Abstract:
The use of a refrigerant in organic Rankine cycle systems including at least one hydrofluoroolefin, having at least four carbon atoms represented by the formula (I) R1CH═CHR2 in which R1 and R2 independently represent alkyl groups having from 1 to 6 carbon atoms, substituted with at least one fluorine atom, optionally with at least one chlorine atom.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
       [0001]    The present application is a continuation of U.S. application Ser. No. 13/386,719, filed on Jan. 24, 2012, which is a U.S. national stage of International Application No. PCT/FR2010/051283, filed on Jun. 23, 2010, which claims the benefit of French Application No. 0955267, filed on Jul. 28, 2009. The entire contents of each of U.S. application Ser. No. 13/386,719, International Application No. PCT/FR2010/051283 and French Application No. 0955267 are hereby incorporated herein by reference in their entirety. 
     
    
     TECHNICAL FIELD 
       [0002]    The present invention relates to a process for energy conversion by means of a composition containing hydrofluoroolefins. It relates more particularly to the use of a composition containing hydrofluoroolefins in organic Rankine cycle systems. 
       BACKGROUND 
       [0003]    With the constant increase in energy prices, there is a growing need to optimize energy usage and recovery. Moreover, campaigns for increasing awareness of the need to reduce carbon dioxide emissions show the importance of energy recovery. 
         [0004]    The principle of energy recovery is conversion of unused energy into electricity. The expansion of a fluid such as gas transforms kinetic energy into mechanical energy. Thus, turbines produce electricity by utilizing the phenomenon of expansion to drive a wheel and produce electricity. 
         [0005]    The Rankine cycle constitutes the elementary cycle at an industrial level for producing energy from liquid water/steam. It is composed of the following phases: (i) heating, (ii) evaporation at constant temperature until saturation is attained, (iii) isentropic expansion (ideal case), (iv) condensation at constant temperature and (v) isentropic compression. 
         [0006]    The Rankine cycle can be applied to other thermodynamic systems, in particular using fluids other than steam. Organic Rankine cycles make it possible to exploit the properties of these other fluids. 
         [0007]    The problems posed by substances depleting the ozone layer of the atmosphere (having ozone depletion potential, ODP) were discussed in Montreal, where the protocol was signed requiring a reduction of the production and use of chlorofluorocarbons (CFCs). Amendments have been made to this protocol, requiring abandonment of CFCs and extending the controls to other products. 
         [0008]    Hydrofluorocarbons (HFCs) have replaced CFCs and/or hydrochlorofluorocarbons (HCFCs). 
         [0009]    Thus, 1,1,3,3,3-pentafluoropropane (HFC-245fa) has been proposed as fluid for organic Rankine cycle systems in which HFC-245fa is heated at a temperature between 140° F. and 300° F. (60 and 149° C.) (WO 2006/113902). 
         [0010]    Document WO 2005/085398 discloses the use of polyfluorinated ethers and polyfluorinated ketones as fluid for converting thermal energy to mechanical energy, in particular for organic Rankine cycle systems, at the critical temperature or above the critical temperature of HFC-245fa (154° C.). 
         [0011]    The problem encountered with these polyfluorinated ethers or ketones is the low pressure at the condenser, thus promoting infiltration of air into the installations. The presence of moisture and oxygen in the installations leads to corrosion and to destruction of the mechanical parts. 
     
