WO2022031274A1

WO2022031274A1 - Low gwp heat transfer fluid coordination entities

Info

Publication number: WO2022031274A1
Application number: PCT/US2020/044912
Authority: WO
Inventors: Bob Lee DAVIS
Original assignee: Davis Bob Lee
Priority date: 2020-08-04
Filing date: 2020-08-04
Publication date: 2022-02-10

Abstract

A low GWP heat transfer fluid coordination entity is disclosed comprising at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500, including a coordination entity composition comprising at least one heat transfer fluid including at least hydrofluoroolefm, and being complexed under heat and pressure in a closed vessel with at least one activated organic oil fatty acid in the presence of a catalytic material surface. A preferred aspect of the coordination entity includes hydrofluoroolefm blends, singly or in combination with any hydrofluorocarbon thereof.

Description

LOW GWP HEAT TRANSFER FLUID COORDINATION ENTITIES

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation-In-Part (CIP) of US Application No.: 15/847,878 filed on December 19, 2017, and this application claims the benefit of priority to US Application No.: 15/847,878 filed on December 19, 2017, and this and the materials discussed therein are incorporated herein by reference in their entirety. Where a definition or use of a term in that incorporated reference is inconsistent or contrary to the definition of that term provided in this instant application, the definition of that term provided herein applies and the definition of that term in the reference does not apply.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to heat transfer fluids, and more particularly, the invention relates to heat transfer fluids suitable for use as refrigerants, fire suppressants, medical propellants, and blowing agents, among other common uses for heat transfer fluids.

2. Description of the Prior Art

There has been a multi-decade quest for addressing environmental concerns when researching for capable heat transfer fluids used as refrigerants. However, there has not yet been found a single perfect refrigerant for diverse air conditioning, refrigeration, medical and industrial applications that does not present new environmental challenges.

Early on, the predominant environmental concerns were the holes being formed in the ozone layer, which allowed solar radiation to penetrate the ozone layer, as well as the build-up of greenhouse gases, which trap solar radiation and contribute to global warming. To address these concerns, researchers developed chemical compositions that exhibited low ozone depletion potentials (ODP’s) and low global warming potentials (GWP’s). Although achieving a low ODP was a relatively simple task, achieving low GWP’s without high flammability has been more of a challenge. Further confounding the quest is the desire for a refrigerant that exhibits energy savings along with a high capacity, ie. a refrigerant that is capable of bringing down the temperature of the containment area to be cooled. Some refrigerants are less capable than others in this regard, so some corporate researchers found that adding flammable gases, such as propane, butane and the like, gave more “capacity”, although these additions increased the undesired flammability.

The focus of refrigerant development has shifted to a next-generation refrigerant with low GWP that still offers the efficiency and affordability that the market demands. New refrigerants were examined for their capacity, chemical compatibility, low flammability values, and future utility as a lower GWP replacement for existing HCFCs and as a more energy conserving replacement for existing HFCs. Research institutions produced many scholarly papers focusing on various potential options including “natural” refrigerants such as carbon dioxide (CO2), hydrocarbons (HC), and ammonia (NH3) as well as hydrofluoro olefins (HFO’s) and HFO/HFC blends. All of the evidence to date has shown that “natural” refrigerants, although lowest in GWP, are difficult and costly to work with, and have been found to be often flammable. HFO’s, although very low in GWP, carry distinct disadvantages in that they are flammable, and, by themselves, lack capacity when compared to HFCs.

As can be noted, more is needed to be considered than the GWP value alone. Environmental policy throughout developed countries are now considering the indirect effects of increased CO2 emissions for less efficient refrigerants, and not just the direct global warming (GWP) of the refrigerant.

The metrics of a more inclusive standard for the effect of a chemical on global warming has been designated as Total Equivalent Warming Impact (TEWI), which is considered to be a more reliable indicator when determining the ultimate environmental impact of a refrigerant. The TEWI method balances a refrigerant’s direct GWP, charge level, leakage emissions, and efficiency and energy use of the refrigerant in actual systems. New refrigerants must be designed to address both of these metrics in determining the best possible comparison of refrigerants for each application.

