WO2013134603A1 - Complexes d'halogénoalcène - Google Patents

Complexes d'halogénoalcène Download PDF

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Publication number
WO2013134603A1
WO2013134603A1 PCT/US2013/029786 US2013029786W WO2013134603A1 WO 2013134603 A1 WO2013134603 A1 WO 2013134603A1 US 2013029786 W US2013029786 W US 2013029786W WO 2013134603 A1 WO2013134603 A1 WO 2013134603A1
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Prior art keywords
oil
composition
activated
organic
fatty acid
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PCT/US2013/029786
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English (en)
Inventor
Bob Lee DAVIS
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Davis Bob Lee
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Priority claimed from US13/731,608 external-priority patent/US20130234059A1/en
Priority claimed from US13/774,908 external-priority patent/US20130233001A1/en
Priority claimed from US13/774,838 external-priority patent/US20130234061A1/en
Priority claimed from US13/774,751 external-priority patent/US20130234060A1/en
Priority claimed from US13/774,950 external-priority patent/US20130233012A1/en
Application filed by Davis Bob Lee filed Critical Davis Bob Lee
Priority to CA2866711A priority Critical patent/CA2866711A1/fr
Priority to EP13758697.0A priority patent/EP2823012A1/fr
Publication of WO2013134603A1 publication Critical patent/WO2013134603A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the field of the invention is haloalkene complexes, and more specifically haloalkene complexes for use as a refrigerant composition, and especially in refrigeration systems.
  • Existing commercially available refrigerant compositions generally comprise specific chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs), and can have some uses beyond refrigeration.
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • HFCs hydrofluorocarbons
  • U.S. Patent Application Publication No. 2007/0092545 to Bale teaches an aerosol coolant spray comprising an essential oil, HFC, and diluent material, for killing and removing ticks.
  • Bale apparently fails to teach a complex formed via activation of the mixture.
  • Van Horn and Bale each fail to address the global warming concerns associated with refrigerant compositions and do not appear to teach the user of a catalyst in producing a refrigerant composition.
  • compositions, apparatus, systems and methods of haloalkene complexes that can be used for refrigeration, heating, air conditioning, or any other commercially suitable uses.
  • haloalkene complex means two or more molecules held together through Van der Waals forces (also known as Van der Waals interactions), wherein at least one of the molecules is a haloalkene, or at least one molecule is a haloalkane and at least one molecule is an alkene.
  • the complex is formed upon activation, in a controlled environment, of at least one of the molecules. It is contemplated that a haloalkene complex's molecular arrangement can change when pressure is increased or decreased.
  • a composition comprises a polar heat transfer fluid, such as a hydro fluorocarbon, complexed with an organic oil fatty acid.
  • organic oil fatty acid can include a fatty acid of an organic oil or a fatty acid of an organic oil blend.
  • the heat transfer fluid is complexed with at least some of the organic oil fatty acid through Van der Waals forces, upon activation of the fatty acid under heat and pressure.
  • a polar heat transfer fluid can be complexed with at least 1, 5, or even 10 or more % of a first organic oil of a composition. This complexing can exist between polar heat transfer fluid molecules and fatty acids of the oil blend via Van der Waals forces.
  • the fatty acid molecules of an oil blend are activated in an open or closed vessel under heat and pressure.
  • a composition made by this complexing can comprise approximately 95-99 weight percent (wt%) of the polar heat transfer fluid, and approximately 1-5 wt% of the oil blend.
  • the composition can comprise an oil blend to polar heat transfer fluid ratio of 1 : 99 or 5:95, or any ratio in between.
  • polar heat transfer fluid to oil blend including for example: 0.1 : 99.9; 10:90; 25:75; 50:50; 75:25; or 99: 1 (e.g., where a small amount of polar heat transfer fluid is included with the oil blend, in the vessel, under heat and pressure, etc.), among others.
  • oil complexes contemplated herein include food and other natural oils, as well as synthetic oils.
  • fatty acid refers to a substituted or non-substituted, saturated or unsaturated, carboxylic acid with a long aliphatic tail (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.
