# Patent

## Title
Heat transfer process

## Abstract

The present invention relates to the use of a refrigerant in organic Rankine cycle systems comprising 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.

## Background
FIELD OF THE INVENTION
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 OF THE INVENTION
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.
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.
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.
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.
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.
Hydrofluorocarbons (HFCs) have replaced CFCs and/or hydrochlorofluorocarbons (HCFCs).
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).
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.).
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 OF THE INVENTION
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 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.
A fluid'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.
Organic Rankine cycle systems operate with fluids called refrigerants in one or more stages.
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) R1CH═CHR2 in which R1 and R2 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.
Preferably, at least one alkyl group of the hydrofluoroolefin is completely substituted with fluorine atoms.
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.
Preferably, the temperature of evaporation of the refrigerant is between 60 and 150° C., and advantageously between 80° C. and 150° C.
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.
The preferred hydrofluoroolefins of formula (I) can be in the cis or trans form or mixture of the two.
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.
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.
Hydrocarbons having at least three carbon atoms are preferred. Hydrocarbons with five carbon atoms such as pentane, isopentane, cyclopentane are particularly preferred.
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.
The preferred hydrofluoroethers are those having from three to six carbon atoms.
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-methoxy butane, 1,1,1,2,3,3-hexafluoro-2-(trifluoromethyl)-3-methoxybutane, and 1,1,1,2,2,3,3-heptafluoromethoxypropane.
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).
The ethers can be selected from dimethyl ether, diethyl ether, dimethoxymethane or dipropoxymethane.
The alcohols can be selected from ethanol, isopropanol, butanol and isobutanol.
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.
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.
Preferably, the refrigerant comprises at least 10 wt. % of hydrofluoroolefins of formula (I).
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.
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.
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.
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.
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 Al2O3 or of TiO2.
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
Evap: 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
F: pentane
G: 1,1,1,4,4,4-hexafluorobut-2-ene
PFE-PFIPK (perfluoroethyl perfluoroisopropyl ketone)
MPFBE (methyl perfluorobutyl ether)
























Temp
Temp
Temp
Temp
Temp
Temp









cond
cond
pump
evap
turbine
turbine



inlet
outlet
outlet
inlet
inlet
outlet
evap
cond

isentropic
% Power
Efficiency,



(° C.)
(° C.)
(° C.)
(° C.)
(° C.)
(° C.)
P (bar)
P (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









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.

## Claims

1. An energy conversion process employing a turbine system having at least one stage comprising successively:
evaporating a refrigerant;
expanding said refrigerant in a turbine;
desuperheating said refrigerant in an internal exchanger;
condensing said refrigerant; and
compressing said refrigerant in a pump,
wherein
the energy conversion process is an organic Rankine cycle;
the refrigerant comprises at least one hydrofluoroolefin having at least 4 carbon atoms represented by the formula R1CH═CHR2 in which R1 and R2 represent, independently, alkyl groups having from 1 to 6 carbon atoms, substituted with at least one fluorine atom, optionally substituted with at least one chlorine atom; and
the evaporation temperature is between 60 and 150° C.

2. The process as claimed in claim 1, wherein the refrigerant further comprises at least one compound selected from the group consisting of hydrofluorocarbons, hydrocarbons, (hydro)fluoroethers, hydrochlorofluoropropenes, hydrofluoropropenes, ethers, methyl formate, carbon dioxide and trans-1,2-dichloroethylene.

3. The process as claimed in claim 1, wherein the refrigerant further comprises at least one hydrofluorocarbon selected from the group consisting of 1,1,3,3,3-pentafluoropropane and 1,1,3,3,3-pentafluorobutane.

4. The process as claimed in claim 1, wherein the refrigerant further comprises at least one hydrocarbon selected from the group consisting of pentane, isopentane and cyclopentane.

5. The process as claimed in claim 1, wherein 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 the group consisting of pentane, isopentane, cyclopentane and trans-1,2-dichloroethylene.

6. The process as claimed in claim 1, wherein the refrigerant comprises 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.

7. The process as claimed in claim 1, wherein the refrigerant further comprises a stabilizer.

8. The process as claimed in claim 1, wherein the refrigerant further comprises a lubricant.

9. The process as claimed in claim 8, wherein the lubricant is polyalkylene glycol, polyol ester or polyvinyl ether.

10. The process as claimed in claim 1, wherein the evaporation temperature is between 80 and 150° C.

11. The process as claimed in claim 1, wherein the refrigerant is condensed in a condenser distinct from the internal heat exchanger.

12. The process as claimed in claim 1, wherein the refrigerant is condensed in a condenser distinct from the internal heat exchanger.