It has been found that in the United States, about 20% of the electrical energy we use goes to air conditioning. One consideration for addressing the reduction of the costs of energy, both from an economic standpoint, but also from the environmental cost, would be to simply develop a substantially non-flammable refrigerant that is low in GWP, while substantially reducing the energy consumption of most standard air conditioner and refrigeration units in existence today. Higher energy demands on power plants generally mean that more more power plants are needed, also meaning that more greenhouse gases are produced in order to provide sufficient air conditioning. SUMMARY OF THE INVENTION

A first aspect of the invention discloses a new and non-obvious inventive subject matter regarding complexing at least one low GWP feedstock heat transfer fluid having a GWP value less than 1500, especially including a coordination entity composition comprising a heat transfer fluid, such as a hydrofluoroolefin, blends thereof, and like chemical compositions, with at least one organic oil fatty acid, preferably selected from the group consisting of food grade walnut, almond, canola and safflower oil. As used herein, the term "organic oil fatty acid" can include a fatty acid of an organic oil or a fatty acid of an organic oil blend. Preferably, the heat transfer fluid is complexed with at least some of the organic oil fatty acid upon activation of the fatty acid under heat and pressure in a closed vessel. Preferably the closed vessel may include a catalytic material surface in contact with the reactants, for instance a vessel having an interior copper construction.

As used herein, the term “HFO” shall mean HFO’s, HFO blends such as R-448 and R-449, or other heat transfer fluids, including HFC’s, and any combinations thereof, shall find suitability as a feedstock for use in the present invention.

In a second aspect of the present invention, said HFO< hydrofluorool efin, or a blend such as R-448 or R-449, or any like composition heat transfer fluid can be complexed with at least 1, 5, or even 10 or more % of a blend of a first, second and even third organic oil of a food grade oil composition. This complexing can exist between heat transfer fluid molecules and fatty acids of the oil blend. In some aspects, the fatty acid molecules of an oil blend are activated in a closed vessel under heat and pressure and then subsequently subjected to the heat transfer fluid under heating conditions from 60°F to over 200°F in a closed vessel, preferably made of copper, under pressure. In some aspects, the composition made by this complexing can comprise approximately 95-99 weight percent (wt%) of the heat transfer fluid, and approximately 1-5 wt% of the oil blend. Thus, the composition can comprise a heat transfer fluid to oil blend ratio of 1:99 or 5:95, or any ratio in between. Moreover, all commercially suitable ratios of heat transfer fluid to oil blend is contemplated, including for example: 0.1 : 99.9; 10:90; 25:75; 50:50; 75:25; or 99: 1, among others.

It should be appreciated that the oil complexes contemplated herein include food and other natural oils, as well as synthetic oils. As used herein the term “fatty acid” refers to a substituted or non- substituted, saturated or unsaturated, carboxylic acid with a long aliphatic tail (chain) having from 10 to 20 carbons in the aliphatic chain. This would include, for example, a fatty acid ester, a fatty acid having no double bonds, and a fatty acid having multiple double bonds. As used herein a simple fatty acid is a non-substituted, saturated or unsaturated fatty acid. Oleic acid and linoleic acid are examples of simple fatty acids. It is contemplated that the inventive concepts herein, including those embodied in the originally filed claims, could apply to the more general type of fatty acid, and to simple fatty acids.

In some aspects of the inventive subject matter, compositions at least 0.1 wt%, 1 wt%, 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 50 wt%, or at least 95 wt% of the heat transfer fluid therein is complexed with an organic oil fatty acid. A heat transfer fluid can be complexed with at least 1%, at least 5%, at least 10%, at least 25%, at least 50%, or at least 80% of the fatty acid composing the composition.

Each of the organic oils or the oil blend as a whole can compose at least 0.1 wt%, at least 1 wt%, at least 2.5 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 50 wt%, or at least 95 wt% or more of the composition. A heat transfer fluid can be complexed with at least 1%, at least 5%, at least 10%, at least 25%, at least 50%, or at least 80% of the organic oil(s) composing the composition.

A preferred aspect of the present invention includes an activated blend of equal portions of walnut, almond and canola oils that is then heated in the presence of a hydrofluorool efin (HFO) or similar composition in a pressurized vessel made of at least copper and other transition metals at temperatures of from 60°F to over 200°F.

