greater than about 0 wt.% to about 15 wt.% HFC-134 a.

In certain non-limiting aspects, the first component comprises HFC-245fa, which may be provided with HFO-1234 ze. In certain embodiments, such compositions may comprise from about 60 wt.% to about 87 wt.% HFC-245fa, and from about 13 wt.% to about 40 wt.% HFO-1234 ze. In a further aspect, such compositions comprise from about 60 wt.% to about 85 wt.% HFC-245fa, and from about 15 wt.% to about 40 wt.% HFO-1234 ze. In a further aspect, the composition comprises from about 70 wt.% to about 85 wt.% HFC-245fa, and from about 15 wt.% to about 30 wt.% HFO-1234 ze. In a further aspect, the composition comprises from about 85 wt.% to less than about 100 wt.% HFC-245fa, and from greater than about 0 wt.% to about 15 wt.% HFO-1234 ze.

In a further aspect of the invention, HFC-245fa may be provided with HFC-134 a. To this end, in certain embodiments, such compositions comprise from about 60 wt.% to about 87 wt.% HFC-245fa, and from about 13 wt.% to about 40 wt.% HFC-134 a. In a further aspect, the composition comprises from about 60 wt.% to about 85 wt.% HFC-245fa, and from about 15 wt.% to about 40 wt.% HFC-134 a. In a further aspect, the composition comprises from about 70 wt.% to about 85 wt.% HFC-245fa, and from about 15 wt.% to about 30 wt.% HFC-134 a. In a further aspect, the composition comprises from about 85 wt.% to less than about 100 wt.% HFC-245fa, and from greater than about 0 wt.% to about 15 wt.% HFC-134 a.

The term HFO-1234ze as used herein generally refers to 1,1,1, 3-tetrafluoropropene, regardless of whether it is the cis or trans form. As used herein, the terms "cis HFO-1234 ze" (also known as HFO-1234ze (Z)) and "trans HFO-1234 ze" (also known as HFO-1234ze (E)) describe the cis and trans forms of 1,1,1, 3-tetrafluoropropene, respectively. Accordingly, the term "HFO-1234 ze" includes within its scope cis HFO-1234ze, transHFO-1234 ze, and all combinations and mixtures of these. In certain preferred aspects, HFO-1234ze comprises, consists essentially of, or consists of transHFO-1234 ze (i.e., HFO-1234zd (E)).

The term HFO-1233zd is used herein to refer generally to 1-chloro-3, 3, 3-trifluoropropene, regardless of whether it is cis-or trans-form. As used herein, the terms "cis HFO-1233 zd" (also known as HFO-1233zd (Z)) and "trans HFO-1233 zd" (also known as HFO-1233zd (E)) describe the cis and trans forms of 1-chloro-3, 3, 3-trifluoropropene, respectively. Thus, the term "HFO-1233 zd" includes within its scope cis HFO-1233zd, trans HFO-1233zd and all combinations and mixtures of these. In certain preferred aspects, HFO-1234ze comprises, consists essentially of, or consists of transHFO-1233 zd.

The present invention also provides methods and systems for using the compositions of the present invention, including methods and systems for heat transfer, methods and systems for replacing existing heat transfer fluids in existing heat transfer systems, and methods for selecting a heat transfer fluid according to the present invention to replace one or more existing heat transfer fluids. Whilst in certain embodiments the compositions, methods and systems of the present invention may be used in place of any known heat transfer fluid, in further and in some cases preferred embodiments the compositions herein may be used as a replacement for CFC-114, particularly but not exclusively for medium to high temperature heat pump systems.

Other embodiments and advantages will be readily apparent to those skilled in the art based on the disclosure provided herein.

Detailed Description

CFC-114 is commonly used in refrigerant and heat pump systems, particularly those of moderate to high heating temperatures. It is estimated that its Global Warming Potential (GWP) is 10,000, well above the target or requirement. Applicants have found that the compositions of the present invention particularly and unexpectedly meet the need for new compositions for such applications, particularly but not exclusively heat pump systems, especially those having moderate to high heating temperatures, with improved environmental impact while providing other important performance characteristics, such as but not limited to: capacity, efficiency, glide (glide), flammability and toxicity. In a preferred embodiment, the compositions of the present invention provide an alternative and/or substitute for the working fluids currently used in such applications (particularly and preferably CFC-114), which at the same time have lower GWP values and in such systems the capacity is very well matched to CFC-114.

