JP2017226855A - Method for converting heat energy to mechanical energy, organic rankine cycle device, and method for substituting working fluid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new working fluid composition incombustible, also reduced in a load to the environment and further improved in the power generation cycle efficiency of an organic Rankine cycle and the size parameters of a heat expander.SOLUTION: Provided is a method for converting heat energy to mechanical energy using an organic Rankine cycle system stored with a working fluid composition where the operations of vaporizing the working fluid composition, expanding the working fluid composition, condensing the working fluid composition and pressure-rising and transferring the working fluid composition are successively performed. The working fluid composition converts heat energy in which the mass ratio of cis-1,3,3,3-tetrafluoropropene is 92.0 to 99.9 mass%, the mass ratio of trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene is 0.1 to 8.0 mass%, and also evaporation temperature is 60 to 150°C to mechanical energy.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a working fluid composition containing cis-1,3,3,3-tetrafluoropropene and a method for converting thermal energy into mechanical energy in an organic Rankine cycle device containing the working fluid, the organic Rankine cycle device, And a method for replacing a working fluid having a large global warming potential.

  The Kyoto Protocol, which regulates greenhouse gas emissions such as carbon dioxide, methane, dinitrogen monoxide, and chlorofluorocarbon alternatives, has come into effect, and greenhouse gas emissions are currently restricted. For this reason, the development of waste heat power generation by utilizing unused energy to suppress greenhouse gases has become an important issue. Waste heat generated from various industries such as steel, petroleum, chemicals, cement, pulp and paper, ceramics, and biomass, or waste heat from gas turbines, engines and other prime movers, and low temperature waste gas and hot water waste heat are sufficient today It is hard to say that is being used.

  In general, an organic Rankine cycle (ORC) using an organic compound as a working medium is a closed Rankine cycle that does not discharge the working medium to the outside, and an evaporator that vaporizes the working medium, a generator, an expander, a condenser, and a recirculation Consists of a pump and the like. In the Rankine cycle, the working fluid circulates inside the apparatus through four processes of adiabatic compression, constant pressure heating (evaporation), adiabatic expansion, and constant pressure cooling (condensation) in the pump. In the constant pressure heating process, heat exchange with an external heat source is performed, the vaporized working medium is carried to the expander, adiabatically expanded, energy (work) is given to the outside, and taken out as electric energy or the like.

  Conventionally, water has been used as a working medium for Rankine cycle, and has been put into practical use for a long time (for example, US Pat. No. 3,393,515). However, since water has a high freezing point of 0 ° C and a large specific volume of steam, when using a heat source with a relatively low operating temperature range (about 200 ° C or less), the equipment becomes large and the cycle efficiency is high. Has the disadvantage of lowering.

  Under such circumstances, various studies have been made on organic Rankine cycle (ORC) using an organic compound having a boiling point lower than that of water as a working fluid as a low-temperature waste heat utilization technology. A technique using an organic fluorine compound as a fluid has been proposed.

  Patent Document 1 discloses hydrogen-containing halogenated saturated hydrocarbons having 3 carbon atoms, such as 1,1,1,3,3-pentafluoropropane, as a working fluid for organic Rankine cycle.

  Patent Document 2 discloses an organic Rankine cycle apparatus using 2,2-dichloro-1,1,1-trifluoropropane and 1,1,1,3,3-pentafluoropropane as a working fluid. Yes.

  Patent Document 3 discloses an organic Rankine cycle device using fluoroolefins such as 1-chloro-3,3,3-trifluoropropene and monochlorononafluoropentene as a working fluid.

  Patent Document 4 discloses an organic Rankine cycle system using a hydrofluoroolefin having four carbon atoms such as 1,1,1,4,4,4-hexafluoro-2-butene as a working fluid. Yes.

Japanese Patent Laid-Open No. 2-27086 JP 2007-6684 A Special table 2012-511087 gazette Special table 2013-500374 gazette

  In Patent Document 1, hydrogen-containing halogenated saturated hydrocarbons having 3 carbon atoms have been proposed as a working fluid. However, since the global warming potential (GWP) is large, there is a concern about permanent use in the future. ing.

  Patent Document 2 proposes an organic Rankine cycle apparatus using 2,2-dichloro-1,1,1-trifluoropropane and 1,1,1,3,3-pentafluoropropane as a working fluid. These compounds are concerned about their permanent use in the future because they have a large environmental impact from the viewpoint of ozone layer destruction or having a very large global warming potential.

  In patent document 3 or 4, the organic Rankine cycle which uses the composition containing unsaturated halogenated hydrocarbons with a small global warming potential as a working fluid is proposed. Compared to 1,1,1,3,3-pentafluoropropane, which is currently widely used as an organic Rankine cycle working fluid, Rankine cycle efficiency is improved, but the capacity of the expander is increased. It has drawbacks and is not yet fully comprehensive from the viewpoint of performance, and further improvement in performance is desired.

  Thus, the performance of the organic Rankine cycle using a working fluid with high environmental compatibility is still insufficient. Therefore, it is desired to find a working fluid composition mainly composed of a low GWP compound that realizes heat transfer from unused heat of 150 ° C. or less and has better heat transfer performance than conventional working fluids. Yes.

  An object of the present invention is to provide a further improved working fluid composition and organic Rankine cycle device and a method for replacing a working fluid having a large global warming potential. An object of the present invention is to provide a working fluid composition and an organic Rankine cycle device that do not substantially contribute to global warming as compared with many hydrofluorocarbons currently used.

  The inventors diligently studied to solve the above problems. As a result, paying attention to unsaturated halogenated hydrocarbons, in particular, a composition containing a binary halogenated hydrocarbon mainly composed of cis-1,3,3,3-tetrafluoropropene is subjected to a predetermined temperature and pressure. Thus, the present invention has been completed by obtaining the knowledge that if used as a working fluid, it becomes a very effective thermal energy conversion method.

  According to an embodiment of the present invention, the operation sequentially vaporizes the working fluid composition, expands the working fluid composition, condenses the working fluid composition, and pressurizes the working fluid composition. A thermal energy conversion method using an organic Rankine cycle system containing a fluid composition, wherein the working fluid composition has a cis-1,3,3,3-tetrafluoropropene mass ratio of 92.0 masses % To 99.9% by mass, and the mass ratio of trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene is 0.1% to 8.0% by mass. % And a method of converting thermal energy having an evaporation temperature of 60 ° C. or higher and 150 ° C. or lower into mechanical energy.

  According to an embodiment of the present invention, the operation sequentially vaporizes the working fluid composition, expands the working fluid composition, condenses the working fluid composition, and pressurizes the working fluid composition. A thermal energy conversion method using an organic Rankine cycle system containing a fluid composition, wherein the working fluid composition has a cis-1,3,3,3-tetrafluoropropene mass ratio of 80.0 mass % To 99.9% by mass, the mass ratio of 1,1,1,3,3-pentafluoropropane is 0.1% to 20.0% by mass, and the evaporation temperature is 60 ° C. There is provided a method for converting thermal energy of 150 ° C. or lower into mechanical energy.

  In the method of converting thermal energy into mechanical energy, the working fluid composition has a cis-1,3,3,3-tetrafluoropropene mass ratio of 90.0 mass% or more and 99.9 mass% or less, The mass ratio of 1,1,1,3,3-pentafluoropropane may be 0.1% by mass or more and 10.0% by mass or less.