Also in some aspects, a first fatty acid (e.g., linoleic acid or oleic acid, etc.) can compose at least 0.1 wt%, at least 1 wt%, at least 2.5 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt %, at least 20 wt%, or at least 25 wt% of the composition. In less preferred aspects, the first fatty acid can compose less than 0.1 wt% of the composition.

Contemplated compositions can comprise two or more different organic oils, and each organic oil can comprise one or more fatty acids having one, two, three, or even more carbon-to- carbon double bonds. In some aspects, the fatty acid(s) compose at least one food oil of an oil blend, including for example, walnut, canola, sunflower or almond oil.

The heat transfer fluid can comprise any commercially suitable heat transfer fluid, but is preferably a hydrofluoroolefin (HFO), either alone or in combination with other heat transfer fluids, such as a halo-ethane such as 1,1, 1,2 tetrafluoroethane, R-404A and/or R-410A.

The present invention contemplates that by using an HFO, HFO blend such as R-448 and R-449, or other heat transfer fluids, including HFC’s, as a feedstock to be complexed with the fatty acid combination disclosed hereinabove, either alone or in combination with other low GWP refrigerants, the resulting refrigerant fluid will yield an energy saving low GWP refrigerant that provides energy economies of up to 50% savings that were unknown previusly. Since HFO refrigerants, or Hydrofluro-Olefins, are a class of refrigerants that have a much lessened global warming potential than HFC alternatives, the resulting composition exhibits lower on the global warming potential scale and only slightly higher than standard carbon dioxide, which is increasingly being viewed as an alternative.

Regulations are limiting the use of R- 134a, making it go away. Furthermore, many companies are working on eliminating R-404A HFC Refrigerant as well. Since the market for 404A isn’t as large as R-134a, it is still substantial for applications in larger commercial buildings, super markets, and even refrigerated trucks.

There have been some concerns from various companies that the HFO refrigerants have a much higher flammability rate than their HFC predecessors, however there have been many tests across the world from various agencies and they have not been able to find a significant danger.

At least one of the organic oil(s), the fatty acid(s) and the heat transfer fluid can be activated in any suitable apparatus, including for example, a tube or pipe or closed vessel apparatus comprising at least one of a copper, nickel, palladium, zinc, platinum, rhodium, iridium, or an alloy thereof, or a copper mesh, a steel mesh, or Nylon scrub pads. It is also contemplated that the activation can occur under heat and pressure. As used herein, the term "under heat and pressure" means at least 15°C, and at least 1.25 atmosphere (atm). Other contemplated heating temperatures include at least any of 10°C, 20°C, 30°C, 50°C, 100°C, 150°C, or even 200°C or more. Other contemplated pressures include at least any of 1.5 atm, 5 atm, 10 atm, 25 atm, lOOatm, or even 150 or more atm. Where an oil blend is activated (e.g., in a closed vessel having a catalyst), it is contemplated that the oil blend can be a composition of the inventive subject matter, even without the addition of a polar heat transfer fluid.

In one aspect, a small amount of heat transfer fluid can be added before or during activation of an oil blend. It is also contemplated that a small amount of polar heat transfer fluid can be added shortly after activation (e.g., within one hour, within two hours, etc.). Still further, the activated oil blend and small amount of polar heat transfer fluid can then be injected into a large quantity of the polar heat transfer fluid for further complexing.

It is contemplated that a composition of the inventive subject matter can have a superior compressibility factor than existing refrigerants and refrigerant compositions.

In the following description, the term “HFO” may be construed to relate to HFO, individually as well as collectively with other combinations of HFO related compositions, as well as combinations of HFO’s with any HFC, such as R-134A, R404A, R-410A, and any other myriad of combinations of heat transfer fluids that are commercially available.

It has been discovered by the present inventor that feedstocks of various refrigerant compositions, including HFO’s, hydrofluoroolefins, when complexed with the fatty acid compositions described in greater detail herein, a superior energy saving refrigerant is produced showing demonstrably higher capacities for cooling applications, while maintaining a low GWP product suitable for use in many applications worldwide.