Heat transfer composition

The compositions of the present invention are generally suitable for use in heat transfer applications, that is, as heating and/or cooling media, but are particularly well suited for use in the heat pump systems described above heretofore utilizing CFC-114.

Applicants have found that the use of the components of the present invention within the specified ranges is important to achieve the important, but difficult to achieve, combination of properties exhibited by the compositions of the present invention, particularly in the preferred systems and methods.

In certain embodiments, the compositions of the present invention comprise a first component selected from the group consisting of 1-chloro-3, 3, 3-trifluoropropene (HFO-1233zd), 1,1,1,3, 3-pentafluoropropane (HFC-245fa), and combinations thereof. In certain preferred aspects, HFO-1233zd comprises, consists essentially of, or consists of trans-HFO-1233 zd or HFO-1233zd (E). The compositions of the present invention also include a second component selected from the group consisting of 1,3,3, 3-tetrafluoropropene (HFO-1234ze), 1,1,1, 2-tetrafluoroethane (HFC-134a), and combinations thereof.

The first component may be provided in an amount of about 40 wt.% to about or less than 100 wt.%, and the second component may be provided in an amount of about or more than 0 wt.% to about 60 wt.%. In a further aspect, the first component may be provided in an amount of about 60 wt.% to about or less than 100 wt.%, and the second component may be provided in an amount of about or more than 0 wt.% to about 40 wt.%.

As noted above, in certain aspects of the invention, one or more first components may be provided alone or together with one or more second components. To this end, the combination of the first and second components may include, but is not necessarily limited to: (1) HFO-1233zd and either or both HFO-1234ze and/or HCE-134 a; (2) HFC-245fa and either or both HFO-1234ze and/or HCE-134 a; (3) HFO-1233zd and HFC-245fa with HFO-1234ze or HCE-134 a; (4) and both HFO-1233zd and HFC-245fa and HFO-1234ze and HCE-134 a.

In certain embodiments, the first component comprises, consists of, or consists essentially of HFO-1233zd, and in certain preferred aspects, comprises, consists essentially of, or consists of HFO-1233zd (E). HFO-1233zd may be provided in an amount of from about 40 wt.% to about or less than 100 wt.%, and in certain preferred embodiments may be in an amount of from about 60 wt.% to about or less than 100 wt.%. In a further aspect, for example, when HFO-1233zd is used as a component of existing systems used to retrofit CFC-114, it may be provided in an amount of from about 60 wt.% to about 85 wt.%, in certain aspects from about 65 wt.% to about 85 wt.%, and in further aspects from about 70 wt.% to about 85 wt.%. In a further aspect, for example, when HFO-1233zd is used as a component of a new system that replaces existing CFC-114 based systems, it can be provided in an amount from about 85 wt.% to about or less than 100 wt.%.

In further embodiments, the first component comprises, consists of, or consists essentially of HFC-245 fa. HFC-245fa may be provided in an amount of from about 40 wt.% to about or less than 100 wt.%, and in certain preferred embodiments, may be in an amount of from about 60 wt.% to about or less than 100 wt.%. In a further aspect, for example, when HFC-245fa is used as a component of an existing system used to retrofit CFC-114, it may be provided in an amount of from about 60 wt.% to about 87 wt.%, in certain aspects in an amount of from about 60 wt.% to about 85 wt.%, and in further aspects in an amount of from about 70 wt.% to about 85 wt.%. In a further aspect, for example, when HFC-245fa is used as a component of a new system for replacing existing CFC-114 based systems, it can be provided in an amount of from about 85 wt.% to about or less than 100 wt.%.

