WO1997020902A1 - Melange refrigerant ameliore et son procede d'utilisation dans des systemes de refrigeration - Google Patents

Melange refrigerant ameliore et son procede d'utilisation dans des systemes de refrigeration Download PDF

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Publication number
WO1997020902A1
WO1997020902A1 PCT/US1995/015643 US9515643W WO9720902A1 WO 1997020902 A1 WO1997020902 A1 WO 1997020902A1 US 9515643 W US9515643 W US 9515643W WO 9720902 A1 WO9720902 A1 WO 9720902A1
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WIPO (PCT)
Prior art keywords
percent
butane
refrigerant
point
liquid volume
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Ceased
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PCT/US1995/015643
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English (en)
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Gary Lindgren
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Individual
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Individual
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Priority to PCT/US1995/015643 priority Critical patent/WO1997020902A1/fr
Publication of WO1997020902A1 publication Critical patent/WO1997020902A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09K5/042—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 compounds containing carbon and hydrogen only
    • 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
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures
    • C09K2205/42—Type R12
    • 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

  • This invention relates to a novel, improved refrigerant mixture and its use in refrigeration systems.
  • the refrigerant mixture is not harmful to the ozone layer, and is particularly applicable in systems such as automobile air-conditioning and home refrigeration.
  • R-12 also commonly known as dichlorodifluoromethane.
  • R-12 and other fluorchlorocarbon refrigerants can contribute to the formation of acids under as a result of decomposition in a refrigerant system. Formation of such acids is not uncommon, and when it occurs, severe damage to metal surfaces in a refrigerant system can result. Moisture in an R-12 based refrigeration system can contribute to such acid formation, as can use of contaminated lubricating oils.
  • any new refrigerant useful as a direct replacement of R-12 could be useable without the need to change lubricating oils in the system.
  • Many of the heretofore proposed refrigerant substitutes have undesirable lubrication requirements, and may require expensive cleanup of existing systems, as well as the use of more costly refrigerant types.
  • the R-12 substitutes which have been proposed have been various substituted hydrocarbons, utilizing addition of bromine or other atoms, primarily in an attempt to produce a non- flammable refrigerant.
  • Such substitutes have their own problems, such as undesirable toxicological effects on exposed individuals, particularly with respect to products (and incomplete products) of combustion.
  • the refrigerant may be used as a direct, "drop-in" substitute for R-12 in automotive air conditioning and in home refrigeration units. Such use results in significant energy savings, normally on the order of an ten (10) to twelve (12) percent reduction in power consumption while delivering equivalent refrigeration capacity.
  • the refrigerant provides a significant, demonstrated improvement with regard to protection against release of ozone depleting compounds. Another important feature is the fact that my refrigerant is not conducive to formation of undesirable acid compounds while in use in a refrigeration system. This provides a unique safety feature when compared to many previously known refrigerants used in automotive air conditioning and home refrigeration applications.
  • my novel refrigerant mixture are propane and butane.
  • a mixture from about forty eight and one-half (48.5) to about sixty five point seven (65.7) percent propane by liquid volume, and forty four (44) to about thirty two point six (32.6) percent butane by liquid volume is desirable.
  • Other components of my novel refrigerant mixture include about one and one-half (1.5) percent to about two (2.0) percent ethane by liquid volume, and about one point seven (1.7) to about two point three (2.3) percent by liquid volume of a preselected friction reducing petroleum based oil fortifying composition.
  • the petroleum based oil fortifying composition includes about forty to sixty (40-60) percent by liquid volume of chloro paraffin waxes and hydrocarbon waxes, and about twenty to thirty five (20- 35) percent of a chlorinated octadecanoic acid, and about five to fifteen (5-15) percent of zinc salts of phosphorodithioic acid,0,0-di-Cl-14-alkyl esters, and about fifteen to twenty (15-20) percent of a hydrogenated 1-decene homopolymer.
  • my invention is the discovery that a mixture of propane, butane, ethane, and friction fighting petroleum oil fortifiers may be directly substituted for R-12 in an existing refrigeration system at great energy saving advantage when compared to other proposed replacements. Also, my refrigerant mixture provides superior physical properties, as well as improved compatibility with lubricating oils and existing materials of construction, in R-12 replacement applications.