In some aspects of the inventive subject matter, up to 95 wt% of hydrofluorool efin (also known as HFO) is mixed with 0.5 to 25 wt% of one or more organic oil(s) is complexed with some of the organic oil(s) (e g., the HFO is presumed to interact with a hydrogen of a carbonyl group of a fatty acid of the organic oil, or a carbon-to-carbon double bond of the organic oil). Without wishing to be limited to any particular theory or mechanism of action, it is contemplated that an absorptive process can occur wherein the HFO is complexed to the fatty acid(s) of the organic oil(s) via an attraction to the carbon-to-carbon double bonds, and that such complexing can tend to inhibit oxidation or other deterioration of the fatty acid. The double carbon bond is a relatively stable zone, where the atoms on either side generally do not spin as rapidly about as with comparable singly bonded carbons. This is borne out in experimental data, where the complexing of molecules with a double carbon bond of a fatty acid can create a unique signature that is detectable with H-NMR and x-ray diffraction. While not wishing to be limited by any particular mechanism of action or theory of operation, in this or other recitations of theory herein, it appears that some type of significant complexing is taking place when the activated oil blend is dissolved.

In some aspects, the HFOcan be mixed with 0.1 to 25 wt% of at least two different organic oils. It is contemplated that the first and second organic oils can be activated in a tubing apparatus under a heat of 10 to 200 or more °C and a pressure of 1 to 150 or more atm for a period of time between one minute and twenty-four or more hours. This activation can occur prior to mixing and/or complexing with the HFO, or can occur with HFO already mixed with the first and second organic oils (e.g., the oils and at least some of the HFO can be activated and complexed within the apparatus). It is also contemplated that the oils can be activated first, and mixed or complexed with HFO at a later time, ranging from immediately after activation to days, months, or even years later.

Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred aspects, along with the accompanying drawing FIG.'s in which like numerals represent like components.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic of a typical refrigeration cycle.

DETAIEED DESCRIPTION OF THE INVENTION

The following discussion provides many example aspects of the inventive subject matter. Although each aspect represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus if one aspect comprises elements A, B, and C, and a second aspect comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.

It should be noted that while the below description sometimes focuses on an oil blend, wherein the oil blend is injected into a large quantity of at least an HFO or HFO blend, such as R-448 or R-449, besides all the inventive subject matter should be interpreted to include other combinations of heat transfer fluid complexes comprising a heat transfer fluid and at least one fatty acid.

A fatty acid composition of the inventive subject matter could be made by blending a first, second and a third fatty acid and then processing the blend in a closed vessel under heat and pressure, such vessel apparatus having a controlled environment, to form an activated blend of organic oils. In certain aspects of the present invention, some or all of the fatty acid composition is a nano-sized composition after blending, especially if the fatty acids are blended at high speeds, or injected into the closed vessel at 50 or more PSI, preferably more than 100 PSI, up to 500 PSI. In another aspect of the present invention, it is contemplated to nano-size the blended oils prior to introduction into the vessel.

The controlled environment under which one or more of the fatty acids are processed can include, among other things, predetermined materials, temperatures, pressures, or times. One example of a predetermined material can comprise material that the processing apparatus composes (e g., copper, iron, steel, wood, plastic, etc.) or a catalyst may be inserted into the processing apparatus. A predetermined temperature or pressure can be the temperature/pressure or range of temperatures/pressures that the organic oil(s) or fatty acid(s) are exposed to during processing. A predetermined time can be the length of time the organic oil(s) or fatty acid(s) are processed, the length of time the organic oil(s) or fatty acid(s) are processed under a given temperature, the length of time the organic oil(s) or fatty acid(s) are processed under a given pressure, and so forth.