In further embodiments, the second component comprises, consists of, or consists essentially of HFO-1234ze, and in certain preferred aspects, comprises, consists essentially of, or consists of HFO-1234ze (E). HFO-1234ze may be provided in an amount of about or greater than 0 wt.% to about 60 wt.%, and in certain preferred embodiments in an amount of about or greater than 0 wt.% to about 40 wt.%. In a further aspect, for example, when HFO-1234ze is used as a component in existing systems used to retrofit CFC-114, it may be provided in an amount of from about 13 wt.% to about 40 wt.%, in certain aspects from about 15 wt.% to about 40 wt.%, and in further aspects from about 15 wt.% to about 35 wt.%. In a further aspect, for example, when HFO-1234ze is used as a component of a new system that replaces existing CFC-114 based systems, it may be provided in an amount of from about or greater than 0 wt.% to about 15 wt.%.

In further embodiments, the second component comprises, consists of, or consists essentially of HFC-134 a. HFC-134a may be provided in an amount of from about or greater than 0 wt.% to about 60 wt.%, and in certain preferred embodiments in an amount of from about or greater than 0 wt.% to about 40 wt.%. In a further aspect, for example, when HFC-134a is used as a component of existing systems used to retrofit CFC-114, it may be provided in an amount of from about 13 wt.% to about 40 wt.%, in certain aspects in an amount of from about 15 wt.% to about 35 wt.%, and in further aspects in an amount of from about 15 wt.% to about 30 wt.%. In a further aspect, for example, when HFC-134a is used as a component of a new system for replacing existing CFC-114 based systems, it may be provided in an amount of from about or greater than 0 wt.% to about 15 wt.%.

In certain preferred aspects, HFO-1233zd, and in certain embodiments HFO-1233zd (E), is provided alone or in combination with HFO-1234 ze. In this aspect, HFO-1233zd may be provided in an amount from about 60 wt.% to less than about 100 wt.%, and HFO-1234ze may be provided in an amount from greater than about 0 wt.% to about 40 wt.%. In a further aspect, for example, when the composition is used as a component in retrofitting an existing system used for CFC-114, HFO-1233zd is provided in an amount of from about 60 wt.% to about 85 wt.% and HFO-1234ze is provided in an amount of from about 15 wt.% to about 40 wt.%. In a further aspect, HFO-1233zd is provided in an amount from about 65 wt.% to about 85 wt.%, HFO-1234ze is provided in an amount from about 15 wt.% to about 35 wt.%, in a further aspect, HFO-1233zd is provided in an amount from about 70 wt.% to about 85 wt.%, and HFO-1234ze is provided in an amount from about 15 wt.% to about 30 wt.%. In a further aspect, for example, when the composition is used as a component of a new system that replaces existing CFC-114 based systems, HFO-1233zd may be provided in amounts of from about 85 wt.% to about or less than 100 wt.% and HFO-1234ze in amounts of from greater than 0 wt.% to about 15 wt.%.

In a further preferred aspect, HFO-1233zd is provided alone or in combination with HFC-134a, and in certain embodiments, HFO-1233zd (E) is provided alone or in combination with HFC-134 a. In this aspect, HFO-1233zd may be provided in an amount from about 60 wt.% to less than about 100 wt.%, and HFC-134a may be provided in an amount from greater than about 0 wt.% to about 40 wt.%. In a further aspect, for example, when the composition is used as a component in retrofitting an existing system used with CFC-114, HFO-1233zd is provided in an amount of from about 60 wt.% to about 85 wt.% and HFC-134a is provided in an amount of from about 15 wt.% to about 40 wt.%. In a further aspect, HFO-1233zd is provided in an amount from about 65 wt.% to about 85 wt.%, HFC-134a is provided in an amount from about 15 wt.% to about 35 wt.%, and in a further aspect, HFO-1233zd is provided in an amount from about 70 wt.% to about 85 wt.%, HFC-134a is provided in an amount from about 15 wt.% to about 30 wt.%. In a further aspect, for example, when the composition is used as a component of a new system that replaces an existing CFC-114 based system, HFO-1233zd may be provided in amounts of from about 85 wt.% to about or less than 100 wt.% and HFC-134a is provided in amounts of from greater than 0 wt.% to about 15 wt.%.