  According to an embodiment of the present invention, the operation sequentially vaporizes the working fluid composition, expands the working fluid composition, condenses the working fluid composition, and pressurizes the working fluid composition. A thermal energy conversion method using an organic Rankine cycle system containing a fluid composition, wherein the working fluid composition has a mass ratio of cis-1,3,3,3-tetrafluoropropene of 50.0 mass % To 99.9% by mass, the mass ratio of trans-1-chloro-3,3,3-trifluoropropene is 0.1% to 50.0% by mass, and the evaporation temperature is A method is provided for converting thermal energy from 60 ° C. to 150 ° C. into mechanical energy.

  In the method of converting thermal energy into mechanical energy, the mass ratio of cis-1,3,3,3-tetrafluoropropene in the working fluid composition is 80.0 mass% or more and 99.9 mass% or less, The mass ratio of trans-1-chloro-3,3,3-trifluoropropene may be 0.1% by mass or more and 20.0% by mass or less.

  In the method of converting thermal energy into mechanical energy, the working fluid composition may include a lubricant.

  In the method for converting thermal energy into mechanical energy, the lubricant may be a mineral oil (paraffinic oil or naphthenic oil) or a synthetic oil alkylbenzene (AB), poly (alpha-olefin), ester, polyol ester. (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE) and combinations thereof.

  In the method of converting thermal energy into mechanical energy, the working fluid composition may further include a stabilizer.

  In the method of converting thermal energy into mechanical energy, the stabilizer is a nitro compound, an epoxy compound, a phenol, an imidazole, an amine, a diene compound, a phosphate, an aromatic unsaturated hydrocarbon, or an isoprene. , Propadiene, terpene and the like and combinations thereof.

  In the method of converting thermal energy into mechanical energy, the working fluid composition may further include a flame retardant.

  In the method of converting thermal energy into mechanical energy, the flame retardant may be selected from phosphates, halogenated aromatic compounds, fluorinated iodocarbons, fluorinated bromocarbons, and combinations thereof.

  In the method of converting thermal energy into mechanical energy, hot water, pressurized hot water or superheated steam having a temperature of 60 ° C. or higher and 150 ° C. or lower may be used as a heating source of the evaporator.

  Moreover, according to one Embodiment of this invention, the organic Rankine-cycle apparatus using the method of converting the thermal energy in any one of the said to mechanical energy is provided.

  According to another embodiment of the present invention, there is provided a method for replacing a working fluid in an organic Rankine cycle device, wherein the working fluid mainly includes 1,1,1,3,3-pentafluoropropane (R245fa), A method is provided comprising supplying any of the working fluid compositions to the organic Rankine cycle apparatus that uses, uses or is designed to use the working fluid.

  According to the working fluid composition of the present invention, it is possible to provide a mixed working fluid for organic Rankine cycle which is nonflammable or slightly flammable, has a small influence on the environment, and has excellent heat transfer and thermal energy conversion characteristics. it can. Moreover, the organic Rankine cycle apparatus excellent in heat transfer and thermal energy conversion characteristics can be provided using the working fluid composition of the present invention. Further, according to the present invention, it is possible to provide a method for replacing a working fluid having a large global warming potential with a novel working fluid composition.

It is the schematic of the organic Rankine cycle which can apply the working fluid which concerns on this invention. It is a Ts diagram in Example 1 of the present invention. It is a Ts diagram in Example 2 of the present invention. It is a Ts diagram in Example 3 of the present invention. It is a Ts diagram in Example 4 of the present invention. It is a Ts diagram in Example 5 of this invention. It is a Ts diagram in Example 6 of this invention. It is a Ts diagram in Example 7 of the present invention. It is a Ts diagram in Example 8 of the present invention. It is a Ts diagram in Example 9 of the present invention. It is a Ts diagram in Example 10 of this invention. It is a Ts diagram in Example 11 of this invention. It is a Ts diagram in Example 12 of this invention. It is a Ts diagram in comparative example 1 of the present invention. It is a Ts diagram in comparative example 2 of the present invention. It is a Ts diagram in comparative example 3 of the present invention. It is a Ts diagram in comparative example 4 of the present invention. It is a Ts diagram in comparative example 5 of the present invention. It is a Ts diagram in comparative example 6 of the present invention. It is a Ts diagram in comparative example 7 of the present invention. It is a Ts diagram in comparative example 8 of the present invention. It is a Ts diagram in comparative example 9 of the present invention. It is a Ts diagram in comparative example 10 of the present invention. It is a Ts diagram in comparative example 11 of the present invention. It is a Ts diagram in comparative example 12 of the present invention.

  Hereinafter, an organic Rankine cycle device and a method for converting thermal energy into mechanical energy according to the present invention will be described with reference to the drawings. However, the organic Rankine cycle apparatus and the method for converting thermal energy into mechanical energy of the present invention are not construed as being limited to the description of the embodiments and examples shown below. Note that in the drawings referred to in this embodiment mode and examples, the same portions or portions having similar functions are denoted by the same reference numerals, and repetitive description thereof is omitted.

  The method for converting thermal energy into mechanical energy according to the present invention (hereinafter referred to as thermal energy conversion method) includes cis-1,3,3,3-tetrafluoropropene as the first component as the main component, A working fluid composition containing a binary halogenated hydrocarbon in which trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene is mixed is used. Moreover, the thermal energy conversion method according to the present invention includes cis-1,3,3,3-tetrafluoropropene as the first component as the main component and trans-1-chloro-3,3 as the second component. , 3-trifluoropropene or 1,1,1,3,3-pentafluoropropane is used, and a working fluid composition containing a binary halogenated hydrocarbon is used. Since the working fluid composition according to the present invention is such a two-component mixture, it is nonflammable or slightly flammable, has a low environmental load, and has excellent thermal cycle characteristics and heat transfer characteristics. We have found that it has.

  Cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)) will be described.

<HFO-1234ze (Z)>
HFO-1234ze (Z) contains a carbon-carbon double bond in the molecule and has high reactivity with a hydroxyl radical, and therefore has a very low global warming potential (GWP) and a low environmental load. HFO-1234ze (Z) is slightly flammable or flame retardant and has no toxicity. HFO-1234ze (Z) has a boiling point of 9.8 ° C. under atmospheric pressure, an atmospheric lifetime of 10 days, and a global warming potential (GWP) of 3 (Chemical Physics Letters 2009, Vol. 473, P233-237). It is. The critical temperature is 150.1 ° C. and the critical pressure is 3.54 MPa (4th IIR Conference on Thermophysical Properties and Transfer Processes of Refrigerant Proceedings TP-018).

  Trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)) will be described.

<HFO-1234ze (E)>
HFO-1234ze (E) contains a carbon-carbon double bond in the molecule and has a high reactivity with a hydroxyl radical, and therefore has a very low global warming potential (GWP) and a low environmental load. Moreover, HFO-1234ze (E) is slightly flammable or flame retardant and has no toxicity. The boiling point of HFO-1234ze (E) is −19 ° C. under atmospheric pressure, the atmospheric lifetime is 14 days, and the global warming potential (GWP) is 6 (Chemical Physics Letters 2007, Vol.443, P199-204). is there. The critical temperature is 109.4 ° C., and the critical pressure is 3.63 MPa (Journal of Chemical Engineering Data 2010, Vol55, P1594-1597).

  2,3,3,3-tetrafluoropropene (HFO-1234yf) will be described.

<HFO-1234yf>
Since HFO-1234yf contains a carbon-carbon double bond in the molecule and has high reactivity with a hydroxyl radical, the global warming potential (GWP) is extremely small and the environmental load is small. HFO-1234yf is slightly flammable and nontoxic. HFO-1234yf has a boiling point of −29 ° C. under atmospheric pressure, an atmospheric life of 11 days, and a global warming potential (GWP) of 4 (Chemical Physics Letters 2007, Vol. 439, P18-22). The critical temperature is 94.7 ° C. and the critical pressure is 3.38 MPa (International Journal of Refrigeration 2010, Vol33, P474-479).