    
     DETAILED DESCRIPTION 
       [0012]    The applicant has now discovered that compositions containing hydrofluoroolefins are quite particularly suitable as fluid for energy conversion in organic Rankine cycle systems, especially systems operating at low temperature between 60 and 150° C. Moreover, these compositions have a negligible ODP and a GWP (Global Warming 
         [0013]    Potential) less than that of the existing fluids. These mixtures also have critical temperatures above 150° C., and can therefore be used at higher temperatures in organic Rankine cycle systems. 
         [0014]    A fluid&#39;s contribution to the greenhouse effect is quantified by a criterion, GWP, which summarizes the warming effect, taking a reference value of 1 for carbon dioxide. 
         [0015]    Organic Rankine cycle systems operate with fluids called refrigerants in one or more stages. 
         [0016]    The present invention relates to an energy conversion process using a turbine system having at least one stage comprising successively a step of evaporation of a refrigerant, an expansion step in a turbine, a step of desuperheating in an internal exchanger, a step of condensation of said fluid and a step of liquid compression in a pump, characterized in that the refrigerant comprises at least one hydrofluoroolefin, having at least 4 carbon atoms represented by the formula (I) R 1 CH═CHR 2  in which R 1  and R 2  represent, independently, alkyl groups having from 1 to 6 carbon atoms, substituted with at least one fluorine atom, optionally with at least one chlorine atom. 
         [0017]    Preferably, at least one alkyl group of the hydrofluoroolefin is completely substituted with fluorine atoms. 
         [0018]    Preferably, the temperature of condensation of the refrigerant is greater than or equal to the ambient temperature of the air or else of a natural cold source (lake or flow of water), normally between −40° C. and 50° C. depending on the seasons and the geographical location. 
         [0019]    Preferably, the temperature of evaporation of the refrigerant is between 60 and 150° C., and advantageously between 80° C. and 150° C. 
         [0020]    As hydrofluoroolefins of formula (I) that are particularly advantageous, we may notably mention 1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,5,5,5-octafluoropent-2-ene, 1,1,1,4-tetrafluorobut-2-ene, 1,1,1,4,4-pentafluorobut-2-ene, 1,1,4-trifluorobut-2-ene, 1,1,1-trifluorobut-2-ene, 4-chloro-1,1,1-trifluorobut-2-ene, 4-chloro-4,4-difluorobut-2-ene. 
         [0021]    The preferred hydrofluoroolefins of formula (I) can be in the cis or trans form or mixture of the two. 
         [0022]    Besides the hydrofluoroolefin(s) of formula (I), the refrigerant can comprise at least one compound selected from hydrofluorocarbons, hydrocarbons, (hydro)fluoroethers, hydrochlorofluoropropenes, hydrofluoropropenes, ethers, alcohols, methyl formate, carbon dioxide and trans-1,2-dichloroethylene. 
         [0023]    As hydrofluorocarbons, we may notably mention 1,1,1,3,3-pentafluorobutane, 1,1,1,2-tetrafluoroethane, pentafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2,3-pentafluoropropane, 1,1,1,2,2-pentafluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1,1,2,2,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane and 1,1,1,2,3,3,3-heptafluoropropane. 
         [0024]    Hydrocarbons having at least three carbon atoms are preferred. Hydrocarbons with five carbon atoms such as pentane, isopentane, cyclopentane are particularly preferred. 
         [0025]    The preferred hydrochlorofluoropropenes are 2-chloro-3,3,3-trifluoroprop-1-ene and 1-chloro-3,3,3-trifluoroprop-1-ene, in particular trans-1-chloro-3,3,3-trifluoroprop-1-ene. 
         [0026]    The preferred hydrofluoroethers are those having from three to six carbon atoms. 
         [0027]    As hydrofluoroethers, we may notably mention heptafluoromethoxypropane, nonafluoromethoxybutane and nonafluoroethoxybutane. The hydrofluoroether is available in several isomeric forms such as 1,1,1,2,2,3,3,4,4-nonafluoro-ethoxybutane, 1,1,1,2,3,3-hexafluoro-2-(trifluoromethyl)-3-ethoxybutane, 1,1,1,2,2,3,3,4,4-nonafluoro-methoxybutane, 1,1,1,2,3,3-hexafluoro-2-(trifluoromethyl)-3-methoxybutane, and 1,1,1,2,2,3,3-heptafluoromethoxypropane. 
         [0028]    The preferred hydrofluoropropenes are trifluoropropenes such as 1,1,1-trifluoropropene, tetrafluoropropenes such as 2,3,3,3-tetrafluoropropene (HFO-1234yf), and 1,3,3,3-tetrafluoropropene (cis and/or trans). 
         [0029]    The ethers can be selected from dimethyl ether, diethyl ether, dimethoxymethane or dipropoxymethane. 
         [0030]    The alcohols can be selected from ethanol, isopropanol, butanol and isobutanol. 
         [0031]    Preferably, the refrigerant comprises at least one hydrofluoroolefin of formula (I) and at least one hydrofluorocarbon. The hydrofluorocarbon is advantageously selected from 1,1,1,3,3-pentafluorobutane and 1,1,1,3,3-pentafluoropropane. 
         [0032]    Azeotropic compositions of 1,1,1,4,4,4-hexafluorobut-2-ene or of 1,1,1,4,4,5,5,5-octafluoro-pent-2-ene with methyl formate, pentane, isopentane, cyclopentane or trans-1,2-dichloroethylene may also be suitable. 
         [0033]    Preferably, the refrigerant comprises at least 10 wt. % of hydrofluoroolefins of formula (I). 
         [0034]    According to one embodiment of the invention, the refrigerant comprises from 40 to 100 wt. % of 1,1,1,4,4,4-hexafluorobut-2-ene and from 0 to 60 wt. % of at least one compound selected from pentane, isopentane, cyclopentane and trans-1,2-dichloroethylene. 
         [0035]    As refrigerants that are particularly preferred, we may mention those comprising from 60 to 100 wt. % of 1,1,1,4,4,4-hexafluorobut-2-ene and from 0 to 40 wt. % of cyclopentane, pentane, isopentane or trans-1,2-dichloroethylene. 
         [0036]    The refrigerant used in the present invention can comprise a stabilizer of the hydrofluoroolefin. The stabilizer represents at most 5 wt. % relative to the total composition of the fluid. 
         [0037]    As stabilizers, we may notably mention nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-ter-butyl-4-methylphenol, epoxides (alkyl optionally fluorinated or perfluorinated or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones. 
         [0038]    The refrigerant used in the process according to the present invention can comprise lubricants such as mineral oil, alkylbenzene, polyalfaolefin, polyalkylene glycol, polyol ester and polyvinyl ether. The lubricants used with the refrigerant can comprise nanoparticles for improving the thermal conductivity of the fluid as well as its compatibility with the lubricants. As nanoparticles, we may notably mention particles of Al 2 O 3  or of TiO 2 . 
         [0039]    The lubricants used with the refrigerant can comprise dehumidifying agents of the zeolite type. The zeolites absorb water, which prevents corrosion and deterioration of performance. 
       Experimental Section 
       [0040]    Eva p: evaporator,
 
