US008974688B2
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`(12) United States Patent
`Yana Motta et al.
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`(10) Patent No.:
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`(45) Date of Patent:
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`US 8,974,688 B2
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`Mar. 10, 2015
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`(54)
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`(75)
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`COMPOSITIONS AND METHODS FOR
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`REFRIGERATION
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`Inventors: Samuel F. Yana Motta, East Amherst,
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`NY (US); Mark W. Spatz, East
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`Amherst, NY (US); Rajiv Ratna Singh,
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`Getzville, NY (US); Robert Gerard
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`Richard, Hamburg, NY (US); Elizabet
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`del Carmen Vera Becerra,
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`Williamsville, NY (US); Daniel Burger,
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`Hamburg, NY (US)
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`(73)
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`Assignee: Honeywell International Inc.,
`Morristown, NJ (US)
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`(*)
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`Notice:
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`Subject to any disclaimer, the term of this
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`patent is extended or adjusted under 35
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`U.S.C. 154(b) by 0 days.
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`(21)
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`Appl. No.: 12/776,320
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`(22)
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`(65)
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`(60)
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`Filed:
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`May 7, 2010
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`Prior Publication Data
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`US 2011/0023507 A1
`Feb. 3, 2011
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`Related U.S. Application Data
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`Continuation-in-part of application No. 12/511,954,
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`filed on Jul. 29, 2009.
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`Provisional application No. 61/240,786, filed on Sep.
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`9, 2009, provisional application No. 61/247,816, filed
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`on Oct. 1, 2009.
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`Int. Cl.
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`C09K 5/04
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`C09K 3/30
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`F25B 1/00
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`F25B 40/00
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`U.S. Cl.
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`CPC . C09K3/30 (2013.01); C09K 5/045 (2013.01);
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`F25B 1/00 (2013.01); C09K 2205/I26
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`(2013.01); C09K 2205/22 (2013.01); F25B
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`40/00 (2013.01); F25B 2400/I2] (2013.01);
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`F25B 2400/I8 (2013.01)
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`USPC .......................................................... .. 252/67
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`(58) Field of Classification Search
`USPC .................................................... .. 252/67, 68
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`See application file for complete search history.
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`(56)
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`References Cited
`U.S. PATENT DOCUMENTS
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`4/2012 Singh et al.
`8,148,317 B2
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`11/2006 Minor et al.
`2006/0243944 A1
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`2009/0253820 A1* 10/2009 Bowman et al.
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`FOREIGN PATENT DOCUMENTS
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`WO 00/56834
`9/2000
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`WO 2010/059677
`5/2010
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`2011056824 A2
`5/2011
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`WO 2011/056824
`5/2011
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`............ .. 521/170
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`*
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`* cited by examiner
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`Primary Examiner — John Hardee
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`(74) Attorney, Agent, or Firm — Colleen D. Szuch
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`(57)
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`ABSTRACT
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`Heat transfer systems, methods and compositions which uti-
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`lize a heat transfer fluid comprising: (a) from about 30% to
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`about 65% by weight of HFC-134a; (b) from about 0% to
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`about 70% by weight of HFO1234ze; and (c) from about 0%
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`to about 70% by weight of HFO-1234yf, provided that the
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`amount of HFO-1234ze and HFO- 1 234yf in the composition
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`together is at least about 35% by weight, with the weight
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`percent being based on the total of the components (a)-(c) in
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`the composition.
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`32 Claims, 1 Drawing Sheet
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`Ex anaion
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`Compressor
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`Page 1 of 11
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`Arkema Exhibit 1025
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`Arkema Exhibit 1025
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`Page 1 of 11
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`U.S. Patent
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`Mar. 10, 2015
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`US 8,974,688 B2
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`Ex ansion
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`evica
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`Compressor
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`FIGURE 1
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` I__iquid line I suction
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`Compressnr
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`evicii .
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`Ex ansbn "
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`4.
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`line heat exchanger
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`FIGURE 2
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`Page 2 of 11
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`Page 2 of 11
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`US 8,974,688 B2
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`2
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`safer substitutes for, CFCs and HCFCs. It is generally con-
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`sidered important, however, at least with respect to heat trans-
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`fer fluids, that any potential substitute must also possess those
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`properties present in many of the most widely used fluids,
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`such as excellent heat transfer properties, chemical stability,
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`low- or no-toxicity, non-flarnmability and/or lubricant com-
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`patibility, among others.