Examples of fatty acids include for example, oleic acid, linoleic acid, linolenic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, vaccenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, and palmitic acid, linolaidic acid, a- linolenic acid, mineral oil and combinations thereof. In some aspects, unsaturated fatty acids are preferred. Each acid can be derived from any suitable source, including for example, an organic oil (e.g., a plant oil, food oil, etc.). As used herein, an "organic oil" is any oil produced by plants, animals, and other organisms through natural metabolic processes. In addition, mineral oils of light mixtures of higher alkanes are disclosed in combination with organic fatty acids found to be suitable herein. Contemplated food oils include walnut oil, almond oil, canola oil, beech nut oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, cashew oil, hazelnut oil, macadamia oil, pecan oil, pine nut oil, pistachio oil, grapefruit seed oil, lemon oil, orange oil, pumpkin seed oil, watermelon seed oil, and other suitable food based oils. It is contemplated that a composition having only a single type of fatty acid, or a predominantly single type of fatty acid, can comprise a higher or lower wt% of the fatty acid, or the organic oil(s) comprising the fatty acid, depending on the type used. For example, a composition having at least predominantly oleic acid can have less than, twice as many, or even three times or more fatty acids than a composition having at least predominantly linoleic acid, or some other acid.

It should also be noted that it may be possible to manufacture a wide variety of synthetic oils that can be activated and complexed with a heat transfer agent. Such oils could have an odd number of carbons, an even number of carbons, no double carbon bonds, two or more double bonds, etc.

Once the fatty acid, or the oil comprising the fatty acid, is processed and activated, the activated blend can be infused, injected into, or otherwise combined with the heat transfer fluid to produce a refrigerant composition. As discussed above, certain aspects of the present invention disclose a small amount of heat transfer fluid mixed with the fatty acids in the processing apparatus, and complexed therein upon activation of the fatty acids.

All commercially suitable heat transfer fluids are contemplated, including for example, hydrofluorool efins (HFO’s), blends of HFO’s with other refrigerants, such as R-448 and R-449 compositions, methane-based (r-(000-099)) refrigerants, ethane-based (r-(100-199)) refrigerants, propane-based (r-(200-299)) refrigerants, cyclic organic (r-(300-399)) refrigerants, zeotropes (r- (400-499)), azeotropes (r-(500-599)), organic (r-(600-699)) refrigerants, inorganic (r-(700-709)) refrigerants, and unsaturated organic (r-(1000-1099)) refrigerants. It is contemplated that a composition of the inventive subject matter can be used in an existing refrigeration system that is compatible with R-134a, R-404A, R-410A or R-22, or some other refrigerants. However, some modifications, preferably minor, can be required (e.g., a small part change, addition, etc.). An inferior refrigerant can be completely removed from the system, and the system can be recharged with a composition of the inventive subject matter. Moreover, a composition of the inventive subject matter can be added to a system without complete removal of a prior refrigerant from the system. This is due to the fact that the compositions appears to be more energy efficient and self-sealing than existing refrigerants, even when combined with one or more contaminants, e.g., an inferior refrigerant or refrigerant composition, such as R-134a, R- 410A, R-22, etc.

Moreover, a composition of the inventive subject matter could be used in a novel unit comprising a different ratio of compressor size to coil size. For example, as compared to an existing refrigeration unit having a compressor size to coil size ratio of X:Y, a new unit can have a ratio of X-Z:Y, X+Z:Y, X:Y-W, or X:Y+W, wherein Z is at least 10%, 20%, 30%, 50%, or even 75% or more of X, and wherein W is at least 10%, 20%, 30%, 50%, or even 75% or more of Y. As another example, a new unit can have a greater number of, or a different configuration of, coils.

One possible composition of the inventive subject matter is the novel refrigerant fluid comprising a mixture of approximately 95-99 wt% of HFO, i.e. R-448, R-449, and combinations thereof, at least partially complexed with approximately 1-5 wt% of a non-toxic oil blend comprising one or more organic oils, wherein the oil blend has an oleic acid to linoleic acid ratio of between 70:30 and 50:50, and preferably approximately 60:40 wt%. The organic oils can include one or more of a canola oil, a walnut oil, an almond oil, and a sunflower oil, among others. One contemplated blend comprises canola, almond and walnut oils ("CAW blend").