Cond: condenser,
 
Temp: temperature,
 
P: pressure,
 
Efficiency: this is the ratio of the power supplied by the turbine to the useful high-temperature power supplied to the system.
 
The performance of the refrigerant in the operating conditions in an energy conversion cycle with temperature at the evaporator maintained at 11.7° C. and at the condenser at 149° C. are given below.
 
Isentropic efficiency of the turbine: 100%
 
       C: Isopentane 
     D: TDCE 
       [0041]    F: pentane
 
G: 1,1,1,4,4,4-hexafluorobut-2-ene
 
PFE-PFIPK (perfluoroethyl perfluoroisopropyl ketone)
 
MPFBE (methyl perfluorobutyl ether)
 
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                 Temp  
                 Temp  
                 Temp  
                 Temp  
                 Temp  
                 Temp  
                   
                   
                   
                   
                   
                   
               
               
                   
                   
                 cond  
                 cond  
                 pump  
                 evap 
                 turbine  
                 turbine  
                 evap 
                   
                   
                   
                   
                   
               
               
                   
                   
                 inlet  
                 outlet  
                 outlet  
                 inlet  
                 inlet  
                 outlet  
                 P  
                 cond P  
                   
                 isentropic  
                 % Power  
                 Efficiency,  
               
               
                   
                   
                 (° C.) 
                 (° C.) 
                 (° C.) 
                 (° C.) 
                 (° C.) 
                 (° C.) 
                 (bar) 
                 (bar) 
                 Lapse 
                 efficiency 
                 supplied 
                 % 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 245fa 
                 11.7 
                 11.7 
                 12.7 
                 149 
                 149 
                 25.7 
                 33.5 
                 0.86 
                 0.00 
                 1.00 
                 100 
                 100 
               