  Next, trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) will be described.

<HCFO-1233zd (E)>
HCFO-1233zd (E) contains a carbon-carbon double bond in the molecule and has high reactivity with a hydroxyl radical, and therefore has a very low global warming potential (GWP) and a low environmental load. HCFO-1233zd (E) is nonflammable and nontoxic. The boiling point of HCFO-1233zd (E) is 18.3 ° C. under atmospheric pressure, the atmospheric lifetime is 26 days, and the global warming potential (GWP) is 7 (Journal of Photochemistry and Photobiology A: Chemistry 2008, Vol.199). , P92-97). The critical temperature is 165.6 ° C., and the critical pressure is 3.77 MPa (Journal of Chemical Engineering Data 2012, Vol57, P3581-3586).

  Next, 1,1,1,3,3-pentafluoropropane (HFC-245fa) will be described.

<HFC-245fa>
HFC-245fa is nonflammable and has low toxicity. The boiling point of HFC-245fa is 15.3 ° C. under atmospheric pressure, the atmospheric lifetime is 7.6 years, and the global warming potential (GWP) is 1030 (IPCC Fourth Assessment Report 2007).

  Since HFC-245fa has a high global warming potential (GWP), when HFC-245fa is used, it is preferable to include 1% by mass or more and 20% by mass or less, particularly 1% by mass or more and 10% by mass or less. desirable.

  In one embodiment, the working fluid composition of the present invention has a mass ratio of cis-1,3,3,3-tetrafluoropropene of 92.0% by mass or more from the viewpoint of heat transfer efficiency in the heat exchanger. 9% by mass or less, and the mass ratio of trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene is 0.1% by mass or more and 8.0% by mass or less. It is characterized by that. By having such a composition, the working fluid composition of the present invention has a global warming potential of less than 150, and has a smaller influence on the environment than HFC-245fa which is widely used.

  In one embodiment, the working fluid composition of the present invention has a cis-1,3,3,3-tetrafluoropropene mass ratio of 80.0 mass% or more and 99.9 mass% or less, The amount of 1,1,3,3-pentafluoropropane is 0.1% by mass or more and 20.0% by mass or less. By having such a composition, the working fluid composition of the present invention has a global warming potential of less than 150, and has a smaller influence on the environment than HFC-245fa which is widely used.

  In one embodiment, the working fluid composition of the present invention has a mass ratio of cis-1,3,3,3-tetrafluoropropene of 50.0% by mass to 99.9% by mass, 1-chloro-3,3,3-trifluoropropene is characterized by being 0.1 mass% or more and 50.0 mass% or less. By having such a composition, the working fluid composition of the present invention has a global warming potential of less than 150, and has a smaller influence on the environment than HFC-245fa which is widely used.

  Cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene or 1,1,1,3,3-pentafluoropropane have a critical temperature relative to each other. Are close to each other, and the working fluid composition according to the present invention including these has a small influence on the critical temperature of the composition. On the other hand, when cis-1,3,3,3-tetrafluoropropene is compared with trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene, trans-1 , 3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene has a low critical temperature. Therefore, in the working fluid composition according to the present invention containing these, as the mass ratio of trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene increases, The critical temperature decreases. Therefore, in the present invention, cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene are used. In the working fluid composition containing, trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene may be 0.1 mass% or more and 8.0 mass% or less. preferable.

  On the other hand, in a working fluid composition containing cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene, cis-1,3,3, The mass ratio of 3-tetrafluoropropene is 50.0 mass% or more, preferably 90.0 mass% or more and 99.9 mass% or less, and the mass of trans-1-chloro-3,3,3-trifluoropropene The ratio is 0.1 mass% or more and 50.0 mass% or less, preferably 0.1 mass% or more and 10.0 mass% or less.

  In a working fluid composition containing cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, cis-1,3,3,3-tetrafluoro The mass ratio of propene is 80.0 mass% or more, preferably 90.0 mass% or more and 99.9 mass% or less, and the mass ratio of 1,1,1,3,3-pentafluoropropane is 0.1 mass. % To 20.0% by mass, preferably 0.1% to 10.0% by mass.

<Lubricant>
When the working fluid composition of the present invention is used as a working fluid for an organic Rankine cycle, the lubricating oil used in the expander sliding portion is a mineral oil (paraffinic oil or naphthenic oil) or a synthetic oil alkylbenzene ( AB), poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE) can be used.

  Alkylbenzenes include n-octylbenzene, n-nonylbenzene, n-decylbenzene, n-undecylbenzene, n-dodecylbenzene, n-tridecylbenzene, 2-methyl-1-phenylheptane, 2-methyl- 1-phenyloctane, 2-methyl-1-phenylnonane, 2-methyl-1-phenyldecane, 2-methyl-1-phenylundecane, 2-methyl-1-phenyldodecane, 2-methyl-1-phenyltridecane Etc.

  Esters include aromatic esters such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and mixtures thereof, dibasic acid esters, polyol esters, complex esters, carbonate esters, etc. It is done.

  Examples of alcohols used as starting materials for polyol esters include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, and di- (penta). And esters of hindered alcohols such as erythritol and tri- (pentaerythritol).

  Examples of the carboxylic acid used as a raw material for the polyol esters include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2- Examples include ethylhexanoic acid and 3,5,5-trimethylhexanoic acid.

  Polyalkylene glycol is methanol having 1 to 18 carbon atoms, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, linear Alternatively, a compound obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide or the like to a branched aliphatic alcohol such as hexanol.

  Examples of polyvinyl ethers include polymethyl vinyl ether, polyethyl vinyl ether, poly n-propyl vinyl ether, polyisopropyl vinyl ether and the like.

<Stabilizer>
In addition, the working fluid composition of the present invention can use a stabilizer in order to improve thermal stability, oxidation resistance and the like. Examples of the stabilizer include nitro compounds, epoxy compounds, phenols, imidazoles, amines, hydrocarbons and the like.

  Examples of the nitro compound include known compounds, and examples thereof include aliphatic and / or aromatic derivatives. Examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. As aromatic nitro compounds, for example, nitrobenzene, o-, m- or p-dinitrobenzene, trinitrobenzene, o-, m- or p-nitrotoluene, o-, m- or p-ethylnitrobenzene, 2,3-, 2 , 4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylnitrobenzene, o-, m- or p-nitroacetophenone, o-, m- or p-nitrophenol, o- , M- or p-nitroanisole and the like.

  Examples of the epoxy compound include ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, 2 -Monoepoxy compounds such as ethylhexyl glycidyl ether, polyepoxy compounds such as diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane tolglycidyl ether Etc.

  Examples of the phenols include phenols containing various substituents such as alkyl groups, alkenyl groups, alkoxy groups, carboxyl groups, carbonyl groups, and halogens in addition to the hydroxyl groups. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, p-t-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol , Eugenol, isoeugenol, butylhydroxyanisole, monovalent phenols such as phenol and xylenol, or divalent tert-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone, etc. Examples of phenol and the like.

  Examples of imidazoles include 1-methylimidazole, 1-n-butylimidazole, 1 to 18 carbon atoms having a linear or branched alkyl group, a cycloalkyl group, or an aryl group as the N-position substituent. -Phenylimidazole, 1-benzylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2 -Dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-ethyl-2-methylimidazole and the like can be mentioned. These compounds may be used alone or in combination.