  • Figure 1 is a process flow diagram illustrating my process of directly substituting my novel, improved refrigerant mixture in an automobile air-conditioning system.
  • Figure 2 is a process flow diagram illustrating my process of directly substituting my novel, improved refrigerant mixture in a residential refrigerator system.
  • R-12 Widely utilized refrigerant systems which heretofore typically utilize R-12 include automotive and home refrigeration systems. Although the novel, improved refrigerant mixture disclosed herein may be used in other types of refrigerant circuits, my invention will be disclosed primarily with reference to direct substitution of R-12 with my novel, improved refrigerant mixture in the above types of refrigeration systems.
  • FIG. 1 there is shown an automotive type refrigeration system 10. That type of system is commonly utilized to cool the passenger compartment of cars and trucks.
  • Critical components of the refrigeration system 10 include the compressor 11 which is used to raise the pressure (and the temperature) of a circulating refrigerant 12 from the cold, low pressure suction side 14 to the high temperature, high pressure discharge side 16 of the compressor 11.
  • the pressure of refrigerant 12 is raised by compressor 11 so that the refrigerant 12 it is capable of being condensed based at a convenient temperature and pressure in the condenser 18.
  • Actual operating temperatures and pressures will vary widely and may be reviewed in a variety of textbooks and handbooks on refrigeration.
  • the high pressure circuit (from compressor 11 discharge to expansion valve 23) may operate at about 220 to 270 pounds per square inch gauge (about 1508 to 1851 kPA)
  • the low pressure circuit (from expansion valve 23 to suction side inlet 14 of compressor 11) may operate at about 20 to 30 psig (about 137 to 206 kPA)
  • the operating conditions in the low pressure circuit correspond to a temperature of the cold, evaporating refrigerant B of roughly -6.7°C to -1.1°C (20°F to 30°F) .
  • Low pressure refrigerant 12 vapors D are compressed by compressor 11 to form high pressure vapors A, which are then condensed in condenser 18.
  • Condensed refrigerant B is then passed through a receiver 20, to accumulate the liquid refrigerant B.
  • the receiver may also include a desiccant for removal of water from the circulation refrigerant 12, so as to minimize the tendency of the refrigerant to form harmful, normally acid decomposition products, such a desiccant is not normally needed when using my refrigerant, and thus is not shown.
  • the refrigerant is metered through a thermal expansion valve 23.
  • the high pressure liquid refrigerant B is allowed to escape into the lower pressure evaporator 22, and most of the refrigerant 12 will enter as a liquid to a pool C at the bottom of the evaporator 22.
  • the liquid refrigerant boils, forming bubbles 24 which rise to become a low pressure vapor stream D. That low pressure vapor stream D travels to the low pressure side suction side 14 of the compressor 11, to repeat the process.
  • R-12 has been largely discontinued, as urged or as required by specific limitations in legislation in the United States, Europe, and elsewhere, in accord with international treaty.
  • a hydrocarbon refrigerant mixture the primary components of which are propane and butane
  • a mixture from about forty eight and one-half (48.5) to about sixty five point seven (65.7) percent propane by liquid volume, and forty four point one (44.1) to about thirty two point five (32.5) percent butane by liquid volume, is desirable.
  • my novel refrigerant mixture include about one and one-half (1.5) percent to about two (2.0) percent ethane by liquid volume, and about one point seven (1.7) to about two point three (2.3) percent by liquid volume of a preselected friction reducing petroleum based oil fortifying composition.
  • the petroleum based oil fortifying composition includes about forty to sixty (40-60) percent by liquid volume of chloro paraffin waxes and hydrocarbon waxes, and about twenty to thirty five (20-35) percent of a chlorinated octadecanoic acid, and about five to fifteen (5-15) percent of zinc salts of phosphorodithioic acid,0,0-di-Cl-14-alkyl esters, and about fifteen to twenty (15-20) percent of a hydrogenated 1-decene homopolymer.
  • These percentages of the said components are the liquid volume percentages of the overall mixture.
  • the preferred composition assumes that analysis is carried out in accord with the International Standard ISO 7941, Commercial Propane and Butane Analysis by Gas Chromotography, 1st Edition, 1988-08-01. This is the equivalent of British Standard BS7278:1990, with sample introduction of the liquid phase sample performed in accordance with the gaseous injection option of ISO 7941, Section 8.3.2.2.
  • a vapor pressure curve (vapor pressure versus temperature) for my hydrocarbon refrigerant mixture very closely approximates the vapor pressure curve for R-12.
  • my refrigerant is compatible with common materials of construction for R-12 systems, including hoses, seals, and tubing, thus eliminating concern for replacing parts in existing systems.
  • the size of the molecules in my mixture is such that leakage, primarily due to porosity of components such as hoses and seals, is minimal, when compared to other refrigerants now used, or to most other substitutes for R-12 which have been proposed.