Another contemplated blend comprises canola and sunflower oil ("CS blend"), preferably at an approximate ratio of between 5: 1 and 2: 1 (e.g., 3:1). Yet another contemplated blend comprises walnut, almond and canola oils, and a small amount of heat transfer fluid, such as HFO, HFO blends, R-448, R-449, among others. Further contemplated blends comprise CAW, CS and mineral oil combinations. Although blending these components together yields solid energy savings, it has also been seen that nano-sizing of the fatty acid and oil compositions reduces energy consumption during operations as well.

On the other hand, HFO’s, HFO blends such as R-448, and R-449, have been shown experimentally to provide significant improvements in refrigeration efficiency when mixed with the oils of an oil blend, possibly due to its highly polar nature as compared with other refrigerants. In particular, a mixture comprising approximately 95-99 wt% of HFO’s or HFO blends with approximately 1-5 wt% of the oil blend, which can also include approximately 50% of an oleic acid and 33% of a linoleic acid) was found to be very efficient.

The oils of one possible blend comprising walnut oil, almond oil, and canola oil, the CAW blend, are quite similar in chemical composition, as shown in Tables 1A-B (below). The Oleic acid accounts for approximately 50% of the “fatty acids” in the blend comprising precursor or feedstock oils, and are an alkene with an 18 long carbon chain. Oleic acid has one double carbon bond. Linoleic acid accounts for around 34% of the fatty acids in the blend and is also 18 carbons long, with two double carbon bonds. Linolenic acid is around 9% of the fatty acids in the blend and is 18 carbons long, with three double carbon bonds. Palmitic acid is around 5% of the fatty acids in the blend and is 16 carbons long.

Table 1A Feedstock Oil Ratios

Table IB Preferred Oil Blend

These food oils predominantly consist of relatively long-chain carbon molecules or fatty acids bonded to a glycerol. Fatty acids in free form have a carboxyl group (COOH) at the first (Alpha) carbon on the carbon chain, making them carboxylic acids.

One important discovery from an H-NMR application in an HFO blend containing a percentage of R-134a was the presence of a coordination entity of R -134a to the oils of the oil blends, potentially by inter-molecular hydrogen bonding and/or Van der Waals forces. The chemical complexing of the R-134a to the oils leaves a detectable signature, and is relatively stable and remains intact even after days in a depressurized state Surprisingly, the amount of tightly complexed R-134a to the oils apparently increased over time when used in an air conditioning system, thereby inhibiting degradation of the oils.

A catalyst can be used to cause a reaction between the R-134a and a fatty acid. When an HFO blend containing some portion of R- 134a is bubbled intensively through the oil, it is possible that no reaction occurs, even at 300 degrees F and over long periods of time. This is likely due to the rapid spinning along the axis of the carbon to carbon single bonds on both the R-134a and fatty acid molecules. In the liquid oil, the singly bonded carbons can spin relative to each other many thousands of times a second. In the HFO containing some portion of R-134a gas, the relative spin rate can be magnitudes faster, and it is likely that the two molecules simply bounce off each other. The coordination entity may be formed in the presence of a copper, nylon or stainless steel catalyst. Especially useful is a copper wool or a copper closed vessel, whereby the copper vessel may act as a catalyst. A composition of the inventive subject matter can produce the same amount of heating or cooling in a system using less than 90%, less than 75%, less than 50%, or even less than 33% of conventional refrigerants, for example HFO, HFO blends, R-134a, R-40A, R-410A, R-22, etc. For example, sensor arrays and data streams recorded show that the sample can produce the same amount of cooling in a system for somewhere between 35% and 60% of the wattage compared to some conventional refrigerants. A composition of the inventive subject matter can also keep a space colder or hotter for longer periods of time than conventional refrigerants. For example, it has been found that the present invention can keep a space colder or hotter for longer periods of time than existing refrigerants or refrigerant compositions. Thus, a system utilizing the present invention or other composition of the inventive subject matter can provide the same cooling or heating as a system utilizing R-410A, while running for approximately 10-30 minutes less per hour. Moreover, compositions of the inventive subject matter charged refrigeration units and systems can produce significantly less condensation off evaporative coils.