  Examples of amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methyl. Benzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, diventylamine, triventylamine, 2-ethylhexylamine, aniline N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethyl Npentamin, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamine and the like. These may be used alone or in combination of two or more.

  Examples of hydrocarbons include α-methylstyrene, p-isopropenyltoluene, isoprenes, propadiene, terpenes and the like. These may be used alone or in combination of two or more.

  The stabilizer may be added in advance to one or both of the refrigerant and the lubricant, or may be added alone in the evaporator. At this time, although the usage-amount of a stabilizer is not specifically limited, 0.001 mass% or more and 10 mass% or less are preferable with respect to a main refrigerant | coolant (100 mass%), 0.01 mass% or more and 5 mass% or less Is more preferable, and 0.02 mass% or more and 2 mass% or less is further more preferable. If the added amount of the stabilizer exceeds the upper limit value or is less than the lower limit value, the stability of the refrigerant, the thermal cycle performance, etc. cannot be obtained sufficiently.

<Flame Retardant>
In addition, the working fluid composition of the present invention can use a flame retardant in order to improve combustibility. Examples of the flame retardant include phosphates, halogenated aromatic compounds, fluorinated iodocarbons, fluorinated bromocarbons, and the like.

  The evaporation temperature of the working fluid composition of the present invention having such a composition is 60 ° C. or higher and 150 ° C. or lower, preferably 80 ° C. or higher and 130 ° C. or lower.

  The evaporation pressure of the working fluid composition of the present invention having such a composition is determined by the composition of the working fluid composition and the evaporation temperature. That is, the evaporation pressure is equal to the saturated vapor pressure of the working fluid composition at the evaporation temperature. Generally, when the evaporation pressure exceeds 5.0 MPa, high pressure resistance is required for the compressor, the condenser and the piping parts, and these devices are expensive, which is not preferable. When using the working fluid composition according to the present invention, the evaporation pressure can be made lower than 5.0 MPa, and known expanders, condensers, pumps, and piping parts can be used.

  The working fluid composition of the present invention is nonflammable, has a low environmental load, and is excellent in thermal cycle characteristics. Therefore, working fluid for organic Rankine cycle used for power generation system, etc., heat medium for high-temperature heat pump used for generation of pressurized hot water or superheated steam, refrigerant for vapor compression refrigeration cycle system, absorption heat pump, heat pipe Or a cleaning agent for cycle cleaning of a cooling system or a heat pump system, a metal cleaning agent, a flux cleaning agent, a diluting solvent, a foaming agent, an aerosol, or the like.

  Note that the heat transfer and thermal energy conversion method of the present invention is not limited to package-type small devices (such as Rankine cycle systems and heat pump cycle systems), but also factory-scale large-scale power generation systems, heat pump hot water systems, and heat pump steam generation. Applicable to systems and the like.

Hereinafter, the organic Rankine cycle apparatus using the working fluid composition of the present invention will be described in detail.
<Organic Rankine cycle equipment>
The organic Rankine cycle device is an evaporator that supplies thermal energy from a heating source to a working fluid, adiabatically expands the working fluid that has become steam in a high-temperature and high-pressure state by an expander, and performs work generated by this adiabatic expansion. It is a device that drives a generator to generate electricity. The working fluid vapor after adiabatic expansion is condensed in a condenser to become a liquid, and is transferred to the evaporator by a pump. In addition, as heat energy of a heating source, you may use the exhaust heat of medium and low temperature of 200 degrees C or less, and renewable heat energy.

  In the evaporator or the condenser of the organic Rankine cycle apparatus, examples of the fluid to be cooled or the fluid to be heated that exchanges heat with the working fluid composition include air, water, brine, and silicone oil. These are preferably selected and used according to the cycle operating temperature conditions.

  FIG. 1 is a schematic view showing an example of an organic Rankine cycle apparatus to which the working fluid composition of the present invention can be applied. The configuration and operation (repetition cycle) of the organic Rankine cycle 100 of FIG. 1 will be described below.

  The organic Rankine cycle system 100 of the present invention includes an evaporator 10 (boiler) that receives heat, and a condenser 11 (condenser) that supplies heat. Furthermore, the organic Rankine cycle system 100 has an expander 12 that is operated by a working fluid that circulates through the system, and a circulation pump 13 that increases the pressure of the liquid exiting the condenser 11 and consumes power. The generator 14 that generates electric power is driven by the expander 12.

When the organic Rankine cycle is repeated using the working fluid of the present invention, heat energy can be converted into mechanical energy through the following (a) to (e), and taken out as electrical energy through a generator.
(A) In the heat exchanger (evaporator 10), the liquid working fluid exchanges heat with the fluid to be cooled (heating source) to be vaporized (phase change from liquid to gas).
(B) Remove the vaporized working fluid from the heat exchanger.
(C) The vaporized working fluid is expanded through an expander (power generation turbine 12) and converted into mechanical (electrical) energy.
(D) The working fluid exiting from the expander is passed to the condenser, and the gaseous working fluid is condensed (phase change from gas to liquid).
(E) The liquefied working fluid is pressurized and transferred by the pump 13 and recirculated to the step (a).

  The organic Rankine cycle system containing the working fluid has at least one evaporator 10, an expander 12, a condenser 11, a pump 13, and piping for transporting the working fluid between these elements. In addition, you may have an internal heat exchanger in a system.

  The type of expander is not particularly limited, but a single-stage or multi-stage centrifugal expander, rotary piston expander, rotary vane expander, scroll expander, screw expander or piston / crank expander is used. it can.

  By using the working fluid composition of the present invention as the working fluid of the organic Rankine cycle system, heat energy of 60 ° C. or more and 150 ° C. or less can be converted into mechanical energy. Mechanical energy may be converted into electrical energy by a generator.

  In addition, the working fluid composition of the present invention was used using a working fluid having a large global warming potential (high GWP working fluid) mainly containing 1,1,1,3,3-pentafluoropropane (R245fa). Or it can be applied to an organic Rankine cycle device designed to be used. By replacing the high GWP working fluid with the working fluid composition of the present invention in the organic Rankine cycle device, the GWP can be reduced and the load on the environment can be reduced.

  One aspect of the method of replacing the working fluid contained in the organic Rankine cycle apparatus is a method in which all of the contained high GWP working fluid is recovered and then filled with the working fluid composition of the present invention. . The method for replacing the working fluid is not particularly limited, but it is preferable to perform the method when the operation of the organic Rankine cycle apparatus is stopped. In order to recover the high GWP working fluid, it is desirable to use a recovery device used when recovering the fluorocarbon refrigerant in order to reduce the burden on the environment. After recovering the high GWP working fluid and before filling the working fluid composition of the present invention, the working fluid container of the organic Rankine cycle device may be decompressed with a vacuum pump. The method of filling the working fluid composition of the present invention is not particularly limited, but the working fluid composition may be filled using the pressure difference between the working fluid and the organic Rankine cycle device, or filled using mechanical power such as a pump. Also good.

  The working fluid composition of the present invention comprises cis-1,3,3,3-tetrafluoropropene as the first component as the main component and trans-1,3,3,3-tetrafluoro as the second component. By being a working fluid composition containing a two-component halogenated carbonization in which propene or 2,3,3,3-tetrafluoropropene is mixed, it is nonflammable or slightly flammable and can be used in a widely used HFC-245fa. The impact on the environment is small. Moreover, the working fluid composition of the present invention is excellent in heat transfer and thermal energy conversion characteristics, and can be suitably used for an organic Rankine cycle apparatus.