  • 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.
  • At least .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 of a composition 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 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 a composition.
  • 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.
  • the fatty acid(s) compose at least one food oil of an oil blend, including for example, walnut, canola, sunflower or almond oil.
  • the polar heat transfer fluid can comprise any commercially suitable heat transfer fluid, but is preferably a hydro fluorocarbon, and even more preferably a halo-ethane such as a tetrafluoroethane.
  • At least one of the organic oil(s), the fatty acid(s) and the polar 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 20°C, 30°C, 50°C, 100°C, 150°C, or even 200°C or more.
  • contemplated pressures include at least any of 1.5 atm, 5 atm, 10 atm, 25 atm, lOOatm, or even 150 or more atm.
  • oil blend is activated (e.g., in a closed vessel having a catalyst)
  • the oil blend can be a composition of the inventive subject matter, even without the addition of a polar heat transfer fluid.
  • a small amount of polar heat transfer fluid can be added before or during activation of an oil blend such that at least some of the polar heat transfer fluid molecules are complexed with a fatty acid molecule of the activated 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. [0022] It is contemplated that a composition of the inventive subject matter can have a superior compressibility factor than existing refrigerants and refrigerant compositions.
  • 0.1 to 95 wt% of 1,1,1,2- tetrafluoroethane (also known as r-134a) is mixed with 27 to 99.9 wt% of one or more organic oil(s), and at least 0.1 % of the r-134a is complexed with some of the organic oil(s) via Van der Waals forces (e.g., the r-134a interacts 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).
  • an absorptive process can occur wherein the r-134a is complexed to the fatty acid(s) of the organic oil(s) via a Van der Waals force 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 an r-134a molecule 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 r-134a.
  • the r-134a can be mixed with 27 to 99.9 wt% of at least two different organic oils.
  • the first and second organic oils can be activated in a tubing apparatus under a heat of 15 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 r-134a, or can occur with r-134a already mixed with the first and second organic oils (e.g., the oils and at least some of the r- 134a can be activated and complexed within the apparatus). It is also contemplated that the oils can be activated first, and mixed / complexed with r-134a at a later time (ranging from immediately after activation to days, months, or even years later).
  • Fig. 1 is a schematic illustrating the production of a composition of the inventive subject matter.
  • Fig. 2A shows the chemical structure of a fatty acid molecule (oleic acid).
  • Fig. 2B is a front perspective view of a r-134a molecule complexed with an fatty acid molecule (oleic acid).
  • Fig. 2C is a top perspective view of a r-134a molecule complexed with a fatty acid molecule (oleic acid).
  • Fig. 3 is a schematic of a r-134a molecule.
  • Fig. 4 is a chart showing a side by side comparison of 3 ton units running
  • Fig. 5 is a chart showing a side by side comparison of 3 ton units running
  • Fig. 6 is a schematic of a typical refrigeration cycle.
  • inventive subject matter provides many example embodiments of the inventive subject matter. Although each embodiment 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 embodiment comprises elements A, B, and C, and a second embodiment 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.
  • inventive subject matter should be interpreted to also include a refrigerant composition comprising a polar heat transfer fluid that is passed through a catalyst in an open or closed vessel.
  • inventive subject matter should also be interpreted to also include an activated oil blend that can be used with various other fluids (e.g., non-heat transfer fluids) having molecules that are sufficiently polar to complex with a fatty acid of the activated oil blend. Examples include hydraulic oils, antifreeze or other suitable fluids having a liquid or gas composition that dissipates heat in mechanical environments.
  • Figure 1 is a schematic illustrating how a composition of the inventive subject matter could be made.
  • First, second and third fatty acids (110, 120, 130) composing at least one of first, second and third organic oils are combined and processed under heat and pressure, in processing apparatus 135 having a controlled environment, to form an activated blend 140 of organic oils.
  • 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.
  • a predetermined material can comprise material that the processing apparatus composes (e.g., copper, iron, steel, wood, plastic, etc.), or a catalyst inserted into the processing apparatus.