  • n-butane ranges from about twelve point eight (12.8) percent to about seventeen point four (17.4) percent by liquid volume of the entire refrigerant mixture
  • n-butane ranges from about nineteen point seven (19.7) to about twenty six point seven (26.7) percent by liquid volume of the entire refrigerant mixture.
  • either compound may be advantageously employed in the invention as disclosed and claimed herein.
  • the aforementioned novel, improved refrigerant mixture is advantageous in that it does not contain appreciable amounts of halogens to cause problems such as acid formation and the resultant metal attack problems internal to the refrigeration circuit, as may be encountered in the case when moisture and/or oxygen contaminate a system using dichlorodifluoromethane (R- 12) .
  • both propane and butane are commonly available, at substantially lower cost than most currently available refrigerants.
  • the flammable properties of propane and butane should not cause particular concern, in the quantities required for small refrigeration circuits, in view of the substantially larger quantities of flammable fuel already successfully used, for example, in propane powered and compressed natural gas powered transport vehicles.
  • FIG. 2 A refrigerator 40 is shown having therein a compressor 42, a condenser 44, an expansion valve 46, an evaporator 48, and a low pressure vapor line 50 which returns refrigerant vapors to the compressor 42. Operation of the system is similar to that set forth above for the automotive refrigeration system, and need not be repeated in detail as it will be quickly understood by those skilled in the art and to whom this specification is addressed.
  • R-12 based refrigerator systems For reference, it is common for R-12 based refrigerator systems to operate in the range of about 120 psig (about 823 kPA) on the high pressure side, and at about 0 psig (about 0 kPA gauge) on the low pressure side.
  • the novel, improved refrigerant mixture disclosed herein provides a change of state, i.e., a boiling range and a condensing range, where the refrigerant effectively mimics the boiling point of a true single component R-12 refrigerant, to within an acceptable extent.
  • a change of state i.e., a boiling range and a condensing range
  • the heat removed at the evaporator (to provide the desired cooling or refrigeration) must be reflected by the enthalpy change of the refrigerant as it passes through the evaporator, and the refrigerant gas carrying such heat must be compressed to a pressure where it can be condensed, and the heat rejected, at the condenser.
  • dichlorodifluoromethane may be advantageously replaced by a novel hydrocarbon mixture which is substantially composed of propane and butane.
  • a mixture from about fifty seven point one (57.1) percent propane by liquid volume, and fifteen point one (15.1) percent iso-butane by liquid volume, and twenty three point two (23.2) percent n-butane by liquid volume, and about one point eight (1.8) percent ethane by liquid volume is desirable.
  • trace hydrocarbon refrigerants are present at less than one (1.0) percent by liquid volume, and such trace hydrocarbon refrigerants most preferably comprise about point one (0.1) percent by liquid volume of iso-butene, about zero point two (0.2) percent by liquid volume of 2-transbutene, and about zero point one (0.1) percent of 2-cisbutene, and about zero point one (0.1) percent of other C-4 hydrocarbons.
  • low level trace amounts most preferably less than zero point one (0.1) percent by liquid volume of propene may be present, and most preferably, less than zero point one (0.1) percent by liquid volume of 1,3 butadiene may be present.
  • the petroleum based oil fortifying composition includes about forty to sixty (40-60) percent by liquid volume of chloro paraffin waxes and hydrocarbon waxes (Chemical Abstracts "CAS” Registry Number 63449-39-8) , and about twenty to thirty five (20-35) percent of a chlorinated octadecanoic acid (Chemical Abstracts "CAS” Registry Number 68611-20-1) , and about five to fifteen (5-15) percent of zinc salts of phosphorodithioic acid,0,0-di-Cl-14-alkyl esters (Chemical Abstracts "CAS” Registry Number 68649-42-3) , and about fifteen to twenty (15-20) percent of a hydrogenated 1-decene homopolymer (Chemical Abstracts "CAS” Registry Number 68037-01-4) .
  • the petroleum based oil fortifying and friction fighting composition is available from Tri- Star Technologies Corporation of Great Falls, Montana, under the Product Name Tri-Star OZ2.
  • the chlorinated paraffin waxes are available under a wide variety of commercial trade names, including Adekacizer E 410, Adekacizer E 450, Adekacizer E470, ADK Cizer E 410 ADK Cizer E 450, ADK Cizer E 470, Cereclor, Chlorez, Chlorowax, and Chloroparaffin waxes.
  • the hydrocarbon refrigerant itself is a better heat conductor than R-12, which normally leads to slightly more heat dissipation by conduction to the compressor and radiation and convection cooling thereof (slightly reducing the load on the condenser) .
  • the friction fighter improves lubrication of the compressor, reducing wear and reducing friction loss, and lowers compressor drive motor electrical consumption.