Examples of indexes for evaluating the characteristics of the working fluid composition used in the organic Rankine cycle apparatus include power generation cycle efficiency (η _cycle ) and expander size parameter (SP).

Power generation cycle efficiency (η _cycle ) is a generally accepted measure of working fluid performance and is particularly useful for representing the relative thermodynamic efficiency of the working fluid composition in the Rankine cycle. The ratio of the electrical energy generated by the working fluid in the expander and the generator to the thermal energy supplied from the heating source when the working fluid evaporates is represented by η _cycle .

  The expander size parameter (SP) is a measure for evaluating the size of the expander and is generally accepted (Energy 2012, Vol. 38, P136-143). When a working fluid composition is replaced in a Rankine cycle under the same conditions, a larger SP value means that the working fluid composition requires a larger size expander. That is, a smaller SP value is more preferable because a smaller expander can be employed and contributes to the miniaturization of the Rankine cycle system.

  On the other hand, when the value of the power generation cycle efficiency is high, the value of SP is also high. Conversely, when the value of the power generation cycle efficiency is low, the value of SP is low. That is, the power generation cycle efficiency and the SP value are in a trade-off relationship. In the working fluid composition used in the organic Rankine cycle apparatus, it is preferable that the power generation cycle efficiency is high, but in order to satisfy the demand for downsizing the Rankine cycle system, the SP value is preferably low. In the conventional working fluid composition, it was difficult to satisfy this condition in a practical range.

  The working fluid composition of the present invention contains a two-component halogenated hydrocarbon mainly composed of cis-1,3,3,3-tetrafluoropropene, so that power generation cycle efficiency and SP can be improved within a practical range. It is a novel composition whose value can be adjusted.

  In addition, the working fluid composition of the present invention is mainly composed of cis-1,3,3,3-tetrafluoropropene, so that the expander inlet volume flow rate and the expander outlet volume flow rate are widely used. Since it can be used as an alternative to HFC-245fa in an existing organic Rankine cycle apparatus, the load on the environment of the existing organic Rankine cycle apparatus can be reduced at low cost.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the Example which concerns.

[Example 1]
<Composition for mixed heat transfer of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, the conditions shown in Table 1 were used. Power generation cycle efficiency and expander size parameters were calculated. The physical property values of the working fluid composition were determined by REFPROP ver. 9.0 of the National Institute of Standards and Technology (NIST).

  The organic Rankine cycle calculation condition 1 is shown in Table 1 below.

  The organic Rankine cycle condition 1 assumes that the temperature of the heat source water supplied to the evaporator is 90 ° C. and the temperature of the cooling water supplied to the condenser is 30 ° C.

  It is known that non-azeotropic working fluid mixtures exhibit a temperature gradient in evaporation or condensation. The temperature gradient is the temperature difference (difference between the heat exchanger outlet temperature and the heat exchanger inlet temperature) that occurs at the inlet and outlet of the heat exchanger when the non-azeotropic working fluid mixture evaporates or condenses at a constant pressure. When applying a non-azeotropic working fluid mixture to an organic Rankine cycle, gradient effects on evaporation and condensation temperatures must be considered.

  A temperature gradient that is the difference between the boiling point temperature and the dew point temperature of a non-azeotropic mixture at constant pressure is a characteristic of the refrigerant. The working fluid composition of the present invention is an azeotrope-like or non-azeotropic composition with a very small temperature gradient. From the viewpoint of heat transfer efficiency in the heat exchanger, it is desirable that the temperature gradient is small, and specifically, 5K or less is more preferable.

In calculating the power generation cycle efficiency (η _cycle ) and the expander size parameter (SP) of the organic Rankine cycle, the following items were assumed.
(A) The ideal expansion process of Rankine cycle is isentropic expansion, and expander adiabatic efficiency η _T is introduced in consideration of actual machine loss.
(B) The generator loss due to the expander is taken into account by the generator efficiency η _G.
(C) The circulation pump power is driven by generated electricity, and pump efficiency η _P including motor efficiency is introduced. The pump is a can type and the loss is included in the cycle as heat.
(D) Since the circulating pump power of the bearing lubricating oil is very small, it is ignored.
(E) Ignore heat loss and pressure loss of piping.
(F) The working fluid at the outlet of the evaporator is saturated steam.
(G) The working fluid at the outlet of the condenser is a saturated liquid.

When the working fluid was a non-azeotropic mixture, the following items were further assumed.
(H) Let the dew point of the evaporation step be the evaporation temperature, and let the pressure be the evaporation pressure.
(I) The dew point of the condensation step is defined as the condensation temperature, and the pressure is defined as the condensation pressure.

The basic formula for calculating the power generation cycle efficiency (η _cycle ) of the organic Rankine cycle is described in detail below. The basic formula is Ebara Times No. 211 (2006-4), p. The calculation formula of “Development of waste heat power generation equipment (examination of working medium and expansion turbine)” on page 11 was used. In addition, when the working fluid is a non-azeotropic mixture, a dew point method is adopted in which the evaporation temperature and the condensation temperature are determined by the dew point. The dew point method is adopted in JIS B8600 “Rated temperature condition of refrigerant compressor”.

The theoretically generated power L _Tth of the expander by the working fluid circulation amount G is
L _Tth = G × (h ₁ −h _2th ) (1)
It becomes.

Generated in consideration of the expansion machine efficiency η _T power L _T is,
L _T = L _Tth × η _T = G × (h ₁ −h ₂ ) (2)
It becomes.

Power generation amount E _G considering the generator efficiency eta _G is
E _G = L _T × η _G (3)
It becomes.

Circulation pump, intended for feeding the working medium fluid of the condenser outlet to the condenser pressure P _C higher evaporator pressure of the pressure from the P _E, the theoretical power requirement L _Pth is
L _{P th} = (P _E −P _C ) × G / ρ ₃ (4)
It becomes.

Required power E _P in consideration of pump efficiency eta _P is
E _P = L _{P th} / η _P = G × (h ₄ −h ₃ ) (5)
It becomes.

Effective power generation E _cycle is
E _cycle = E _G -E _P (6)
It becomes.

The amount of heat Q _E supplied to the evaporator is
Q _E = G × (h ₁ − h ₄ )
= G × (h ₁ −h ₃ ) − (P _E −P _C ) × G / (ρ ₃ × η _P ) (7)
It becomes.

Efficiency as a power generation cycle is
η _cycle = (E _G −E _P ) × 100 / Q _E (8)
It becomes.

  Next, the expander size parameter (SP) will be described in detail. The basic formula used was a calculation formula described in non-patent literature (Energy 2012, Vol. 38, P136-143).

When the working fluid circulation amount is G, the working fluid volume flow rate V _{2th at the} expander outlet in the isentropic expansion is
V _2th = G / ρ _2th (9)
It becomes.

The theoretical heat drop ΔH _th of the expander is
ΔH _th = h ₁ −h _2th (10)
It becomes.

The expander size parameter (SP) is
SP = (V _2th ) ^0.5 / (ΔH _th ) ^0.25 (11)
It becomes.