In certain preferred aspects, HFC-245fa is provided, either alone or in combination with HFO-1234 ze. In this aspect, HFC-245fa may be provided in an amount of from about 60 wt.% to less than about 100 wt.%, and HFO-1234ze may be provided in an amount of from greater than about 0 wt.% to about 40 wt.%. In a further aspect, for example, when the composition is used as a component of an existing system used to retrofit CFC-114, HFC-245fa is provided in an amount of from about 60 wt.% to about 87 wt.% and HFO-1234ze is provided in an amount of from about 13 wt.% to about 40 wt.%. In a further aspect, HFC-245fa is provided in an amount of from about 60 wt.% to about 85 wt.%, HFO-1234ze is provided in an amount of from about 15 wt.% to about 40 wt.%, and in a further aspect, HFC-245fa is provided in an amount of from about 70 wt.% to about 85 wt.%, HFO-1234ze is provided in an amount of from about 15 wt.% to about 30 wt.%. In a further aspect, for example, when the composition is used as a component of a new system that replaces existing CFC-114 based systems, HFC-245fa can be provided in an amount of from about 85 wt.% to about or less than 100 wt.% and HFO-1234ze in an amount of from greater than 0 wt.% to about 15 wt.%.

In a still further preferred aspect, HFC-245fa is provided, either alone or in combination with HFC-134 a. In this aspect, HFC-245fa may be provided in an amount of from about 60 wt.% to less than about 100 wt.%, and HFC-134a may be provided in an amount of from greater than about 0 wt.% to about 40 wt.%. In a further aspect, for example, where the composition is used as a component of an existing system used to retrofit CFC-114, HFC-245fa is provided in an amount of from about 60 wt.% to about 87 wt.% and HFC-134a is provided in an amount of from about 13 wt.% to about 40 wt.%. In a further aspect, HFC-245fa is provided in an amount of from about 60 wt.% to about 85 wt.%, HFC-134a is provided in an amount of from about 15 wt.% to about 40 wt.%, in a further aspect, HFC-245fa is provided in an amount of from about 70 wt.% to about 85 wt.%, and HFC-134a is provided in an amount of from about 15 wt.% to about 30 wt.%. In a further aspect, for example, where the composition is used as a component of a new system that replaces existing CFC-114 based systems, HFC-245fa can be provided in an amount of from about 85 wt.% to about or less than 100 wt.%, HFC-134a being provided in an amount of from greater than 0 wt.% to about 15 wt.%.

In a further aspect of the present invention, applicants have surprisingly and unexpectedly found that the capacity, efficiency and slip of the compositions of the present invention are similar to CFC-114, or within commercially acceptable tolerances. The compositions of the invention also have the advantage of low GWP. By way of non-limiting example, table a below illustrates the significant GWP superiority of certain compositions of the present invention, described in terms of weight fraction of each component in parentheses, as compared to the GWP of CFC-114, which has a GWP of 10,000.

TABLE A

The compositions of the present invention may include other components in order to enhance or provide certain functions of the compositions of the present invention, or in some cases, to reduce the cost of the compositions. For example, a heat transfer composition comprising a preferred composition of the present invention as a refrigerant (particularly one used in a vapor compression system), and one or more lubricants, typically present in an amount of from about 30 to about 50 wt.%, in some cases, possibly in an amount greater than about 50 wt.%, and in other cases, in an amount as low as about 5 wt.% of the total heat transfer composition.

Applicants have found that polyol esters (POE) and polyvinyl ethers (PVE), PAG oils, silicone oils, lubricants used in refrigeration machinery possessing previously used Hydrofluorocarbon (HFC) refrigerants, may be advantageously used in the heat transfer compositions of the present invention in certain embodiments. Commercially available esters include neopentyl glycol dipelargonate, available as Emery 2917 (registered trade mark) and Hatcol 2370 (registered trade mark). Other esters used include phosphate esters, diesters, and fluoroesters. Preferred lubricants include POE and PVE. Of course, different mixtures of different types of lubricants may be used.