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`With regard to efficiency in use, it is important to note that
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`a loss in refrigerant thermodynamic performance or energy
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`efliciency may have secondary environmental
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`through increased fossil fuel usage arising from an increased
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`demand for electrical energy.
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`Furthermore, it is generally considered desirably for CFC
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`refrigerant substitutes to be effective without major engineer-
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`ing changes to conventional vapor compression technology
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`currently used with CFC refrigerants.
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`Flammability is another important property for many
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`applications. That is, it is considered either important or
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`essential in many applications, including particularly in heat
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`transfer applications, to use compositions which are non-
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`flamrnable. Thus, it is frequently beneficial to use in such
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`compositions compounds which are nonflammable. As used
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`herein, the term “nonflammable” refers to compounds or
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`compositions which are determined to be in Class 1 as deter-
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`mined in accordance with ASHRAE Standard 34-2007,
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`including ANSI/ASHRI Addenda, which is incorporated
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`herein by reference. Unfortunately, many HFC’s which might
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`otherwise be desirable for used in refrigerant compositions
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`are not nonflarnmable and/or not Class 1. For example, the
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`fluoroalkane difluoroethane (HFC-152a) and the fluoroalk-
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`ene 1,1,1-trifluorpropene (HFO-1243zf) are each flammable
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`and therefore not viable for use in many applications.
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`Applicants have thus come to appreciate a need for com-
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`positions, systems, and methods and particularly heat transfer
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`compositions that are highly advantageous in vapor compres-
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`sion heating and cooling systems and methods, particularly
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`refrigerant and heat pump systems of the type that have her-
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`ertofore been used with or designed for use with HFC-134a.
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`SUMMARY
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`Applicants have found that the above-noted need, and other
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`needs, canbe satisfied by compositions, methods and systems
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`which comprise or utilize a multi-component mixture which
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`comprises HFC-134a and at
`least one fluorinated olefin
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`selected from the group consisting of HFO-1234ze and HFO-
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`1234yf
`In preferred embodiments, the compostions of the present
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`invention comprise: (a) from about 30% to about 65% by
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`weight of HFC-134a; (b) from about 0% to about 70% by
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`weight of HFO-1234ze, preferably trans-HFO-1234ze; and
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`(c) from about 0% to about 70% by weight of HFO-1234yf,
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`provided that the amount of HFO-1234ze plus HFO-1234yf
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`in the composition is at least about 35% by weight, with the
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`weight percent being based on the total of the components
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`(a)-(c) in the composition. Applicants have unexpectedly
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`found the combination of components in the present compo-
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`sitions, especially within the preferred ranges specified
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`herein, are capable of at once achieving a combination of
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`important and difficult to achieve refrigerant performance
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`properties that can not be achieved by any one of the compo-
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`nents alone. For example, the preferred compositions of the
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`present invention are at once Class 1 with respect to flamma-
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`bility and have a desirably low GWP.
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`If the amount of HFC-134 is greater than the preferred
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`range identified above, for example, the composition will not
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`satisfy the environmental requirements for many applica-
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`1
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`COMPOSITIONS AND METHODS FOR
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`REFRIGERATION
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`RELATED APPLICATIONS
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`The present application is related to and claims the priority
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`benefit of each of U.S. Provisional Application Ser. Nos.
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`61/240,786, filed Sep. 9, 2009 and 61/247,816, filed Oct. 1,
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`2009, and is a continuation-in-part pending of U.S. applica-
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`tion Ser. No. 12/511,954, filed Jul. 29, 2009, each ofwhich is
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`incorporated in its entirety herein by reference.
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`FIELD OF THE INVENTION
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`This invention relates to compositions, methods and sys-
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`tems having utility in many applications, including in domes-
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`tic and small refrigeration and/or air conditioning applica-
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`tions and/or heat pump applications, and in particular aspects
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`to refrigerant compositions for replacement of refrigerant
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`HFC-134a for heating and/or cooling applications and to
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`retrofitting refrigerant and/or air conditioning systems,
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`including systems designed for use with HFC-134a.