In addition, in said (1)-(11), various symbols mean the following.
G: Working fluid circulation rate
L _Tth : The theoretically generated power of the expander
L _T : Power generated by the expander
E _G : Power generation amount
E _P : Circulating pump power requirement
P _c : Condenser pressure
P _E : Evaporator pressure
L _Pth : Theoretical power required to operate the circulation pump
E _cycle : Effective power generation
Q _E : Heat input η _cycle : Power generation cycle efficiency
V _2th : Theoretical volume flow at the outlet of the expander ΔH _th : Theoretical heat drop of the expander
SP: Expander size parameter ρ: Working fluid density h: Specific enthalpy
_1,2,3,4 : Cycle points

  FIG. 2 shows a Ts diagram in Example 1 (mass ratio of cis-1,3,3,3-tetrafluoropropene: 1,1,1,3,3-pentafluoropropane is 95: 5). In the figure, cycle points 1, 2, 3, and 4 indicate organic Rankine cycle calculation condition 1.

[Example 2]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene>
Table 1 shows the performance of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene. The power generation cycle efficiency and expander size parameters were calculated under the conditions. In FIG. 3, the Ts line in Example 2 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1-chloro-3,3,3-trifluoropropene is 95: 5). The figure is shown.

[Example 3]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, the conditions shown in Table 2 were used. Power generation cycle efficiency and expander size parameters were calculated. In FIG. 4, the Ts diagram in Example 3 (mass ratio of cis-1,3,3,3-tetrafluoropropene: 1,1,1,3,3-pentafluoropropane is 95: 5) is shown. Show.

  The organic Rankine cycle calculation condition 2 is shown in Table 2 below.

  The organic Rankine cycle condition 2 assumes that the temperature of the heat source water supplied to the evaporator is 110 ° C. and the temperature of the cooling water supplied to the condenser is 30 ° C.

[Example 4]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene>
Table 2 shows the performance of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene. The power generation cycle efficiency and expander size parameters were calculated under the conditions. In FIG. 5, the Ts line in Example 4 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1-chloro-3,3,3-trifluoropropene is 95: 5). The figure is shown.

[Example 5]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, the conditions shown in Table 3 were used. Power generation cycle efficiency and expander size parameters were calculated. In FIG. 6, the Ts diagram in Example 5 (mass ratio of cis-1,3,3,3-tetrafluoropropene: 1,1,1,3,3-pentafluoropropane is 95: 5) is shown. Show.

  The organic Rankine cycle calculation condition 3 is shown in Table 3 below.

[Example 6]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene>
Table 3 shows the performance of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene. The power generation cycle efficiency and expander size parameters were calculated under the conditions. In FIG. 7, the Ts line in Example 6 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1-chloro-3,3,3-trifluoropropene is 95: 5). The figure is shown.

[Example 7]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene, the conditions shown in Table 1 were used. Power generation cycle efficiency and expander size parameters were calculated. In FIG. 8, the Ts diagram in Example 7 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1,3,3,3-tetrafluoropropene is 95: 5) is shown. Show.

[Example 8]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene>
In the performance evaluation of the organic Rankine cycle using the mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene, the conditions shown in Table 2 were used. Power generation cycle efficiency and expander size parameters were calculated. In FIG. 9, the Ts diagram in Example 8 (the mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1,3,3,3-tetrafluoropropene is 95: 5) is shown. Show.

[Example 9]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene, the conditions shown in Table 3 were used. Power generation cycle efficiency and expander size parameters were calculated. In addition, in FIG. 10, the Ts diagram in Example 9 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1,3,3,3-tetrafluoropropene is 95: 5). Show.

[Example 10]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, a power generation cycle under the conditions shown in Table 1 Efficiency and expander size parameters were calculated. In addition, in FIG. 11, the Ts diagram in Example 10 (mass ratio of cis-1,3,3,3-tetrafluoropropene: 2,3,3,3-tetrafluoropropene is 95: 5) is shown.

[Example 11]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, a power generation cycle under the conditions shown in Table 2 Efficiency and expander size parameters were calculated. In addition, in FIG. 12, the Ts diagram in Example 11 (The mass ratio of cis-1,3,3,3-tetrafluoropropene: 2,3,3,3-tetrafluoropropene is 95: 5) is shown.

[Example 12]
<Mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene>
In performance evaluation of an organic Rankine cycle using a mixed working fluid composition of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, a power generation cycle under the conditions shown in Table 3 Efficiency and expander size parameters were calculated. In addition, in FIG. 13, the Ts diagram in Example 12 (The mass ratio of cis-1,3,3,3-tetrafluoropropene: 2,3,3,3-tetrafluoropropene is 95: 5) is shown.

[Comparative Example 1]
<1,1,1,3,3-pentafluoropropane>
In the performance evaluation of an organic Rankine cycle using 1,1,1,3,3-pentafluoropropane as a working fluid instead of the working fluid composition of the present invention, the power generation cycle efficiency and the expander were evaluated under the conditions shown in Table 1. Size parameters were calculated. In addition, in FIG. 14, the Ts diagram in the comparative example 1 is shown.

[Comparative Example 2]
<1,1,1,3,3-pentafluoropropane>
In the performance evaluation of the organic Rankine cycle using 1,1,1,3,3-pentafluoropropane as the working fluid instead of the working fluid composition of the present invention, the power generation cycle efficiency and the expander were evaluated under the conditions shown in Table 2. Size parameters were calculated. In addition, in FIG. 15, the Ts diagram in the comparative example 2 is shown.

[Comparative Example 3]
<1,1,1,3,3-pentafluoropropane>
In the performance evaluation of the organic Rankine cycle using 1,1,1,3,3-pentafluoropropane as the working fluid instead of the working fluid composition of the present invention, the power generation cycle efficiency and the expander were evaluated under the conditions shown in Table 3. Size parameters were calculated. In addition, in FIG. 16, the Ts diagram in the comparative example 3 is shown.

[Comparative Example 4]
<Cis-1-chloro-3,3,3-trifluoropropene>
In the performance evaluation of the organic Rankine cycle using cis-1-chloro-3,3,3-trifluoropropene as the working fluid instead of the working fluid composition of the present invention, the power generation cycle efficiency and the conditions shown in Table 1 The expander size parameter was calculated. In addition, in FIG. 17, the Ts diagram in the comparative example 4 is shown.

[Comparative Example 5]
<Cis-1-chloro-3,3,3-trifluoropropene>
In the performance evaluation of the organic Rankine cycle using cis-1-chloro-3,3,3-trifluoropropene as the working fluid instead of the working fluid composition of the present invention, the power generation cycle efficiency and the conditions shown in Table 2 The expander size parameter was calculated. In addition, in FIG. 18, the Ts diagram in the comparative example 5 is shown.

[Comparative Example 6]
<Cis-1-chloro-3,3,3-trifluoropropene>
In the performance evaluation of the organic Rankine cycle using cis-1-chloro-3,3,3-trifluoropropene as the working fluid instead of the working fluid composition of the present invention, the power generation cycle efficiency and the conditions shown in Table 3 The expander size parameter was calculated. In addition, in FIG. 19, the Ts diagram in the comparative example 6 is shown.

[Comparative Example 7]
<Mixed working fluid composition of cis-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane>
Table 1 shows the performance of an organic Rankine cycle using a mixed working fluid composition of cis-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane. The power generation cycle efficiency and expander size parameters were calculated under the conditions. In FIG. 20, the Ts line in Comparative Example 7 (mass ratio of cis-1-chloro-3,3,3-trifluoropropene: 1,1,1,3,3-pentafluoropropane is 95: 5). The figure is shown.

[Comparative Example 8]
<Mixed working fluid composition of cis-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane>
Table 2 shows the performance of an organic Rankine cycle using a mixed working fluid composition of cis-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane. The power generation cycle efficiency and expander size parameters were calculated under the conditions. In FIG. 21, the Ts line in Comparative Example 8 (the mass ratio of cis-1-chloro-3,3,3-trifluoropropene: 1,1,1,3,3-pentafluoropropane is 95: 5). The figure is shown.