As shown in FIG. 1, air conditioning systems generally utilize a refrigerant cycle having two main parts, the condenser cycle and the evaporator cycle. The following description is for a standard air conditioner system. The condenser cycle starts at the compressor, where the warmed gas from the evaporator cycle is compressed back into a semi-liquid. This semi-liquid is then pumped through condenser coils, where a fan removes the heat into the outer environment and the gas becomes fully liquefied. This liquefied cooled fluid then flows to the expansion valve, where it changes from a liquid into a gas and adiabatically cools. This cooled gas then flows into the evaporator coils, where a fan blows cooled air into the controlled environment and the gas is warmed.

Increased pumping efficiency in the compressor is likely the most significant cause of the increased efficiencies and other compositions of the inventive subject matter. One reason for this increased efficiency is the highly viscous characteristics of the oil blends of the inventive subject matter, CAW, and CS. The oil blends can increase the sealing around the piston in a reciprocal pump, the spinning blades in a centrifugal pump or internals of a scroll pump. Another minor reason, is it takes less energy to pump an incompressible liquid, than it takes to pump a compressible gas. The oil blend is always or almost always going to be liquid, as the temperature of the oils will never come remotely close to their vaporization points. Some atomization likely occurs at the expansion valve, but will quickly re-liquefy onto the internal surface of the evaporator. In an HFO blend application containing at least a portion of R-134A, the R-134A is driven into a liquid at the compressor and also likely dissolves more rapidly into the oil blend.

In some preferred oil mixtures, the ratio of oleic acid to linoleic acid is approximately 3:2. These two acids have quite different heat capacities despite their close chemical structure of 18 carbon units. This is due to the number of double (C=C) carbon bonds. Oleic acid has a heat capacity of 2.88 kJ/(kg»K) (kilojoules perKilogramsK), to linoleic acid's heat capacity of 0.37 kJ/ (kg*K).R-134a is only two carbon units long and its heat capacity is 1.34 kJ/(kg»K).

These organic oil fatty acids generally have melting points around the temperatures that air conditioning unit evaporators operate. Oleic acid has a melting point of approximately 55°F, while that of linoleic acid is approximately 23°F and linolenic acid is at approximately 12°F. The expansion valves on standard air conditioner units are adjusted to take the evaporator toward the freezing point of water, but not so cold that ice forms on the outer surface of the evaporator. Therefore, the heat transfer fluid will not reach its full potential cooling, but will vaporize above the melting points of the high acid oils. The oils are generally almost always or always going to be liquid, although some atomization likely occurs at the expansion valve.

Another reason for the significant increase in refrigerant efficiency can be attributed to surface binding, and other compositions of the inventive subject matter, to the metal of the refrigerant system. This is evident from the fact that when a unit was switched from the present invention to R-410A, there was a temporary improvement in efficiency, most likely due to the present haloalkane complexes closely binding to the internal surfaces of the cooling system, until it was removed by the various constituents of R-410A. A smaller amount of efficiency is also gained by this lubrication effect, due to the smoother flow of gas and oils through the system.

It is contemplated that the ratio of at least one fatty acid to at least one heat transfer fluid can comprise any suitable ratio, including for example, 1:1000, 1 :100, 1 :10, 1:5 or even 100:1 or more. It is also contemplated that the ratio of one food oil (from which at least one fatty acid is derived) to another food oil, of a mixture (non-activated) or activated blend, can comprise any suitable ratio including for example, 1 :1, 1:2, 1 :3, 1 :4, or even 1 : 100 or less. In some aspects, a chemical marker can also be included above 80 °F. Therefore, in accordance with the present invention, a low GWP heat transfer fluid coordination entity is disclosed comprising at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500, including a coordination entity composition comprising at least one heat transfer fluid including at least hydrofluoroolefin, and being complexed under heat and pressure in a closed vessel with at least one activated organic oil fatty acid in the presence of a catalytic material surface. A preferred aspect of the coordination entity includes hydrofluoroolefin blends, singly or in combination with any hydrofluorocarbon thereof.

The coordination entity is complexed with at least one activated organic oil fatty acid that includes at least walnut oil. In addition, another aspect of the present invention provides for the inclusion of at least walnut oil and canola oil or the at least one activated organic oil fatty acid including at least walnut oil, almond oil and canola oil. In certain circumstances, the at least one activated organic oil fatty acid includes a blend of food grade oils including at least walnut oil, almond oil, sunflower oil, safflower oil and canola oil. Especially, the blending proportions of food grade oils preferably include at least 1/3 walnut oil, 1/3 almond oil, and 1/3 canola oil.