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`BACKGROUND
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`Mechanical refrigeration systems, and related heat transfer
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`devices such as heat pumps and air conditioners, using refrig-
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`erant liquids are well known in the art for industrial, commer-
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`cial and domestic uses. Fluorocarbon based fluids have found
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`widespread use in many residential, commercial and indus-
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`trial applications, including as the working fluid in systems
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`such as air conditioning, heat pump and refrigeration sys-
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`tems, including relatively small systems such as are used for
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`domestic refrigerators and freezers and in automobile air
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`conditioning. Because of certain suspected environmental
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`including the relatively high global warming
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`potentials, associated with the use of some of the composi-
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`tions that have heretofore been used in these applications, it
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`has become increasingly desirable to use fluids having low or
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`even zero ozone depletion potential, such as hydrofluorocar-
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`bons (“HFCs”). For example, a number of governments have
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`signed the Kyoto Protocol to protect the global environment
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`and setting forth a reduction of CO2 emissions (global warm-
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`ing). Thus, there is a need for a low- or non-flamrnable,
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`non-toxic alternative to replace certain of high global warm-
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`ing HFCs.
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`One important type of refrigeration system is known as
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`“small refrigeration” or “domestic refrigeration” systems,
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`which encompasses systems that are typically used in resi-
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`dential homes, apartments and the like for consumer use in
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`refrigerators, freezers, and the like. Also frequently included
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`in this group are vending machines and the like. Another
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`important refrigeration system comprises automotive air con-
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`ditioning systems. In such refrigeration systems a commonly
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`used refrigerant liquid has been HFC-134a, also known as
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`R-134a.
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`There has thus been an increasing need for new fluorocar-
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`bon and hydrofluorocarbon compounds and compositions
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`that are attractive alternatives to the compositions heretofore
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`used in these and other applications. For example, it has
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`become desirable to retrofit chlorine-containing refrigeration
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`systems by replacing chlorine-containing refrigerants with
`non-chlorine-containing refrigerant compounds that will not
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`deplete the ozone layer, such as hydrofluorocarbons (HFC’ s).
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`Industry in general and the heat transfer industry in particular
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`are continually seeking new fluorocarbon based mixtures that
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`offer alternatives to, and are considered environmentally
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`US 8,974,688 B2
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`4
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`(HFCO- l 233xf), both cis- and trans- l , l , l -trifluo-3 ,chlororo-
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`propene (HFCO-l233zd). The term HFCO-l233zd is used
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`herein generically to refer to l,1,1-trifluo-3,chloro-propene,
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`independent of whether it is the cis- or trans-form. The terms
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`“cisHFCO-l233zd” and “transHFCO-l233zd” are used
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`herein to describe the cis- and trans-forms of l,l,l-trifluo,3-
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`chlororopropene, respectively. The term “HFCO-l233zd”
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`therefore includes within its scope cisHFCO-l233zd, transH-
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`FCO-l233zd, and all combinations and mixtures of these.
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`The term “HFC-l34a” is used herein to refer to l,l,l,2-
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`tetrafluoroethane.
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`BRIEF DESCRIPTION OF THE DRAWINGS
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`FIG. 1 is a schematic representation of a simple vapor
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`compression heat transfer cycle.
`FIG. 2 is a schematic representation of a vapor compres-
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`sions heat transfer cycle having a liquid line/suction line heat
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`exchanger.
`DETAILED DESCRIPTION OF PREFERRED
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`EMBODIMENTS
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`Small refrigeration systems are important in many appli-
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`cations, as mentioned above. In such systems, one of the
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`refrigerant liquids which has been commonly used has been
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`HFC-l34a, which has an estimated high Global Warming
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`Potential (GWP) of 1430. Applicants have found that the
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`compositions of the present invention satisfy in an excep-
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`tional and unexpected way the need for alternatives and/or
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`replacements for refrigerants in such applications, particu-
`larly and preferably HFC-l34a. Preferred compositions at
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`once have lower GWP values and provide non-flamrnable,
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`non-toxic fluids that have a close match in cooling capacity to
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`HFC-l34a in such systems.
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`In certain preferred forms, compositions of the present
`
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`invention have a Global Warming Potential (GWP) of not
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`greater than about 1000, more preferably not greater than
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`about 700, and even more preferably about 600 or less. As
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`used herein, “GWP” is measured relative to that of carbon
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`dioxide and over a 100 year time horizon, as defined in “The
`
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`
`Scientific Assessment of Ozone Depletion, 2002, a report of
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`the World Meteorological Association’s Global Ozone
`
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`Research and Monitoring Project,” which is incorporated
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`herein by reference.