  • a predetermined temperature or pressure can be the
  • 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.
  • 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, and a-linolenic acid.
  • 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.).
  • an "organic oil” is any oil produced by plants, animals, and other organisms through natural metabolic processes other than crude oil or petroleum-based oils.
  • Contemplated food oils include walnut oil, almond oil, canola oil, flaxseed 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, or any other suitable food based oil.
  • a composition having only a 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.
  • a composition having only (or predominantly) oleic acid can have less than, twice as many, or even three times or more fatty acids than a composition having only (or predominantly) linoleic acid, or some other acid.
  • oils that can be activated and complexed with a polar 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.).
  • the activated blend 140 can be infused, injected into, or otherwise combined with first heat transfer fluid 150 to produce composition 160 comprising a halo-alkene complex having Van der Waals interactions.
  • first heat transfer fluid 150 a small amount of the heat transfer fluid could have been mixed with the fatty acids in the processing apparatus, and complexed therein upon activation of the fatty acids.
  • Van der Waals force or “Van der Waals interaction” means the sum of the attractive or repulsive forces between molecules (or between parts of the same molecule), other than those due to covalent bonds, or the electrostatic interaction of ions with one another or with neutral molecules. It is true that some authorities use the term more narrowly to exclude hydrogen bonding, but as used herein the term can include hydrogen bonding, forces between two permanent dipoles (Keesom force), forces between a permanent dipole and a corresponding induced dipole (Debye force), and forces between two
  • All commercially suitable heat transfer fluids are contemplated, including for example, 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.
  • a composition of the inventive subject matter can be used in an existing refrigeration system that is compatible with r-134a, r-407, r-410 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.
  • a composition of the inventive subject matter can be added to a system without complete removal of a prior refrigerant from the system.
  • 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-407, r-410, r-22, etc.).
  • an inferior refrigerant or refrigerant composition such as r-134a, r-407, r-410, r-22, etc.
  • a composition of the inventive subject matter could be used in a novel unit comprising a different ratio of compressor size to coil size.
  • 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.
  • a new unit can have a greater number of, or a different configuration of, coils.
  • composition of the inventive subject matter is the novel BluonTM
  • Bluon TdX comprises a mixture of approximately 95-99 wt% of 1, 1, 1, 2- Tetrafluoroethane (i.e., r-134a) at least partially complexed with approximately 1-5 wt% of BlTM, 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. It can be preferred that the ratio of oleic acid to linoleic acid is approximately 60:40 wt%.
  • a composition can comprise an oil blend comprising an oleic acid to linoleic acid ratio of up to approximately 0.1 : 1, 0.5: 1, 2: 1, or even 60: 1 or more.
  • the organic oils of Bl can include one or more of a canola oil, a walnut oil, an almond oil, and a sunflower oil, among others ("the Bl oils”).
  • One contemplated Bl blend comprises walnut, almond and canola oils (“CAW Bl blend”).
  • Another contemplated Bl blend comprises canola and sunflower oil (“CS Bl blend”), preferably at an approximate ratio of between 5: 1 and 1 :3, and even more preferably at an approximate ratio of between 5: 1 and 2: 1 (e.g., 3: 1).
  • Yet another contemplated Bl blend comprises walnut, almond and canola oils, and a small amount of r-134a.
  • FIG. 2A A perspective view of a fatty acid molecule composing a preferred oil blend of the inventive subject matter (e.g., Bloil blend) is shown in Figure 2A.
  • Figures 2B-2C Perspective views of a r- 134a molecule complexed with a fatty acid molecule are shown in Figures 2B-2C.
  • the complexing can occur in two steps.
  • the first step occurs when the two positively charged hydrogen atoms of r-134 Van der Waals interact with an exposed negatively charged double carbon bond, to form a shared triad/quad. This is a relatively weak form of Van der Waals interaction and relies on surface reaction chemistry to form. This relatively weak interaction could explain an observed effervescence.
  • a second stage bonding apparently occurs when the extremely negatively charged fluoride, attached to the same carbon of the r-134a with the two hydrogens, then bonds to the two positively charged hydrogen atoms which are attached to the two carbons of the double carbon bond.
