1-Ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane refrigerant compositions comprising a hydrocarbon and uses thereof

Abstract

The present invention relates to compositions for use in refrigeration and air-conditioning systems comprising 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane and at least one hydrocarbon. Further, the present invention relates to compositions for use in refrigeration and air-conditioning systems employing a centrifugal compressor comprising 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane and at least one hydrocarbon. The compositions of the present invention may be azeotropic or near-azeotropic and are useful in processes for producing cooling or heat or as heat transfer fluids.

1 . A refrigerant or heat transfer fluid composition comprising C 4 F 9 OC 2 H 5  and at least one hydrocarbon selected from the group consisting of: 
 cyclohexane;    cyclopentane;    3-ethylpentane;    2,2-dimethylbutane;    2,3-dimethylbutane;    n-heptane;    methylcyclopentane;    2-methylhexane;    3-methylhexane;    2-methylpentane;    3-methylpentane; and    n-pentane.    
   
   
       2 . A refrigerant or heat transfer fluid composition as in  claim 1  wherein said composition comprises a composition selected from the group consisting of: 
 C 4 F 9 OC 2 H 5  and cyclohexane;    C 4 F 9 OC 2 H 5  and cyclopentane;    C 4 F 9 OC 2 H 5  and 3-ethylpentane;    C 4 F 9 OC 2 H 5  and 2,2-dimethylbutane;    C 4 F 9 OC 2 H 5  and 2,3-dimethylbutane;    C 4 F 9 OC 2 H 5  and n-heptane;    C 4 F 9 OC 2 H 5  and methylcyclopentane;    C 4 F 9 OC 2 H 5  and 2-methylhexane;    C 4 F 9 OC 2 H 5  and 3-methylhexane;    C 4 F 9 OC 2 H 5  and 2-methylpentane;    C 4 F 9 OC 2 H 5  and 3-methylpentane; and    C 4 F 9 OC 2 H 5  and n-pentane.    
   
   
       3 . A refrigerant or heat transfer fluid composition as in  claim 1  wherein said composition comprises an azeotropic or near-azeotropic composition selected from the group consisting of: 
 about 1 to about 71 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 29 weight percent cyclopentane;    about 1 to about 71 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 29 weight percent 2,2-dimethylbutane;    about 1 to about 77 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 23 weight percent 2,3-dimethylbutane;    about 56 to about 99 weight percent C 4 F 9 OC 2 H 5  and about 44 to about 1 weight percent 3-ethylpentane;    about 25 to about 99 weight percent C 4 F 9 OC 2 H 5  and about 75 to about 1 weight percent methylcyclopentane;    about 51 to about 99 weight percent C 4 F 9 OC 2 H 5  and about 49 to about 1 weight percent 2-methylhexane;    about 54 to about 99 weight percent C 4 F 9 OC 2 H 5  and about 46 to about 1 weight percent 3-methylhexane;    about 1 to about 79 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 21 weight percent 2-methylpentane;    about 1 to about 82 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 18 weight percent 3-methylpentane; or    about 1 to about 62 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 38 weight percent n-pentane.    
   
   
       4 . A refrigerant or heat transfer fluid composition as in  claim 1  wherein said composition comprises an azeotropic or near-azeotropic composition selected from the group consisting of: 
 29.6 weight percent C 4 F 9 OC 2 H 5  and 70.4 weight percent cyclopentane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.1° C.;    32.6 weight percent C 4 F 9 OC 2 H 5  and 67.4 weight percent 2,2-dimethylbutane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.1° C.;    44.7 weight percent C 4 F 9 OC 2 H 5  and 55.3 weight percent 2,3-dimethylbutane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 54.8° C.;    86.0 weight percent C 4 F 9 OC 2 H 5  and 14.0 weight percent 3-ethylpentane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 73.5° C.;    62.1 weight percent C 4 F 9 OC 2 H 5  and 37.9 weight percent methylcyclopentane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 64.5° C.;    81.8 weight percent C 4 F 9 OC 2 H 5  and 18.2 weight percent 2-methylhexane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 72.1° C.;    83.8 weight percent C 4 F 9 OC 2 H 5  and 16.2 weight percent 3-methylhexane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 72.8° C.;    47.9 weight percent C 4 F 9 OC 2 H 5  and 52.1 weight percent 2-methylpentane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 56.5° C.;    52.1 weight percent C 4 F 9 OC 2 H 5  and 47.9 weight percent 3-methylpentane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 58.7° C.; or    9.2 weight percent C 4 F 9 OC 2 H 5  and 90.8 weight percent n-pentane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 35.0° C.    
   
   
       5 . A process for producing cooling, said process comprising evaporating the composition of  claim 1  in the vicinity of a body to be cooled, and thereafter condensing said composition.  
   