[Comparative Example 9]
<Mixed working fluid composition of cis-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane>
Table 3 shows the performance of an organic Rankine cycle using a mixed working fluid composition of cis-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane. The power generation cycle efficiency and expander size parameters were calculated under the conditions. In FIG. 22, the Ts line in Comparative Example 9 (the mass ratio of cis-1-chloro-3,3,3-trifluoropropene: 1,1,1,3,3-pentafluoropropane is 95: 5). The figure is shown.

[Comparative Example 10]
<Combined working fluid composition of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentane>

Cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (Z)) will be described.
<HFO-1336mzz (Z)>
HFO-1336mzz (Z) is nonflammable and has low toxicity. The boiling point of HFO-1336mzz (Z) is 33 ° C. under atmospheric pressure, the atmospheric life is 20 days, and the global warming potential (GWP) is 9 (Journal of Physical chemistry A 2011 vol.115 P10539-10549). .

Next, pentane will be described.
<Pentane>
Pentane is flammable and has low toxicity. Pentane has a boiling point of 36 ° C. under atmospheric pressure and a global warming potential (GWP) of 3.

  In the performance evaluation of the organic Rankine cycle using the mixed working fluid composition of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentane, the power generation cycle efficiency and expansion under the conditions shown in Table 1 Machine size parameters were calculated. In addition, in FIG. 23, the Ts diagram in Comparative Example 10 (mass ratio of cis-1,1,1,4,4,4-hexafluoro-2-butene: pentane is 95: 5) is shown.

[Comparative Example 11]
<Combined working fluid composition of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentane>
In the performance evaluation of the organic Rankine cycle using the mixed working fluid composition of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentane, the power generation cycle efficiency and expansion under the conditions shown in Table 2 Machine size parameters were calculated. In addition, in FIG. 24, the Ts diagram in the comparative example 11 (mass ratio of cis-1,1,1,4,4,4-hexafluoro-2-butene: pentane is 95: 5) is shown.

[Comparative Example 12]
<Combined working fluid composition of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentane>
In the performance evaluation of the organic Rankine cycle using the mixed working fluid composition of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentane, the power generation cycle efficiency and expansion under the conditions shown in Table 3 Machine size parameters were calculated. In addition, in FIG. 25, the Ts diagram in Comparative Example 12 (mass ratio of cis-1,1,1,4,4,4-hexafluoro-2-butene: pentane is 95: 5) is shown.

The calculation results of the organic Rankine cycle performance (η _cycle and SP) of Examples 1 to 12 and Comparative Examples 1 to 12 are shown in Tables 4 to 41.

  In Examples 1-12 and Comparative Examples 7-12, the value of the 1st component of the composition for heat transfer, and the 2nd component is shown by the mass percentage. In Examples 1, 3 and 5, the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is 1,1,1,3,3- Pentafluoropropane.

  In Examples 2, 4 and 6, the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is trans-1-chloro-3,3. 3-trifluoropropene.

  In Examples 7 to 9, the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is trans-1,3,3,3-tetrafluoro. Propen.

  In Examples 10 to 12, the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is 2,3,3,3-tetrafluoropropene. is there.

  In Comparative Examples 7 to 9, the first component of the mixed heat transfer composition is cis-1-chloro-3,3,3-trifluoropropene, and the second component is 1,1,1,3,3- Pentafluoropropane.

  In Comparative Examples 10 to 12, the first component of the mixed heat transfer composition is cis-1,1,1,4,4,4-hexafluoro-2-butene, and the second component is pentane.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP of Example 1 shown in Table 4, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 5 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP of Example 2 shown in Table 6, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 7 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP of Example 3 shown in Table 8, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 9 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Example 4 shown in Table 10, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 11 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP of Example 5 shown in Table 12, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 13 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP of Example 6 shown in Table 14, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 15 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Example 7 shown in Table 16, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. It shows in Table 17.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP of Example 8 shown in Table 18, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 19 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Example 9 shown in Table 20, the relative values are set to 1,1,1,3,3-pentafluoropropane as 1, respectively. It shows in Table 21.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Example 10 shown in Table 22, the relative values are set to 1,1,1,3,3-pentafluoropropane as 1, respectively. Table 23 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Example 11 shown in Table 24, the relative values are set to 1,1,1,3,3-pentafluoropropane as 1, respectively. Table 25 shows.

Regarding the values of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Example 12 shown in Table 26, the relative values are set to 1,1,1,3,3-pentafluoropropane as 1, respectively. It shows in Table 27.

Regarding the value of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP of Comparative Example 7 shown in Table 30, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. It shows in Table 31.

Regarding the value of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Comparative Example 8 shown in Table 32, the relative values are set to 1,1,1,3,3-pentafluoropropane as 1, respectively. Table 33 shows.

Regarding the value of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Comparative Example 8 shown in Table 34, the relative values are set to 1,1,1,3,3-pentafluoropropane as 1, respectively Table 35 shows.

Regarding the value of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Comparative Example 10 shown in Table 36, the relative values are set to 1,1,1,3,3-pentafluoropropane as 1, respectively Table 37 shows.

Regarding the values of the expander inlet volume flow rate, expander outlet volume flow rate, power generation cycle efficiency and SP of Comparative Example 11 shown in Table 38, 1,1,1,3,3-pentafluoropropane is set to 1, and relative values are set. Table 39 shows.

Regarding the value of the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency and the SP of Comparative Example 12 shown in Table 40, 1,1,1,3,3-pentafluoropropane is set to 1, and the relative value Table 41 shows.

  As shown in Tables 4 to 41, the mixed working fluid composition of the present invention has 1,1,1 described in Patent Document 1 (Japanese Patent Laid-Open No. 2-27086) and Patent Document 2 (Japanese Patent Laid-Open No. 2007-6684). The power generation cycle efficiency when applied to the organic Rankine cycle is higher than that of the 3,3-pentafluoropropane working fluid, and the expander size parameter (SP) is lower. That is, when the working fluid composition of the present invention is used as a working fluid in an organic Rankine cycle for converting thermal energy of 60 ° C. to 150 ° C. into mechanical energy (and electrical energy), 1, 1, 1, 3, This means that the cycle efficiency can be improved and the apparatus can be made smaller than the 3-pentafluoropropane working fluid.

  As shown in Tables 4 to 41, the mixed working fluid composition of the present invention is a cis-1-chloro-3,3,3-trifluoropropene working fluid described in Patent Document 3 (Japanese Patent Publication No. 2012-51087). The expander size parameter (SP) when applied to the organic Rankine cycle is a lower value. That is, when the working fluid composition of the present invention is used as a working fluid in an organic Rankine cycle for converting thermal energy of 60 ° C. to 150 ° C. into mechanical energy (and electrical energy), cis-1-chloro-3, This means that the apparatus can be made smaller than 3,3-trifluoropropene working fluid.

  As shown in Tables 4 to 41, the mixed working fluid composition of the present invention has a cis-1,1,1,4,4,4-hexafluoro- described in Patent Document 4 (Japanese Patent Publication No. 2013-500374). The expander size parameter (SP) when applied to the organic Rankine cycle is lower than that of the mixed working fluid composition of 2-butene and pentane, and has the same power generation cycle efficiency. That is, when the working fluid composition of the present invention is used as a working fluid in an organic Rankine cycle for converting thermal energy of 60 ° C. to 150 ° C. into mechanical energy (and electrical energy), cis-1,1,1, It means that a cycle performance equivalent to a mixed working fluid composition of 4,4,4-hexafluoro-2-butene and pentane can be achieved with a smaller apparatus.