  • a synergistic effect of the two oppositely charged/aligned triads can have an overall strengthening effect and could lock in this multi-interaction.
  • any commercially suitable refrigerant(s) can be infused with any suitable oil or oil blend comprising a fatty acid to produce a composition of the inventive subject matter.
  • any commercially suitable refrigerant(s) can be infused with any suitable oil or oil blend comprising a fatty acid to produce a composition of the inventive subject matter.
  • the activated oils and specific complexes discussed in detail herein are only some of the possible compositions of the inventive subject matter.
  • R-134a has been shown experimentally to provide the most significant improvement in refrigeration efficiency when mixed with the oils of a Bl oil blend, possibly due to its highly polar nature as compared with other refrigerants.
  • a mixture comprising approximately 95-99 wt% of r-134a and approximately 1-5 wt% of Bl (which can also include approximately 50% of an oleic acid and 33% of a linoleic acid) was found to be very efficient.
  • the Bl oils of one possible Bl 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 Bl blend (comprising precursor/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.
  • 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.
  • COOH carboxyl group
  • a triglyceride can have different types of oils in various arrangements attached to it. Oleic fatty acids in some plants tend to be mostly bonded in di-glycerides, especially those derived from rapeseed oil (Canola Oil).
  • Mono-glycerides are only present in significant amounts in a few plants, such as peanuts.
  • a catalyst can be used to cause a reaction between the r-134a and a fatty acid.
  • r-134a When 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.
  • the singly bonded carbons In the liquid oil, the singly bonded carbons can spin relative to each other many thousands of times a second. In the 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 measurable signature of the r-134a in the oil measurably increased when used in an air conditioning unit.
  • the signature appears to increase along with the repeated mixing of the oil and r-134a through normal machine operations.
  • a noticeable increase in viscosity and change in color can also occur with an increasing r-134a signature.
  • An end of r-134a that sticks out can apparently form ever shifting double hydrogen bonds with the numerous hydrogen atoms of other oil molecules, which increases viscosity.
  • the complexing apparently does not remove or replace any atoms on either the r-134a or fatty acid molecules, as the signatures of both molecules remained.
  • Bluon TdX shows a slight presence of two quartets at 4.7 and 4.58 in the H-NMR, indicating r-134a bonding.
  • Bluon TdX that was used for 120 days showed much more pronounced quartets at these sites. This shows more r-134a is binding to the oils over time, indicating that Bluon TdX grows even better with use, at least up to a certain point.
  • the molecular Van der Waals behavior of these new halo-alkenes also has been shown to change over time.
  • the halo-alkene Bluon TdX recovered from unused samples is a clear yellow viscous liquid. This clear yellow color indicates whatever bonded water existed in the CAW Bl blend, has been expunged.
  • the Bluon TdX liquid is also more viscous than the CAW Bl, flowing at a noticeably slower rate.
  • the blue-green color of the 120 day used Bluon TdX indicates that as more r-134a binds to the oils, intra-molecular (resonant frequencies) rise, along with viscosity. In testing of the fresh Bluon TdX, the oil was very hydrophobic and would not mix with any amount of water.
  • 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 (e.g., r-134a, r-410, r-22, etc.).
  • conventional refrigerants e.g., r-134a, r-410, r-22, etc.
  • sensor arrays and data streams recorded show that Bluon TdX 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.
  • Bluon TdX can keep a space colder or hotter for longer periods of time than existing refrigerants or refrigerant compositions.
  • a system utilizing Bluon TdX or other composition of the inventive subject matter can provide the same cooling or heating as a system utilizing r-410, while running for approximately 10-30 minutes less per hour.
  • compositions of the inventive subject matter can produce significantly less condensation off evaporate coils.
  • an r-410a charged system had an evaporator coil temperature of 55.2 degrees F and condensate of 5.75 gallons
  • a Bluon TdX charged system had an evaporator coil temperature of 51.4 degrees F and condensate of 1 gallon. This phenomenon of reduced condensation was observed in each Bluon TdX charged air conditioning system. This highly unusual electron resonant effect appears to contribute in making Bluon TdX a novel and very unique halo-alkene.