Further, the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 is complexed with the at least one activated organic oil fatty acid under heat and pressure in a closed vessel in the presence of a copper containing catalytic material surface. Especially, the two components are complexed under a heat of 10 to 200 °C and a pressure of 1 to 150 atm for a period of time between one minute and twenty-four hours.

While the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 includes a hydrofluoroolefin blend comprising hydrofluoroolefin and R-134A, a hydrofluoroolefin blend including R-448A having 21% by weight of R-134A, 26% by weight of R-32, 26% by weight of R-125, 20% by weight of R-1234yf, and 7 % by weight of R-1234ze is also contemplated. Further use of R-449A, having 25.7% by weight of R-134A, 24.3% by weight of R-32, 24.7% by weight of R-125, 25.3% by weight of R-1234yf, also finds utility.

Therefore, in accordance with the present invention, a refrigerant composition comprising a heat transfer fluid such as HFO and like compositions is disclosed comprising a coordination entity with a refrigerant solvent and a fatty acid solute including at least one activated organic oil and a heat transfer fluid, and where the coordination entity is an energy saving refrigerant composition. Preferably the at least one activated organic oil comprises at least one oleic acid and at least one linoleic acid. The composition comprises a heat transfer fluid to activated oil blend ratio of between 95:5 and 99:1 by weight percent. Depending on the suitability of oil blends, blending is achieved by mixing, blending at high speeds with a mixer, and combinations of low and high speed blending. Some aspects of the present invention are desirable after high speed blending of the oil blend compositions with a nano-mixer to achieve minimal nano-particle sizes.

INDUSTRIAL APPLICABILITY

The present invention finds utility in refrigeration systems, air conditioning units, medical applications and other industrial applications.

Claims

1. A low GWP heat transfer fluid coordination entity, comprising: at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500, including a coordination entity composition comprising at least one heat transfer fluid including at least hydrofluoroolefm, and being complexed under heat and pressure in a closed vessel with at least one activated organic oil fatty acid in the presence of a catalytic material surface.

2. The coordination entity of claim 1, wherein the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 includes hydrofluoroolefm blends, singly or in combination with any hydrofluorocarbon thereof.

3. The coordination entity of claim 2, wherein the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 includes a hydrofluoroolefm blend comprising hydrofluoroolefm and R-134A.

4. The coordination entity of claim 3, wherein the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 includes R-448A having 21% by weight of R-134A, 26% by weight of R-32, 26% by weight of R-125, 20% by weight of R-1234yf, and 7 % by weight of R-1234ze.

5. The coordination entity of claim 3, wherein the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 includes R-449A having 25.7% by weight of R- 134A, 24.3% by weight of R-32, 24.7% by weight of R-125, 25.3% by weight of R-1234yf.

6. The coordination entity of claim 1, wherein the at least one activated organic oil fatty acid includes at least walnut oil.

7. The coordination entity of claim 6, wherein the at least one activated organic oil fatty acid includes at least walnut oil and canola oil.

8. The coordination entity of claim 7 wherein the at least one activated organic oil fatty acid includes at least walnut oil, almond oil and canola oil.

9. The coordination entity of claim 8, wherein the at least one activated organic oil fatty acid includes a blend of food grade oils including at least walnut oil, almond oil, sunflower oil and canola oil.

10. The coordination entity of claim 8, wherein the at least one activated organic oil fatty acid includes a blend of food grade oils including at least 1/3 walnut oil, 1/3 almond oil, and 1/3 canola oil.

11. The coordination entity of claim 1, wherein the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 is complexed with the at least one activated organic oil fatty acid under heat and pressure in a closed vessel in the presence of a copper containing catalytic material surface.

12. The coordination entity of claim 11, wherein the at least one low GWP feedstock heat transfer fluid having a GWP value of less than 1500 is complexed under a heat of 10 to 200 °C and a pressure of 1 to 150 atm for a period of time between one minute and twenty-four hours.