Heat transfer method and system

Thus, the methods, systems, and compositions of the present invention are generally suitable for use in a wide variety of heat transfer systems, particularly heat pump systems, and the present invention includes medium to high temperature heat pump systems. Non-limiting examples of such systems include: a medium temperature heat pump system with a condensation temperature above 60 ℃, preferably 70 ℃ to 100 ℃. The high temperature heat pump system includes: those systems with condensation temperatures above 100 ℃. Examples of such systems include, but are not limited to: those systems used as a replacement for industrial boilers. Typical examples include: a water-water heat pump of a shopping mall. They can also be used in the oil or mining industry where heat sources are readily available. The compressor is typically a centrifugal compressor, but other types of compressors, such as screw compressors, may also be used. The heat exchanger may be a direct expansion shell and tube type or a flooded shell and tube type. The compositions of the present invention are not limited to such systems and may be used in any heat transfer system originally designed for use with HCFC or CFC refrigerants (e.g., CFC-114).

Preferred compositions of the present invention tend to exhibit many of the desirable characteristics of CFC-114, but have significantly lower GWP than CFC-114, while having capacity, efficiency and glide substantially similar to or substantially consistent with CFC-114, and preferably as high as, or higher than, CFC-114. In particular, applicants have recognized that certain preferred embodiments of the compositions of the present invention tend to exhibit relatively low global warming potentials ("GWPs"), preferably, less than about 10,000, preferably, no more than 5,000, and more preferably, no more than about 1,500. In certain preferred embodiments, the GWP of the composition is less than 1,000, in certain embodiments less than 500, in further embodiments less than 250, and in still further embodiments less than 150.

As mentioned above, the present invention is particularly advantageous in medium to high temperature heat pump systems. Non-limiting examples of such systems are provided in the following examples. To this end, such a system may include a high temperature heat pump application (example 1). The following examples provide typical conditions and parameters for high temperature heat pumps, but do not limit the application of these blends to high (or medium) temperature heat pump systems. For this reason, these conditions are not considered to limit the invention, and those skilled in the art will appreciate that these conditions may be varied based on one or more of a number of factors, including but not limited to environmental conditions, target application, season, etc. Such embodiments are also not necessarily limited to the definition of the terms "medium temperature heat pump system" or "high temperature heat pump system". The compositions provided herein may be used in similar system types or, in certain embodiments, used with CFC-114 is a heat transfer composition or any alternative system that may be suitable for use as a heat transfer composition.

Also included, in certain embodiments, is a method of retrofitting, the method comprising: at least a substantial portion of the heat transfer fluid (including refrigerant and optional lubricant) in existing systems is replaced with the composition of the present invention without significant system changes. In certain preferred embodiments, the replacement step is a drop-in replacement in the sense that substantial redesign of the system is not required and major parts of the equipment do not need to be replaced in order to adapt the compositions of the present invention for use as heat transfer fluids. In certain preferred embodiments, the method comprises drop-in replacement, wherein the capacity of the system is at least about 70%, preferably at least about 85%, more preferably at least about 90%, and more preferably at least about 95%, and preferably no more than about 130%, more preferably less than about 115%, and more preferably less than about 110% of the capacity of the system prior to replacement. In certain preferred embodiments, the method comprises drop-in replacement, wherein the efficiency (COP) of the system is at least about 70%, more preferably at least about 90%, and more preferably at least about 95%, and preferably no more than about 130%, more preferably less than about 115%, and more preferably about 110% or less than about 110% of the system prior to replacement. In certain preferred embodiments, the method comprises a drop-in replacement wherein the temperature glide, i.e., the difference between the starting and ending temperatures of the phase change process caused by the composition within the heat transfer system, is less than about 5 ℃, in certain aspects less than about 4 ℃, in further aspects less than about 3 ℃, in certain aspects less than about 2 ℃.

In certain other preferred embodiments, the compositions of the present invention may be used in heat pump or refrigerant systems containing lubricants (e.g., polyol ester oils, etc.), or may be used with other lubricants conventionally used with CFC or HCFC refrigerants, as discussed in more detail above. The term "heat pump system" as used herein generally refers to any system or device comprised of a compressor, an expansion device, and a heat exchanger, or any component or portion of such a system or device. Such systems provide heat through a condenser. The compressors may be centrifugal, screw and positive displacement compressors, while the heat exchangers may be dry expansion or flooded heat exchangers. The expansion valve may be an electronic or thermostatic expansion valve and may be determined as required by the design details. These illustrations do not limit any possible variations from a particular application.