  • R-134a is unique among the fluorocarbon refrigerants, in that it is also used as a solvent in the pharmaceutical industry. This solvent ability is due to the polar nature of its molecule as shown in Figure 3. One side of the molecule has the negatively charged fluoride atoms, while the other side has the positively charged hydrogen. The polar nature of water also makes it an excellent solvent.
  • Figure 4 is a series of charts representing a side by side comparison of two 3 ton units, one running continuously using Bluon TdX, and the other running continuously r-22 refrigerant.
  • the Bluon TdX comprises a CAW Bl oil blend.
  • Figure 5 is a series of charts representing a side by side comparison of two 3 ton units, one running continuously using Bluon TdX, and the other running continuously r-410a refrigerant.
  • the Bluon TdX comprises a CAW Bl oil blend.
  • air conditioning systems generally utilize a refrigerant cycle having two main parts, the condenser cycle and the evaporator cycle.
  • 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, were a fan blows cooled air into the controlled environment and the gas is warmed.
  • the oil blend in the Bluon TdX 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.
  • the r-134a is driven into a liquid at the compressor and also likely dissolves more rapidly into the Bluon TdX oil blend, than a mineral oil. At this higher pressure, Van der Waals forces would likely complex the r-134a to the oils, in much the same manner the oils are bonded to each other in a liquid state.
  • the cooled liquid After leaving the condenser, the cooled liquid reaches the expansion value and the r- 134a can begin its transition into a gas.
  • the phase transition can be driven to completion in the evaporator coils. This is also likely where a secondary cause of increased efficiencies of compositions of the inventive subject matter (e.g., Bluon TdX) is found. It is a unique physical process likely dependent on r-134a's polar interaction with the structure of the particular oils. Some preparatory discussion is necessary to delve into this unique process.
  • R-134a is only two carbon units long and its heat capacity is 1.34 kJ/(kg » K). Although smaller than Oleic acid, the key to r-134's usefulness is its heat of vaporization at
  • these organic oil fatty acids can 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.
  • r-134a the relevant value is heat of vaporization at approximately -15.3°F.
  • the expansion valves on standard air conditioner units are generally 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 r-134a is not going to reach its full potential cooling, but will vaporize above the melting points of the high acid oils.
  • the oils in the Bluon TdX are generally almost always or always going to be liquid, although some atomization likely occurs at the expansion valve.
  • This surface binding feature is also apparently responsible for the observed reduced refrigerant composition leakage from the air conditioning units.
  • Most air conditioning system components were designed to use the larger Freon 113 (C 2 CI 3 F 3 ), until it was banned due to it possibly damaging the ozone layer.
  • the significant leakage problems with r-410a or r-134a are due to their smaller molecular geometry than the Freon 113 they were designed to replace.
  • the fluorine atoms of r-410a and r-134a are much smaller than the chlorine atoms of Freon 113.
  • Air conditioning systems charged with r-410a typically leak around 20% of the coolant into the atmosphere annually, r-134a has a slightly lower leakage rate.
  • Bluon TdX partially or substantially seals the system utilizing it, and reduces the need to recharge the system. Moreover, a system can be charged with approximately 35-50% less
  • Bluon TdX and other compositions of the inventive subject matter have the potential to help solve their problem from several angles.
  • An important factor to achieve this is the inventive subject matter's (e.g., Bluon TdX's) ability to significantly reduce leakage in air conditioning systems.
  • Most automobile air conditioning systems will have several recharges over their lifetimes and Direct Emissions can be up to 40% of their Total Equivalent Warming Impact (TEWI).
  • TEWI Total Equivalent Warming Impact
  • An average quality automobile air conditioning system will lose around 12% of its refrigerant annually. From operating the test units using Bluon TdX, observed leakage is greatly reduced. If leakage could be reduced 90%> by Bluon TdX, total TEWI in automobile air conditioning systems could be reduced by 35%.