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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

Mélange réfrigérant hydrocarboné destiné à une substitution directe dans des systèmes conçus pour utiliser un réfrigérant R-12. Le mélange de propane, butane, éthane et des agents anti-friction peut être utilisé de manière avantageuse en tant que substitut du réfrigérant R-12, afin d'éliminer l'utilisation du réfrigérant R-12, lequel appauvrit la couche d'ozone. D'une manière idéale, le mélange contient approximativement 57,1 % de propane, 23,2 % de n-butane, 15,1 % d'iso-butane, environ 1,8 % d'éthane, et environ 2 % d'une composition à base de pétrole d'amélioration de l'huile et de réduction du frottement. L'utilisation, avec économie d'énergie, de ce réfrigérant dans les systèmes d'air conditionné de véhicules automobiles et dans des réfrigérateurs domestiques est décrite.
PCT/US1995/015643 1995-12-01 1995-12-01 Melange refrigerant ameliore et son procede d'utilisation dans des systemes de refrigeration Ceased WO1997020902A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/US1995/015643 WO1997020902A1 (fr) 1995-12-01 1995-12-01 Melange refrigerant ameliore et son procede d'utilisation dans des systemes de refrigeration

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PCT/US1995/015643 WO1997020902A1 (fr) 1995-12-01 1995-12-01 Melange refrigerant ameliore et son procede d'utilisation dans des systemes de refrigeration

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1514915A1 (fr) * 2003-09-09 2005-03-16 A.S. Trust & Holdings Inc. Composition d'hydrocarbures et réfrigérant et détergent la contenant
CN1322090C (zh) * 2003-09-09 2007-06-20 A·S·信托&控股公司 烃组合物及由其组成的制冷剂及清洁剂
WO2007144306A1 (fr) * 2006-06-15 2007-12-21 Elcold Frysere Hobro Aps Réfrigérant et système de réfrigération
US8097182B2 (en) 2009-06-17 2012-01-17 A.S. Trust & Holdings, Inc. Hydrocarbon refrigerant and detergent composition
EP2455439A3 (fr) * 2003-11-13 2014-02-19 E. I. du Pont de Nemours and Company Compositions et procédés de réduction des risques de feu pour réfrigérants inflammables
US10712073B2 (en) 2017-03-01 2020-07-14 Haier Us Appliance Solutions, Inc. Ternary natural refrigerant mixture that improves the energy efficiency of a refrigeration system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1325665A (en) * 1919-12-23 Refrigerant and process of making the same
GB148878A (en) * 1918-02-05 1922-01-10 Halleck Wager Seaman An improved refrigerant
US4482465A (en) * 1983-03-07 1984-11-13 Phillips Petroleum Company Hydrocarbon-halocarbon refrigerant blends
US5104560A (en) * 1989-12-05 1992-04-14 Calumet Industries, Inc. Anti-wear additive for refrigeration oil
US5360566A (en) * 1992-11-06 1994-11-01 Intermagnetics General Corporation Hydrocarbon refrigerant for closed cycle refrigerant systems
DE4329477A1 (de) * 1993-09-02 1995-03-09 Willich F Gmbh & Co Kältemittel - Dortmunder Mischung

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1325665A (en) * 1919-12-23 Refrigerant and process of making the same
GB148878A (en) * 1918-02-05 1922-01-10 Halleck Wager Seaman An improved refrigerant
US4482465A (en) * 1983-03-07 1984-11-13 Phillips Petroleum Company Hydrocarbon-halocarbon refrigerant blends
US5104560A (en) * 1989-12-05 1992-04-14 Calumet Industries, Inc. Anti-wear additive for refrigeration oil
US5360566A (en) * 1992-11-06 1994-11-01 Intermagnetics General Corporation Hydrocarbon refrigerant for closed cycle refrigerant systems
DE4329477A1 (de) * 1993-09-02 1995-03-09 Willich F Gmbh & Co Kältemittel - Dortmunder Mischung

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1514915A1 (fr) * 2003-09-09 2005-03-16 A.S. Trust & Holdings Inc. Composition d'hydrocarbures et réfrigérant et détergent la contenant
CN1322090C (zh) * 2003-09-09 2007-06-20 A·S·信托&控股公司 烃组合物及由其组成的制冷剂及清洁剂
EP2455439A3 (fr) * 2003-11-13 2014-02-19 E. I. du Pont de Nemours and Company Compositions et procédés de réduction des risques de feu pour réfrigérants inflammables
US8758642B2 (en) 2003-11-13 2014-06-24 E I Du Pont De Nemours And Company Compositions and methods for reducing fire hazard of flammable refrigerants
WO2007144306A1 (fr) * 2006-06-15 2007-12-21 Elcold Frysere Hobro Aps Réfrigérant et système de réfrigération
US8097182B2 (en) 2009-06-17 2012-01-17 A.S. Trust & Holdings, Inc. Hydrocarbon refrigerant and detergent composition
US10712073B2 (en) 2017-03-01 2020-07-14 Haier Us Appliance Solutions, Inc. Ternary natural refrigerant mixture that improves the energy efficiency of a refrigeration system

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