               
                   
                 PFE- 
                 11.7 
                 11.7 
                   
                 149 
                 149 
                   
                 12.9 
                 0.29 
                 0.000 
                 1.0 
                 149 
                 95 
               
               
                   
                 PFIPK 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 MPFBE 
                 11.7 
                 11.7 
                   
                 149 
                 149 
                   
                  8.7 
                 0.14 
                 0.000 
                 1.0 
                 164 
                 102 
               
               
                   
                 G 
                 11.7 
                 11.7 
                 12.1 
                 149 
                 149 
                 54.2 
                 19.7 
                 0.42 
                 0.00 
                 1.00 
                 98 
                 107 
               
               
                 F 
                 G 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 20 
                 80 
                 14.3 
                 11.7 
                 12.2 
                 149 
                 149 
                 57.2 
                 21.6 
                 0.67 
                 −2.61 
                 1.00 
                 110 
                 107 
               
               
                 30 
                 70 
                 11.7 
                 11.7 
                 12.2 
                 149 
                 149 
                 57.3 
                 21.5 
                 0.68 
                 −0.01 
                 1.00 
                 121 
                 110 
               
               
                 40 
                 60 
                 14.1 
                 11.7 
                 12.2 
                 149 
                 150 
                 58.7 
                 21.0 
                 0.67 
                 −2.39 
                 1.00 
                 132 
                 109 
               
               
                 50 
                 50 
                 16.5 
                 11.7 
                 12.2 
                 149 
                 151 
                 60.6 
                 20.3 
                 0.67 
                 −4.81 
                 1.00 
                 144 
                 109 
               
               
                 C 
                 G 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 20 
                 80 
                 17.2 
                 11.7 
                 12.3 
                 149 
                 149 
                 57.4 
                 23.0 
                 0.78 
                 −5.50 
                 1.00 
                 106 
                 104 
               
               
                 30 
                 70 
                 13.8 
                 11.7 
                 12.3 
                 149 
                 149 
                 56.3 
                 23.3 
                 0.79 
                 −2.05 
                 1.00 
                 116 
                 107 
               
               
                 40 
                 60 
                 11.8 
                 11.7 
                 12.3 
                 149 
                 149 
                 56.9 
                 23.0 
                 0.79 
                 −0.05 
                 1.00 
                 127 
                 110 
               
               
                 50 
                 50 
                 13.4 
                 11.7 
                 12.3 
                 149 
                 150 
                 58.5 
                 22.5 
                 0.79 
                 −1.70 
                 1.00 
                 138 
                 110 
               
               
                 60 
                 40 
                 15.0 
                 11.7 
                 12.3 
                 149 
                 151 
                 59.9 
                 21.8 
                 0.78 
                 −3.29 
                 1.00 
                 149 
                 109 
               
               
                 D 
                 G 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 10 
                 90 
                 13.4 
                 11.7 
                 12.1 
                 149 
                 149 
                 50.7 
                 20.1 
                 0.51 
                 −1.70 
                 1.00 
                 100 
                 107 
               
               
                 15 
                 85 
                 12.9 
                 11.7 
                 12.1 
                 149 
                 149 
                 48.0 
                 20.2 
                 0.52 
                 −1.19 
                 1.00 
                 102 
                 107 
               
               
                 20 
                 80 
                 12.2 
                 11.7 
                 12.1 
                 149 
                 149 
                 44.9 
                 20.2 
                 0.53 
                 −0.50 
                 1.00 
                 105 
                 108 
               
               
                 30 
                 70 
                 12.6 
                 11.7 
                 12.1 
                 149 
                 150 
                 39.4 
                 19.9 
                 0.53 
                 −0.89 
                 1.00 
                 110 
                 108 
               
               
                 40 
                 60 
                 16.2 
                 11.7 
                 12.1 
                 149 
                 152 
                 35.1 
                 19.4 
                 0.53 
                 −4.46 
                 1.00 
                 116 
                 107 
               
               
                   
               
             
          
         
       
     
         [0042]    The results show the low pressure at the condenser for the two products PEE-PFIPK and MPFBE, which promotes infiltration of air into the installations.