  • a refrigerant composition comprises a polar heat transfer fluid, such as 1,1,1,2-tetrafluoroethane, which is passed through an open or closed vessel containing a catalyst.
  • a polar heat transfer fluid such as 1,1,1,2-tetrafluoroethane
  • the polar heat transfer fluid (or mixture described below) can be passed through a vessel under heat of at least 15°C, 20 °C, 50 °C, or even 100 °C or more, or a pressure of at least 1.25 atm, 5 atm, 25 atm, or even 150 or more atm.
  • the catalyst can comprise at least one of a copper, a polyamide (e.g., Nylon, etc.), or a stainless steel.
  • a composition of the inventive subject matter can comprise a mixture of a polar heat transfer fluid with a long chain fatty acid (i.e., fatty acid having more than 12 carbon molecules) preferably activated by the catalyst.
  • Preferred long chain fatty acids are oleic and linoleic acids, which can advantageously be derived from or included in one or more food oils, including for example walnut oil, almond oil, sunflower oil, or canola oil.
  • a catalyst in the vessel can activate the fatty acid to allow for complexing with polar heat transfer fluid molecules.
  • a haloalkene complex can result.
  • Some contemplated haloalkene complexes can comprise a ketone or an ester.
  • a mixture that is passed through a vessel can comprise any suitable wt/wt ratio of the food oil to polar heat transfer fluid, including for example, 10: 1, 20: 1, 50: 1, 75: 1, or even 99: 1 or more.
  • the polar heat transfer fluid can comprise 10, 5, 1, or even 0.1 or less wt percent of the mixture passed through the vessel.
  • the mixture upon exiting a vessel comprising a catalyst, can be further mixed with any other suitable fluid, including for example, additional amounts of polar heat transfer fluid to thereby obtain a composition of the inventive subject matter.
  • inventive subject matter also provides compositions, apparatus, systems and methods in which an activated oil blend having fatty acid molecules configured to complex with a molecule of another fluid is manufactured.
  • an "oil blend” should be interpreted broadly to include, for example, a composition comprising two or more different types of oils, as well as a composition comprising one type of oil derived from different sources. Thus, it is
  • an oil blend can comprise only one type of oil (e.g., a walnut oil) that is extracted from two or more different sources (e.g., two different walnuts).
  • a walnut oil e.g., a walnut oil
  • Activated oil blends of the inventive subject matter can be manufactured by placing a catalyst and one or more precursor oils in a vessel, and circulating the precursor oil(s) in the vessel with the catalyst.
  • Some preferred catalysts include copper, a polyamide such as Nylon, and stainless steel. However, all catalysts effective to prepare a fatty acid molecule for complexing with another molecule are contemplated.
  • Contemplated oils for use in the claimed subject matter include long chain fatty acids, especially oleic and linoleic acids.
  • Food oils containing long chain fatty acids include, among other things, canola oil, walnut oil, sunflower oil, flaxseed oil, and almond oil.
  • an oil blend comprises oleic and linoleic acids
  • the oleic acid and linoleic acid can be present in a weight to weight (wt/wt) ratio of between 80:20 and 20:80, a ratio of between 70:30 and 50:50, or any other suitable ratio.
  • oils for use in the claimed subject matter can alternatively or additionally comprise other types of fatty acids, including for example, linolenic acid or palmic acid.
  • a contemplated oil blend can comprise: (1) at least 10 wt%, at least 20 wt% or even at least 30 wt% or more of an oleic acid (2) at least 5 wt%, at least 10 wt%, or even at least 20 wt% or more of a linoleic acid, (3) at least 1 wt%, at least 2 wt%, or even at least 5 wt% or more of a linolenic acid; (4) at least 1 wt%, at least 2 wt%, or even at least 5 wt% or more of a palmic acid; or (5) any combination thereof.
  • a refrigerant composition of the inventive subject matter can comprise a mixture, such as the ones described above, wherein at least some of the mixture is blended in a vessel containing a catalyst.
  • the refrigerant compositions comprise haloalkene complexes formed of molecules of a mixture of the inventive subject matter.