`
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`In certain preferred forms, the present compositions also
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`preferably have an Ozone Depletion Potential (ODP) of not
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`greater than 0.05, more preferably not greater than 0.02 and
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`even more preferably about zero. As used herein, “ODP” is as
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`defined in “The Scientific Assessment of Ozone Depletion,
`
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`2002, A report of the World Meteorological Association’s
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`
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`Global Ozone Research and Monitoring Project,” which is
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`incorporated herein by reference.
`
`
`
`Heat Transfer Compositions
`
`
`
`The compositions of the present invention are generally
`
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`
`adaptable for use in heat transfer applications, that is, as a
`
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`heating and/or cooling medium, but are particularly well
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`adapted for use, as mentioned above, in small refrigeration
`
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`systems that have heretofor used HFC-l34a.
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`Applicants have found that use of the components of the
`
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`
`
`present invention within the broad and preferred ranges
`
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`
`
`described herein is important to obtaining the difficult to
`
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`
`
`achieve combinations of properties exhibited by the present
`
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`compositions, particularly in the preferred systems and meth-
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`ods, and that use of these same components but substantially
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`outside of the identified ranges can have a deleterious effect
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`on one or more of the important properties of the composi-
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`10
`
`15
`
`20
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`25
`
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`30
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`35
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`40
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`45
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`50
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`55
`
`
`60
`
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`65
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`
`3
`
`tions. On the other hand, if the fluorinated olefins are used in
`
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`amounts greater than those specified above, the composition
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`will not be Class 1 and/or will not perform acceptable in terms
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`
`of capacity and/or efficiency.
`In certain preferred embodiments, the compositions com-
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`prise a multi-component mixture comprising: (a) from about
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`35% to about 55% by weight of HFC-134a; (b) from about
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`30% to about 60% by weight of HFO-l234ze, preferably
`
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`trans-HFO-l234ze; and (c) from about 5% to about 30% by
`
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`
`
`weight of HFO-l234yf, with the weight percent being based
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`
`on the total of the components (a)-(c) in the composition.
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`In certain preferred embodiments, particularly for use in
`
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`
`connection with systems that have heretofore utilized HFC-
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`l34a as the refrigerant, the present compositions comprise a
`
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`multi-component mixture comprising: (a) from about 35% to
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`
`
`about 50% by weight of HFC-l34a; (b) from about 30% to
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`about 55% by weight ofHFO-l234ze, preferably trans-HFO-
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`l234ze; and (c) from about 5% to about 25% by weight of
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`HFO- l 234yf, with the weight percent being based on the total
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`
`of the components (a)-(c) in the composition. In even more
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`preferred embodiments, the compositions comprise a multi-
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`component mixture comprising: (a) from about 40% to about
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`45% by weight of HFC-l34a; (b) from about 35% to about
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`50% by weight of HFO-l234ze, preferably trans-HFO-
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`l234ze; and (c) from about 10% to about 20% by weight of
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`HFO- l 234yf, with the weight percent being based on the total
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`
`ofthe components (a)-(c) in the composition. Applicants have
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`found that such preferred compositions are highly desirable
`
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`
`in that they are not only low GWP and Class 1 compositions,
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`but they also are capable of exhibiting in many refrigeration
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`applications energy consumption properties that are equal to
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`
`
`or superior to the energy consumption of HFC-l34a, prefer-
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`
`ably as measured in accordance with American National
`
`
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`
`
`Standard “Energy Performance and Capacity of Household
`
`
`
`
`
`
`Refrigerators, Refrigerator-Freezers and Freezers (ANSI/
`
`
`
`
`
`AHAM HRF-l -2007), which is incorporated herein by refer-
`
`
`
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`
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`ence.
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`
`
`In certain preferred embodiments, the present composi-
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`
`
`tions may also include HFO-1233, preferably in amounts of
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`up to about 5% by weight of the composition.