As used herein, the term "refrigeration system" generally refers to any system or device, or any component or portion of such a system or device, that uses a refrigerant to provide heat or cooling. Such air cooling systems include, for example, air conditioners, home refrigerators, supermarket coolers, or any system identified herein or known in the art.

Examples

The following examples are provided for the purpose of illustrating the invention and are not intended to limit the scope of the invention.

EXAMPLE 1 novel System

Coefficient of performance (COP) is a generally accepted measure of refrigerant performance, particularly as a measure of the relative thermodynamic efficiency of a refrigerant in a particular heating or cooling cycle, including evaporation or condensation of the refrigerant. In refrigeration engineering, the term denotes the ratio of the effective refrigeration to the energy used by the compressor in the process of pressing the vapor. The capacity of a refrigerant represents the amount of cooling or heating it provides and, for a given volumetric flow rate of refrigerant, provides some measure of the compressor's ability to pump heat. In other words, a higher capacity refrigerant can deliver more cold or heat for a particular compressor. One method of estimating the COP of a refrigerant under specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, e.g., r.c. Downing, fluor corpon regenerative HANDBOOK, chapter 3, prenotice-Hall, 1988).

Provided is a high temperature heat pump system that heats water. With the system illustrated in this embodiment, the condenser temperature is set to 110 ℃, which generally corresponds to a water temperature of about 90 ℃. The supercooling degree at the inlet of the expansion device was set to 10 ℃. The evaporation temperature was set to 25 ℃. The degree of superheat at the evaporator outlet was set to 15 ℃. The compressor isentropic efficiency is set to 85% and the volumetric efficiency is set to 100%. The pressure drop and heat transfer in the connecting lines (suction and liquid lines) are considered negligible, and heat dissipation through the compressor shell is considered negligible. The operating parameters of the compositions defined in Table 1 were determined according to the invention on the basis of CFC-114(COP value 100%, capacity value 100%, exit temperature 110.5 ℃) and are reported in Table 2 below,

TABLE 1

TABLE 2

As can be seen from table 2 above, the applicants have found that the compositions of the present invention are capable of achieving a number of important performance parameters immediately, which are very close to the parameters of R-114, and thus, the compositions can be used in new high temperature heat pump systems. For example, in such high temperature heat pump systems, the capacity of the compositions in groups A-D is within about 25% of the capacity of R-114, and more preferably within about 15%. It is highly desirable that the efficiency (COP) of all these blends be as much as 10% higher than R-114. The compositions in groups a-D exhibit evaporator glide below about 2 ℃ and about 10 ℃ above the outlet temperature, both of which are well suited for high temperature heat pump applications. In particular, considering the improved GWP of the compositions of groups a-D, these compositions of the present invention are excellent candidates for new devices for high temperature heat pump applications. Further, the compositions of groups a-B exhibit a very low GWP below 150, which provides additional advantages.

It will be appreciated by those skilled in the art that the compositions of the present invention are capable of providing substantial advantages of refrigerants having low GWP and excellent efficiency for use in new or newly designed refrigeration systems, including and preferably high temperature heat pump systems.

Example 2 retrofit System

Also included, in certain embodiments, is a method of retrofitting, the method comprising: at least a portion of the refrigerant present is removed from the system and at least a portion of the removed refrigerant is replaced with the composition of the present invention, preferably without significantly altering the system, and more preferably without any change in major system components such as the compressor, condenser, evaporator and expansion valve. Due to certain features of high temperature heat pump systems, including in particular high temperature heat pump systems containing R114 refrigerant or designed to contain R114 refrigerant, it is important in certain embodiments that such systems exhibit reliable system operating parameters for drop-in refrigerant. The operation parameters include

Evaporator glide is in the range of about 4 deg.c, and more preferably in the range of about 3 deg.c. This parameter is important in this embodiment as it allows the use of existing heat exchangers.

System capacity above about 100%, and more preferably above about 110% of the system capacity using R114. This parameter is important in such embodiments because these new refrigerants with slip can be used in existing heat exchangers.

System efficiency is higher than about 100% of the system efficiency using R114. This parameter is important in such embodiments because it can maintain the same energy consumption associated with operating these systems.