  • a user can manufacture, purchase or otherwise obtain a refrigerant composition of the inventive subject matter, and add a sufficient amount of the refrigerant composition to a refrigeration system or unit to improve operation of the refrigeration system.
  • a user is adding a refrigerant composition of the inventive subject matter to an existing refrigeration system or unit, it is contemplated that the user can optionally at least partially remove a previously utilized commercial refrigerant from the unit prior to adding the novel refrigerant composition.
  • the term "at least partially remove” should be interpreted broadly to include, for example, complete removal, substantially complete removal, or even removal of at least 25%, at least 50%, or even at least 75%.
  • the user can at least partially remove the previously utilized commercial refrigerant using any suitable method, including for example, vapor recovery or liquid recovery methods.
  • Operation of a refrigeration system can be improved by adding a novel refrigerant composition comprising a mixture of activated long chain fatty acids with a polar heat transfer fluid. Activation is preferably accomplished by blending a mixture of the oils and the heat transfer fluid in a vessel containing a catalyst.
  • Contemplated improvements can include, among other things, a reduction in power consumption, a reduction in evaporator coil condensation, or a reduction in leakage of operating fluid.
  • the pressures and concentrations of the operating fluid can be such that the oil blend is a liquid upon exiting the condenser, and a gas when exiting the evaporator.
  • a method of the inventive subject matter can improve operation of the refrigeration system in at least one of the following ways: (1) reducing power consumption of a refrigeration unit relative to a given load on a month over month basis (e.g., by at least 10%>, by at least 25%, by at least 45%, by at least 50%, etc.); (2) reducing evaporator coil condensation rate of a refrigeration unit relative to a given load on a month over month basis (e.g., by at least 10%, by at least 25%, by at least 45%, by at least 50%, etc.); or (3) reducing leakage of operating fluid from a refrigeration unit relative to a given load on a month over month basis (e.g., by at least 10%, by at least 25%, by at least 45%, by at least 50%, etc.).
  • Activated oil blends can optionally be manufactured to include a hydrocarbon, such that fatty acid molecules are activated and complexed with the hydrocarbon in a vessel having a catalyst.
  • Preferred hydrocarbons can comprise hydro-halo-carbons such as a hydro fluorocarbon heat transfer fluid.
  • hydro fluorocarbon includes r-134a, chemically known as 1,1,1,2-tetrafluoroethane.
  • the hydro-halo-carbon can comprise at least 20 wt%, at least 50 wt%, at least 75 wt%, or even at least 90 wt% or more of an operating fluid.
  • an activated oil blend comprises a hydrocarbon
  • oil blends of the inventive subject matter can be injected into or otherwise mixed with larger quantities of hydrocarbon.
  • an activated oil blend can be combined with r-134a molecules that are configured to complex with the activated fatty acid molecules of the oil blend to thereby produce a refrigerant composition.
  • the inventive subject matter also provides refrigeration systems in which an operating fluid is moved between a condenser and an evaporator, and the operating fluid preferably comprises an activated oil blend and a polar heat transfer fluid.
  • Refrigeration systems are configured to utilize an operating fluid comprising an activated oil blend.
  • the activated oil blend can comprise one or more precursor oils that are blended in a closed vessel containing a catalyst.
  • Preferred operating fluids also comprise a polar heat transfer fluid such as r-134a, wherein at least some of the polar heat transfer molecules are complexed to a component of the activated oil blend.
  • the ratio of one fatty acid to 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 embodiments, a chemical marker can also be included.
  • Coupled to is intended to include both direct coupling (in which two elements that are coupled to each other contact each other) and indirect coupling (in which at least one element is interposed between the two elements). Therefore, the terms “coupled to” and “coupled with” are used synonymously. [00105] It should be noted that one having ordinary skill in the art should realize that all numbers herein are approximates, regardless or whether or not the numbers are preceded by the word “approximately”.