`
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`
`The present invention provides also methods and systems
`
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`which utilize the compositions of the present
`invention,
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`including methods and systems for heat transfer and for ret-
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`rofitting existing heat transfer systems. Certain preferred
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`
`method aspects of the present invention relate to methods of
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`providing cooling in small refrigeration systems. Other
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`method aspects of the present invention provide methods of
`
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`
`retrofitting an existing small refrigeration system designed to
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`
`contain or containing R-l34a refrigerant comprising intro-
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`
`
`ducing a composition of the present invention into the system
`
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`
`without substantial engineering modification of said existing
`
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`refrigeration system.
`The term “HFO-1234” is used herein to refer to all tet-
`
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`
`
`the
`rafluoropropenes. Among
`tetrafluoropropenes
`are
`
`
`
`
`
`included l,1,1,2-tetrafluoropropene (HFO-l234yf) and both
`
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`
`
`
`cis- andtrans-1,1,1,3-tetrafluoropropene (HFO-l234ze). The
`
`
`
`
`term HFO-l234ze is used herein generically to refer to 1,1,
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`
`
`1,3-tetrafluoropropene, independent of whether it is the cis-
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`
`
`or trans-form. The terms “cisHFO-l234ze” and “transHFO-
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`
`l234ze” are used herein to describe the cis- and trans-forms
`
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`
`
`of l,l,l,3-tetrafluoropropene respectively. The term “HFO-
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`
`l234ze” therefore includes within its scope cisHFO- l 234ze,
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`transHFO-l234ze, and all combinations and mixtures of
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`these.
`
`The term “HFO-1233” is used herein to refer to all trifluo-
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`
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`ro,monochloropropenes. Among the trifluoro,monochloro-
`
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`included
`l,1,1,trifluoro-2,chloro-propene
`propenes
`are
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`Page 4 of 11
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`Page 4 of 11
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`

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`
`US 8,974,688 B2
`
`5
`
`tions of the invention. In highly preferred embodiments,
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`highly preferred combinations of properties are achieved for
`
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`
`compositions having a weight ratio of HFC-134a:HFC-
`
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`
`
`1234ze, and preferably of transHFC-1234ze, of from about
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`
`0.6:1 to about 1:0.9, with a ratio offrom about 0.65:1 to about
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`
`1 :1 being preferred in certain embodiments. Applicants have
`
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`found that highly preferred combinations of properties are
`
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`
`
`also achieved for compositions having a weight ratio of HFO-
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`
`
`1234ze:HFO-1234yf of from about 6:1 to about 3:1, with a
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`ratio of from about 5:1 to about 4:1 being preferred in certain
`
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`embodiments.
`
`For the purposes of convenience, the combination HFO-
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`
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`1234ze and HFO-1234yf is referred to herein as the “tet-
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`rafluoropropene component” or “TFC,” and in certain
`
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`
`embodiments highly preferred combinations of properties
`can be achieved for composition which comprise a weight
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`ratio of HFC-134a:TFC of from about 0.6:1 to about 1:0.9,
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`
`with a ratio of from about 0.65:1 to about 1:1 being preferred
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`in certain embodiments.
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`
`Although it is contemplated that either isomer of HFO-
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`
`1234ze may be used to advantage in certain aspects of the
`
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`
`
`present invention, applicants have found that it is preferred in
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`
`
`certain embodiments that the HFO-1234ze comprise tran-
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`
`
`sHFO-1234ze, and preferably comprise transHFO-1234ze in
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`
`
`major proportion, and in certain embodiments consist essen-
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`
`
`tially of transHFO-1234ze.
`
`
`As mentioned above, applicants have found that the com-
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`
`
`positions of the present invention are capable of achieving a
`
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`
`
`difficult combination ofproperties, including particularly low
`
`
`
`
`
`
`GWP. By way ofnon-limiting example, the following TableA
`
`
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`
`
`
`illustrates the substantial improvement the GWP of certain
`
`
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`
`
`
`compositions of the present invention in comparison to the
`
`
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`
`
`
`GWP of HFC-134a, which has a GWP of 1430.