[Example 13]
A SUS316 autoclave was charged with 30 g of the working fluid, heated to 150 ° C. and held for 5 weeks. Using gas chromatography, the presence or absence of a decomposition product of the working fluid and an isomer product of the working medium were evaluated. The results obtained are shown in Table 42.

  None of the working fluids showed any pyrolysis products. Further, as is clear from the results shown in Table 42, the isomerization reaction of HFO-1234ze did not proceed in both the trans form and the cis form. A small amount of isomer formation was confirmed in the trans form of HCFO-1233zd, and isomerization of the cis form of HCFO-1233zd into 80% geometric isomer (trans form) was confirmed. It can be seen that the heat transfer composition used in the present invention is excellent in thermal stability under a temperature condition of 150 ° C. or lower.

[Example 14]
A thermal stability test was conducted using cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)). In accordance with the shield tube test of JIS-K-2211 “Refrigerator oil”, 1.0 g of working fluid and metal pieces (iron, copper, and aluminum test pieces) are sealed in a glass test tube and heated to a predetermined temperature. Held for 2 weeks. The heating temperature was 175 or 200 ° C. Appearance of the working fluid after 2 weeks, purity, acid content ^- the (F ions) were measured to evaluate the thermal stability. The results obtained are shown in Table 43.

[Example 15]
A thermal stability test was conducted using 1,1,1,3,3-pentafluoropropane (HFC-245fa). In accordance with the shield tube test of JIS-K-2211 “refrigeration machine oil”, 1.0 g of heat transfer composition and metal pieces (iron, copper, and aluminum test pieces) are sealed in a glass test tube, and a predetermined temperature is obtained. And heated for 2 weeks. The heating temperature was 175 or 200 ° C. Appearance of the working fluid after 2 weeks, purity, acid content ^- the (F ions) were measured to evaluate the thermal stability. The results obtained are shown in Table 44.

As is apparent from the results shown in Tables 43 and 44, no thermal decomposition products of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane were observed. It was. In addition, the by-product acid content (F ⁻ ) after the thermal stability test is extremely small, and it can be seen that the working fluid composition used in the present invention is excellent in thermal stability even under high temperature conditions.

[Example 16]
In accordance with the compatibility test between the heat transfer composition of JIS-K-2211 “refrigeration oil” and the refrigerating machine oil, 1.7 g of working fluid and 0.3 g of refrigerating machine oil were added to a thick glass test tube, and liquid nitrogen was added. The mixture of the heat transfer composition and the refrigerating machine oil was solidified. After the working fluid and refrigeration oil mixture solidified, the upper part of the test tube was connected to a vacuum pump to remove the remaining air, and the upper part of the test tube was sealed with a gas burner. The sealed thick glass test tube was placed in a thermostat cooled to −20 ° C. and allowed to stand until the temperature of the thermostat and the composition in the glass test tube were equal. Thereafter, the compatibility between the heat transfer composition and the refrigerating machine oil was visually evaluated. The compatibility was evaluated by changing the temperature of the thermostatic bath to -20 to + 80 ° C. The results obtained are shown in Tables 45-49. In Tables 45-49, it evaluated by (circle) when it was compatibilized uniformly, and x when two-layer separation or the composition became turbid.

The following five types of lubricating oil were used for the compatibility test.
Mineral oil (MO): Suniso 4GS (manufactured by Nippon San Oil)
Polyol ester oil (POE): SUNICE T68 (manufactured by Nippon San Oil)
Alkylbenzene oil (AB): Atmos 68N (manufactured by JX Nippon Oil & Energy)
Polyalkylene glycol oil (PAG): SUNICE P56 (Nihon Sun Oil Co., Ltd.)
Polyvinyl ether oil (PVE): Daphne Hermetic Oil FVC68D (manufactured by Idemitsu Kosan)

  All working fluids showed good compatibility with the synthetic oils POE, PAG or PVE. In addition, HCFO-1233zd containing chlorine showed good compatibility with both mineral oil and alkylbenzene oil in both trans and cis forms.

  The present invention is a method for converting thermal energy into mechanical energy when a working fluid composition that is nonflammable or slightly flammable and has a low environmental load is used as a working fluid in an organic Rankine cycle system. This method can be suitably used when the evaporation temperature condition is 60 ° C. or higher and 150 ° C. or lower as compared with the conventional thermal energy conversion method using a hydrofluorocarbon working fluid. In addition, excellent cycle efficiency and expander size parameters can greatly contribute to the production of electrical energy from thermal energy. The method of the present invention can be reused as electric energy by utilizing the heat energy in the medium / low temperature range that has not been sufficiently utilized until now.

10: evaporator, 11: condenser, 12: expander, 13: circulation pump, 14: generator, 100: organic Rankine cycle device

Claims (11)

Vaporize the working fluid composition;
Expanding the working fluid composition;
Condensing the working fluid composition;
A method of converting thermal energy into mechanical energy using an organic Rankine cycle system containing the working fluid composition, which sequentially increases the pressure and transfers the working fluid composition with a pump,
In the working fluid composition, the mass ratio of cis-1,3,3,3-tetrafluoropropene is 80.0 mass% or more and 99.9 mass% or less, and 1,1,1,3,3-penta A method for converting thermal energy into mechanical energy, wherein the mass ratio of fluoropropane is 0.1 mass% or more and 20.0 mass% or less, and the evaporation temperature is 60 ° C or more and 150 ° C or less.   The working fluid composition has a cis-1,3,3,3-tetrafluoropropene mass ratio of 90.0% by mass or more and 99.9% by mass or less, and 1,1,1,3,3-pentafluoro The method for converting thermal energy into mechanical energy according to claim 1, wherein the mass ratio of propane is 0.1 mass% or more and 10.0 mass% or less.   The method for converting thermal energy into mechanical energy according to claim 1 or 2, wherein the working fluid composition comprises a lubricant.   The lubricant is a paraffinic oil or a naphthenic oil, a mineral oil or a synthetic oil, alkylbenzenes, poly (alpha-olefin), esters, polyol esters, polyalkylene glycols, polyvinyl ethers and combinations thereof. 4. A method for converting thermal energy into mechanical energy according to claim 3, characterized in that it is selected.   The method for converting thermal energy into mechanical energy according to any one of claims 1 to 4, wherein the working fluid composition further comprises a stabilizer.   The stabilizer is selected from nitro compounds, epoxy compounds, phenols, imidazoles, amines, diene compounds, phosphates, aromatic unsaturated hydrocarbons, isoprenes, propadiene, terpenes and combinations thereof A method for converting thermal energy into mechanical energy according to claim 5.   The method for converting thermal energy into mechanical energy according to claim 1, wherein the working fluid composition further comprises a flame retardant.   8. The thermal energy of claim 7, wherein the flame retardant is selected from phosphates, halogenated aromatic compounds, fluorinated iodocarbons, fluorinated bromocarbons and combinations thereof. Method.   The heat energy according to any one of claims 1 to 8, wherein hot water of 60 to 150 ° C, pressurized hot water or superheated steam is used as a heating source of the evaporator. how to.   The organic Rankine cycle apparatus using the method of converting the thermal energy according to any one of claims 1 to 9 into mechanical energy. A method of replacing a working fluid in an organic Rankine cycle device,
The working fluid mainly comprises 1,1,1,3,3-pentafluoropropane;
A method comprising supplying a working fluid composition according to any one of claims 1 to 8 to the organic Rankine cycle apparatus that uses, uses or is designed to use the working fluid.