  • the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some
  • embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne des compositions comprenant un mélange d'huile activé. La présente invention concerne en outre des compositions comprenant un complexe d'halogénoalcène, qui peuvent être utilisées en tant que réfrigérant, et des compositions comprenant un fluide de transfert thermique polaire qui est passé à travers une cuve contenant un catalyseur. Des catalyseurs préférés peuvent comprendre du cuivre, du polyamide, de l'acier inoxydable, ou une combinaison de ceux-ci. Les compositions peuvent être utilisées pour augmenter l'efficacité énergétique et réduire les taux de fuite de systèmes de réfrigération. Certaines compositions comprennent au moins 0,1 % en poids d'un acide gras d'huile oléique, 0,1 % en poids d'un acide gras d'huile linoléique, et au moins 98 % en poids de r-134a. Au moins une partie du r-134a peut être complexée avec au moins un des acides gras d'huile organique.
PCT/US2013/029786 2012-03-09 2013-03-08 Complexes d'halogénoalcène WO2013134603A1 (fr)

Priority Applications (2)

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CA2866711A CA2866711A1 (fr) 2012-03-09 2013-03-08 Complexes d'halogenoalcene
EP13758697.0A EP2823012A1 (fr) 2012-03-09 2013-03-08 Complexes d'halogénoalcène

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US201261608954P 2012-03-09 2012-03-09
US61/608,954 2012-03-09
US13/731,608 US20130234059A1 (en) 2012-03-09 2012-12-31 Haloalkene Complexes
US13/731,608 2012-12-31
US13/774,908 US20130233001A1 (en) 2012-03-09 2013-02-22 Method of Increasing Efficiency of a Refrigeration System
US13/774,908 2013-02-22
US13/774,950 2013-02-22
US13/774,838 US20130234061A1 (en) 2012-03-09 2013-02-22 Method of Manufacturing an Oil Blend
US13/774,838 2013-02-22
US13/774,751 2013-02-22
US13/774,751 US20130234060A1 (en) 2012-03-09 2013-02-22 Refrigerant Compositions
US13/774,950 US20130233012A1 (en) 2012-03-09 2013-02-22 Refrigeration Systems

Publications (1)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0629687A1 (fr) * 1990-01-31 1994-12-21 Tonen Corporation Esters utilisés comme lubrifiants pour réfrigérant à base d'alkane halogéné
US20020017629A1 (en) * 2000-08-02 2002-02-14 Benjamin Mosier Transesterification composition of fatty acid esters, and uses thereof
US20040206491A1 (en) * 2003-04-17 2004-10-21 Vanderbilt University And Tennessee Valley Authority Compositions with nano-particle size conductive material powder and methods of using same for transferring heat between a heat source and a heat sink
US20070082112A1 (en) * 2005-09-02 2007-04-12 Frank Kincs Edible oils and methods of making edible oils
US20100243969A1 (en) * 2009-03-27 2010-09-30 E. I. Du Pont De Nemours And Company Dielectric heat-transfer fluid
US20110012052A1 (en) * 2008-03-07 2011-01-20 Van Horn Brett L Halogenated alkene heat transfer composition with improved oil return

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0629687A1 (fr) * 1990-01-31 1994-12-21 Tonen Corporation Esters utilisés comme lubrifiants pour réfrigérant à base d'alkane halogéné
US20020017629A1 (en) * 2000-08-02 2002-02-14 Benjamin Mosier Transesterification composition of fatty acid esters, and uses thereof
US20040206491A1 (en) * 2003-04-17 2004-10-21 Vanderbilt University And Tennessee Valley Authority Compositions with nano-particle size conductive material powder and methods of using same for transferring heat between a heat source and a heat sink
US20070082112A1 (en) * 2005-09-02 2007-04-12 Frank Kincs Edible oils and methods of making edible oils
US20110012052A1 (en) * 2008-03-07 2011-01-20 Van Horn Brett L Halogenated alkene heat transfer composition with improved oil return
US20100243969A1 (en) * 2009-03-27 2010-09-30 E. I. Du Pont De Nemours And Company Dielectric heat-transfer fluid

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CA2866711A1 (fr) 2013-09-12

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