`
`
`
`
`
`
`
`TABLE A
`
`
`
`
`Composition of the Invention
`
`
`(Weight fraction, based on
`
`
`
`identified components)
`
`
`R134a
`
`R134a/1234ze (0.42/0.58)
`
`
`R134a/1234ze/1234yf (0.42/0.48/0. 10)
`
`
`
`R134a/1234ze/1234yf (0.42/0.40/0.18)
`
`
`
`Name
`
`R134a
`A1
`
`A2
`
`A3
`
`
`
`
`GWP
`
`1430
`
`604
`
`604
`
`604
`
`
`GWP as a
`
`Percentage of
`
`R134a GWP
`
`
`100%
`
`42%
`
`42%
`
`42%
`
`
`The compositions of the present invention may include
`
`
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`
`
`
`
`other components for the purpose of enhancing or providing
`
`
`
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`
`
`
`certain functionality to the composition, or in some cases to
`
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`
`
`reduce the cost of the composition. For example, the present
`
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`
`
`compositions may include co-refrigerants, lubricants, stabi-
`
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`
`
`lizers, metal passivators, corrosion inhibitors, flammability
`
`
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`
`
`suppressants, and other compounds and/or components, and
`
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`
`the presence of all such compounds and components is within
`
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`
`
`the broad scope of the invention.
`
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`
`
`
`In certain preferred embodiments, the refrigerant compo-
`
`
`
`
`
`
`
`sitions according to the present invention, especially those
`
`
`
`
`
`
`
`used in vapor compression systems, include a lubricant, gen-
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`
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`
`
`
`erally in amounts of from about 30 to about 50 percent by
`
`
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`
`
`
`weight of the composition, and in some case potentially in
`
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`
`
`
`amount greater than about 50 percent and other cases in
`
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`
`
`
`
`
`amounts as low as about 5 percent. Furthermore, the present
`
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`
`
`compositions may also include a compatibilizer, such as pro-
`
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`
`
`
`pane, for the purpose of aiding compatibility and/or solubility
`
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`
`
`
`
`
`of the lubricant. Such compatibilizers, including propane,
`
`
`
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`
`
`
`butanes and pentanes, are preferably present in amounts of
`
`
`
`
`
`
`
`from about 0.5 to about 5 percent by weight of the composi-
`
`
`
`
`
`
`
`tion. Combinations of surfactants and solubilizing agents
`
`
`
`
`
`
`
`may also be added to the present compositions to aid oil
`
`
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`
`
`
`
`
`
`
`10
`
`15
`
`20
`
`
`
`25
`
`30
`
`
`
`35
`
`
`40
`
`
`
`45
`
`
`50
`
`
`
`55
`
`
`60
`
`
`
`65
`
`
`Page 5 of 11
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`
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`6
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`solubility, as disclosed by U.S. Pat. No. 6,516,837, the dis-
`
`
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`
`
`
`
`
`
`closure of which is incorporated by reference. Commonly
`
`
`
`
`
`
`used refrigeration lubricants such as Polyol Esters (POEs)
`
`
`
`
`
`
`
`and Poly Alkylene Glycols (PAGs), PAG oils, silicone oil,
`
`
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`
`
`
`
`mineral oil, alkyl benzenes (ABs) and poly(alpha-olefin)
`
`
`
`
`
`
`
`(PAO) that are used in refrigeration machinery with hydrof-
`
`
`
`
`
`
`
`
`luorocarbon (HFC) refrigerants may be used with the refrig-
`
`
`
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`
`
`
`erant compositions of the present invention. Commercially
`
`
`
`
`
`
`available mineral oils include Witco LP 250 (registered trade-
`
`
`
`
`
`
`
`
`mark) from Witco, Zerol 300 (registered trademark) from
`
`
`
`
`
`
`
`
`Shrieve Chemical, Sunisco 3GS from Witco, and Calumet
`
`
`
`
`
`
`
`
`R015 from Calumet. Commercially available alkyl benzene
`
`
`
`
`
`
`
`lubricants include Zerol 150 (registered trademark). Com-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`mercially available esters include neopentyl glycol dipelar-
`gonate, which is available as Emery 2917 (registered trade-
`
`
`
`
`
`
`
`mark) and Hatcol 2370 (registered trademark). Other useful
`
`
`
`
`
`
`
`
`esters include phosphate esters, dibasic acid esters, and fluo-
`
`
`
`
`
`
`
`
`
`roesters. In some cases, hydrocarbon based oils are have
`
`
`
`
`
`
`
`
`
`sufficient solubility with the refrigerant that is comprised of
`
`
`
`
`
`
`
`an iodocarbon, the combination of the iodocarbon and the
`
`
`
`
`
`
`
`
`hydrocarbon oil might more stable than other types of lubri-
`
`
`
`
`
`
`
`
`cant. Such combination may therefore be advantageous. Pre-
`
`
`
`
`
`
`
`ferred lubricants include polyalkylene glycols and esters.