The outlet temperature is preferably below about 130 ℃ and more preferably below about 125 ℃. This feature has the advantage of allowing the use of existing equipment without activating the thermal protection of the system, which is preferably designed to protect the compressor components. An advantage of such parameters is that expensive control measures, such as liquid injection for lowering the outlet temperature, are avoided.

According to the invention, the above-mentioned and other operating parameters were determined for the compositions of groups E to H identified in Table 3 below, which are reported in Table 4 below

TABLE 3

TABLE 4

In certain preferred embodiments, the replacement step is a drop-in replacement in the sense that substantial redesign or change of the system is not required and major parts of the equipment do not need to be replaced in order to accommodate the refrigerants of the present invention. This is the case with compositions of groups E-H, which can generally be used in most retrofit processes without changing any of the major components. In all compositions of groups E-H, the system capacity and efficiency are similar to R114, or exceed R114. For all compositions of the E-H group, the evaporator glide is below about 4 ℃, so they can be used in most existing high temperature heat pump systems.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims or any claims appended hereto.

Claims

1. A heat transfer composition comprising

From about 60% to about 95% by weight of a first composition selected from the group consisting of HFO-1233zd, HFC-245fa, and combinations of these; and

from about 5% to about 40% by weight of a second composition selected from the group consisting of HFO-1234ze, HFC-134a, and combinations of these;

provided that the composition has one or more of: (1) a capacity of about 90% to about 110% relative to CFC-114 in a high temperature heat pump system; (2) in high temperature heat pump systems, the COP is at least about 95% with respect to CFC-114; or (3) in a high temperature heat pump system, the slip is less than about 3 ℃.

2. The heat transfer composition of claim 1 wherein said component (a) comprises HFO-1233zd (e).

3. The heat transfer composition of claim 2 comprising from about 60 to about 85 wt.% HFO-1233zd and from about 15 to about 40 wt.% HFO-1234 ze.

4. The heat transfer composition of claim 2 comprising from about 60 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 40 wt.% HFC-134 a.

5. The heat transfer composition of claim 2 comprising from about 70 wt.% to about 85 wt.% HFO-1233zd and from about 15 wt.% to about 30 wt.% HFC-134 a.

6. The heat transfer composition of claim 1 wherein said component (a) comprises HFC-245 fa.

7. The heat transfer composition of claim 6 comprising from about 60 to about 87 weight percent HFC-245fa and from about 13 to about 40 weight percent HFO-1234 ze.

8. The heat transfer composition of claim 6 comprising from about 60 wt.% to about 87 wt.% HFC-245fa and from about 13 wt.% to about 40 wt.% HFC-134 a.

9. A high temperature heat pump system, comprising: a compressor, an evaporator and a condenser capable of operating at high temperature conditions wherein a heat transfer composition flows through the system, the heat transfer composition comprising from about 60% to less than about 100% by weight of a first composition selected from the group consisting of HFO-1233zd, HFC-245fa, and combinations of these; and from greater than about 0% to about 40% by weight of a second composition selected from the group consisting of HFO-1234ze, HFC-134a, and combinations of these; provided that the heat transfer composition has one or more of (1) a capacity of about 90% to about 110% relative to CFC-114 in a high temperature heat pump system; (2) in high temperature heat pump systems, the COP is at least about 95% with respect to CFC-114; or (3) in a high temperature heat pump system, the slip is less than about 3 ℃.

10. In a high temperature heat pump system, a method of transferring heat to or from a fluid or object comprising

Providing a high temperature heat pump composition comprising from about 60% to less than about 100% by weight of a first composition selected from the group consisting of HFO-1233zd, HFC-245fa, and combinations of these; and from greater than about 0% to about 40% by weight of a second composition selected from the group consisting of HFO-1234ze, HFC-134a, and combinations of these; provided that the heat transfer composition has one or more of (1) a capacity of about 90% to about 110% relative to CFC-114 in a high temperature heat pump system; (2) in high temperature heat pump systems, the COP is at least about 95% with respect to CFC-114; or (3) in a high temperature heat pump system, slippage is less than about 3 ℃;

placing the high temperature heat pump composition within the system of claim 9 and flowing the high temperature heat pump composition through the system;

causing a phase change in the high temperature heat pump composition, and

exchanging heat with the fluid or object during the phase change.