   
       6 . A process for producing heat, said process comprising condensing the composition of  claim 1  in the vicinity of a body to be heated, and thereafter evaporating said composition.  
   
   
       7 . A process for transferring heat, said process comprising transferring the composition of  claim 1  from the vicinity of a heat source to a heat sink.  
   
   
       8 . The composition of  claim 1 , further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives thereof.  
   
   
       9 . The composition of  claim 8 , further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes; and wherein the refrigerant or heat transfer fluid may not be the same compound as the solubilizing agent.  
   
   
       10 . The composition of  claim 9 , wherein said solubilizing agent is selected from the group consisting of: 
 a) polyoxyalkylene glycol ethers represented by the formula R 1 [(OR 2 ) x OR 3 ] y , wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R 1  is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2  is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3  is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R 1  and R 3  is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units;    b) amides represented by the formulae R 1 CONR 2 R 3  and cyclo-[R 4 CON(R 5 )—], wherein R 1 , R 2 , R 3  and R 5  are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R 4  is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units;    c) ketones represented by the formula R 1 COR 2 , wherein R 1  and R 2  are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units;    d) nitriles represented by the formula R 1 CN, wherein R 1  is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;    e) chlorocarbons represented by the formula RCl x , wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units;    f) aryl ethers represented by the formula R 1 OR 2 , wherein: R 1  is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2  is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units;    g) 1,1,1-trifluoroalkanes represented by the formula CF 3 R 1 , wherein R 1  is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms;    h) fluoroethers represented by the formula R 1 OCF 2 CF 2 H, wherein R 1  is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins are of the type CF 2 ═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF 3  or OR f , wherein R f  is CF 3 , C 2 F 5 , or C 3 F 7 ; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH 2 (CHOH) x (CRR′) y CH 2 OH, wherein R and R′ are hydrogen, CH 3  or C 2 H 5 , x is an integer from 04, y is an integer from 0-3 and z is either zero or 1, and said branched polyols are of the type C(OH) t (R) u (CH 2 OH) v [(CH 2 ) m CH 2 OH] w , wherein R may be hydrogen, CH 3  or C 2 H 5 , m is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4, and also wherein t+u+v+w=4;    i) lactones represented by structures [B], [C], and [D]:                           wherein, R 1  through R 8  are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and    j) esters represented by the general formula R 1 CO 2 R 2 , wherein R 1  and R 2  are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.    
   
   
       11 . A method for introducing an ultraviolet fluorescent dye into a compression refrigeration or air-conditioning apparatus, said method comprising dissolving the ultraviolet fluorescent dye in the composition of  claim 1  in the presence of a solubilizing agent, and introducing the combination into said compression refrigeration or air-conditioning apparatus.  
   
   
       12 . A method for solubilizing ultraviolet fluorescent dye in the composition of  claim 1  said method comprising contacting the ultraviolet fluorescent dye with said composition, in the presence of a solubilizing agent.  
   
   
       13 . A method for detecting leaks, said method comprising providing the composition of  claim 8  into a compression refrigeration apparatus or air-conditioning apparatus, and providing a suitable means for detecting said composition at a leak point, or in the vicinity of said apparatus.  
   
   
       14 . The method of  claim 5  wherein the refrigerant composition further comprises at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives thereof.  
   
   
       15 . The method of  claim 6 , wherein the refrigerant composition further comprises at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives thereof.  
   
   
       16 . The composition of  claim 1  further comprising a stabilizer, water scavenger, or odor masking agent.  
   
   
       17 . The composition of  claim 16  wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones.  
   
   
       18 . A process of  claim 5 , wherein said process comprises producing heat or cooling in a refrigeration or air-conditioning apparatus employing a multi-stage centrifugal compressor.  
   
   
       19 . The method of  claim 18  wherein said multi-stage centrifugal compressor is a two-stage centrifugal compressor.  
   
   
       20 . The composition of  claim 16  wherein said water scavenger is an ortho ester.  
   
   
       21 . A process to produce cooling comprising compressing a composition of  claim 1  in a mini-centrifugal compressor powered by an engine exhaust gas driven turbine; condensing said composition; and thereafter evaporating said composition in the vicinity of a body to be cooled.  
   
   
       22 . A process to produce cooling comprising compressing a composition of  claim 1  in a mini-centrifugal compressor powered by a ratioed gear drive assembly with a ratioed belt drive; condensing said composition; and thereafter evaporating said composition in the vicinity of a body to be cooled.  
   
   
       23 . A method for replacing CFC-113 in existing refrigeration apparatus or air-conditioning apparatus, said method comprising providing a composition of  claim 1  as the replacement.