`
`
`
`
`
`
`
`Polyalkylene glycols are highly preferred in certain embodi-
`
`
`
`
`
`
`
`ments because they are currently in use in particular applica-
`
`
`
`
`
`
`
`
`tions such as mobile air-conditioning. Of course, different
`
`
`
`
`
`
`
`mixtures of different types of lubricants may be used.
`
`
`
`
`
`
`In certain preferred embodiments, the present composi-
`
`
`
`
`
`
`
`tions include, in addition to the compounds described above,
`
`
`
`
`
`
`
`one or more of the following as co-refrigerant:
`
`
`
`
`
`
`Trichlorofluoromethane (CFC-1 1)
`Dichlorodifluoromethane (CFC- 12)
`
`Difluoromethane (HFC-32)
`
`
`Pentafluoroethane (HFC-125)
`
`
`1,1,2,2-tetrafluoroethane (HFC-134)
`
`Difluoroethane (HFC-152a)
`
`
`
`1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)
`
`
`1,1,1,3,3,3-hexafluoropropane (HFC-236fa)
`
`
`1,1,1,3,3-pentafluoropropane (HFC-245fa)
`
`
`
`1,1,1,3,3-pentafluorobutane (HFC-3 65mfc)
`water
`
`CO2
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`Of course, other co-refrigerants may be used in addition to or
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`instead of any or more of the above-notes examples.
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`Heat Transfer Methods and Systems
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`The preferred heat transfer methods generally comprise
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`providing a composition of the present invention and causing
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`heat to be transferred to or from the composition, either by
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`sensible heat transfer, phase change heat transfer, or a com-
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`bination of these. For example, in certain preferred embodi-
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`ments the present methods provide refrigeration systems
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`comprising a refrigerant ofthe present invention and methods
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`ofproducing heating or cooling by condensing and/or evapo-
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`rating a composition of the present invention. In certain pre-
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`ferred embodiments, the systems and methods for heating
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`and/or cooling, including cooling of other fluid either directly
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`or indirectly or a body directly or indirectly comprise com-
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`pressing a refrigerant composition of the present invention
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`and thereafter evaporating said refrigerant composition in the
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`vicinity of the article to be cooled. As used herein, the term
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`“body” is intended to refer not only to inanimate objects but
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`also to living tissue, including animal tissue in general and
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`human tissue in particular. For example, certain aspects ofthe
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`present invention involve application of the present compo-
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`sition to human tissue for one or more therapeutic purposes,
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`such as a pain killing technique, as a preparatory anesthetic,
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`or as part of a therapy involving reducing the temperature of
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`Page 5 of 11
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`US 8,974,688 B2
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`8
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`the system between the evaporator and the compressor
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`whereby at least a portion of the liquid discharged from the
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`condenser, for example in discharge line 3, is diverted to be
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`further cooled by absorbing heat from at least a portion ofthe
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`discharge from the evaporator. Applicants have found that the
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`compositions of the present invention produce unexpectedly
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`advantageous and surprisingly beneficial results when used in
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`connection with heat transfer systems containing an SL-LL
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`heat exchanger. In certain embodiments, such advantage and
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`benefit occurs in connection with improved system capacity
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`and efliciency, and beneficial lowering of compressor dis-
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`charge temperature.
`In another process embodiment of the invention, the com-
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`positions of the invention may be used in a method for pro-
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`ducing heating which comprises condensing a refrigerant
`comprising the compositions in the vicinity of a liquid or
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`body to be heated. Such methods, as mentioned hereinbefore,
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`frequently are reverse cycles to the refrigeration cycle
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`described above. One example of such an embodiment which
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`may be used to produce heat and/or cooling our certain types
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`of devices known as heat pumps. Although such devices are
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`available for use, and have been used, to heat and/or cool
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`many types of fluids or other materials, in certain preferred
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`embodiments the heat pumps of the present invention are
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`utilized to heat and/or cool water, and preferably domestic
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`water.
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`The present methods, systems and compositions are thus
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`adaptable for use in connection with a wide variety of heat
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