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    • 专利摘要:
    heat cycle system and working medium. the present invention relates to a working medium for the heat cycle, in which combustibility is suppressed, which has less influence on the ozone layer, which has less influence on global warming, and which provides a system excellent heat cycle performance in the cycle (capacity), and a heat cycle system, in which safety is guaranteed, and which is excellent in the cycle performance (capacity). a working medium for the heating cycle comprising 1,1,2-trifluorethylene is employed by means of a heat cycle system (such as a rankine cycle system, a heat pump cycle system, a refrigeration cycle 10, or a heat transport system).
    公开号:BR112013029406B1
    申请号:R112013029406-0
    申请日:2012-05-18
    公开日:2020-12-15
    发明作者:Masato Fukushima
    申请人:Agc Inc；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] The present invention relates to a working medium and a heat cycle system that employs the working medium. BACKGROUND OF THE TECHNIQUE
    [0002] Until then, as a working medium for the heat cycle, as a refrigerator for a refrigerator, a refrigerator for an air conditioner, a working fluid for the power generation system (such as the escape of the generation of heat recovery energy), a working medium for a latent heat transport device (such as a heat pipe), or a secondary cooling medium, a chlorofluorocarbon (CFC) such as dichlorodifluoromethane or chlorotrifluoromethane or a hydrochlorofluorocarbon ( HCFC), such as chlorodifluoromethane has been used. However, the influences of CFCs and HCFCs on the ozone layer in the stratosphere have been pointed out, and their use is currently regulated.
    [0003] Thus, as a working medium for the heat cycle, a hydrofluorocarbon (HFC), which has less influence on the ozone layer, such as difluoromethane (HFC -32), tetrafluoroethane or pentafluoroethane, has been used. However, it is stressed that HFC can cause global warming. Therefore, the development of a working environment for the heat cycle that has less influence on the ozone layer and has a low global warming potential is an urgent need.
    [0004] For example, 1,1,1,2-tetrafluoroethane (HFC-134a), used as a coolant for an automobile air conditioner has a global warming potential as high as 1430 (100 years). In addition, in an automobile that has air conditioning, refrigeration is highly likely to leak into the air, for example, from a connecting pipe or a bearing.
    [0005] As a coolant, which replaces HFC-134a, it has been studied that carbon dioxide and 1,1-difluoroethane (HFC-152a) have a global warming potential of 124 (100 years), which is lower in comparison with HFC -134a ,.
    [0006] However, with carbon dioxide, the pressure of the equipment tends to be extremely high, compared to HFC-134a and, consequently, there are many problems to be solved in the application to all automobiles. HFC-152a has a range of flammability, and has a problem to ensure safety.
    [0007] As a working medium for the heat cycle that has less influence on the ozone layer and has less influence on global warming, a hydrofluorolefin (OAF), with a carbon-carbon double bond, which is easily decomposed by of OH radicals in the air is conceivable.
    [0008] As a working medium for the heating cycle comprising an HFO, for example, the following has been known. (1) 3,3,3-Trifluoropropene (HFO-1243zf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-fluoropropene (HFO-1261yf), 2,3,3,3- tetrafluoropropene (HFO-1234yf) and 1,1,2-trifluoropropene (HFO-1243yc) (Patent Document 1). (2) 1,2,3,3,3-Pentafluoropropene (HFO-1225ye), trans- 1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis -1,3,3,3- tetrafluoropropene (HFO-1234ze (Z)) and HFO-1234yf (Patent Document 2).
    [0009] However, each of the HFO's in (1) is insufficient in cycle performance (capacity). In addition, between HFO in (1), having a smaller proportion of one of the fluorine atoms is the fuel.
    [00010] Each HFO in (2) is also insufficient in cycle performance (capacity). PREVIOUS TECHNICAL DOCUMENTS PATENT DOCUMENTS
    [00011] Patent Document 1: JP-A- 04-110388
    [00012] Patent Document 2: JP-A- 2006-512426 DESCRIPTION OF THE PRESENT INVENTION TECHNICAL PROBLEM
    [00013] The present invention relates to a working medium for the heat cycle, from which combustibility is suppressed, which has less influence on the ozone layer, which has less influence on global warming, and which provides a heat cycle system excellent in cycle performance (capacity), and a heat cycle system, of which safety is guaranteed, and which is excellent in cycle performance (capacity). SOLUTION TO THE PROBLEM
    [00014] The present invention provides a working medium for the heat cycle (hereinafter referred to as working medium), which comprises 1,1,2-trifluoroethylene (hereinafter referred to as HFO -1123).
    [00015] The working medium of the present invention preferably also contains a hydrocarbon.
    [00016] The working medium of the present invention preferably also contains an HFC.
    [00017] The working medium of the present invention preferably also contains a hydrochlorofluorolefin (HCFO) or a chlorofluoro-rolefine (CFO).
    [00018] The system of the present invention uses the heat cycle of the working medium of the present invention. ADVANTAGE EFFECTS OF THE PRESENT INVENTION
    [00019] The working medium of the present invention, which comprises HFO -1123 with a carbon-carbon double bond, which is easily decomposed by OH radicals, in the air, has less influence on the ozone layer and has less influence on heating global. In addition, since it comprises HFO -1123, it provides a heat cycle system, which is excellent in cycle performance (capacity).
    [00020] The heat cycle system of the present invention, which employs the working medium of the present invention excellent in thermodynamic properties, is excellent in the performance of the cycle (capacity). In addition, due to the excellent capacity, the reduction of the size of a system can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS
    [00021] Figure 1 is a schematic construction that illustrates an example of a refrigeration cycle system.
    [00022] Figure 2 is a cycle diagram that illustrates the change of state of a working medium in a refrigeration cycle system with a temperature-entropy graph.
    [00023] Figure 3 is a cycle diagram that illustrates the change of state of a working medium in a refrigeration cycle system of a pressure-enthalpy graph. DESCRIPTION OF THE MODALITIES Working environment
    [00024] The working medium of the present invention comprises 1,1,2-trifluorethylene.
    [00025] The working medium of the present invention may contain, as the case may be, another working medium which will be gasified or liquefied together with CFO1132, such as a hydrocarbon, an HFC, a CFO or an HCFO. In addition, the working medium of the present invention can be used in combination with a component other than the working medium, used in conjunction with the working medium (hereinafter, a composition containing the working medium and another component than the working medium will be referred to as a composition containing the medium). The other component of the working medium can be, for example, a lubricating oil, a stabilizer, a leak detection substance, a drying agent or other additives.
    [00026] The HFO -1123 content is preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, especially preferably 100% by weight of the working material. (100% by mass). (Hydrocarbon)
    [00027] Hydrocarbon is a component of the working medium that improves the solubility of the working medium in the form of a mineral lubricating oil.
    [00028] The hydrocarbon preferably has 3 to 5 carbon atoms, and can be straight or branched.
    [00029] The hydrocarbon is preferably specifically propane, propylene, cyclopropane, butane, isobutane, pentane or isopentane.
    [00030] Hydrocarbons can be used alone or in combination of two or more.
    [00031] The hydrocarbon content is preferably 1 to 40% by weight, more preferably 2 to 10% by weight, in the working medium (100% by weight). When the hydrocarbon content is at least 1% by mass, the solubility of the lubricating oil in the working medium will be sufficiently improved. When the hydrocarbon content is at most 40% by mass, an effect of suppressing the combustibility of the working material will be obtained. (HFC)
    [00032] HFC is a working medium component that improves the cycle throughput (capacity) of a heat cycle system.
    [00033] HFC is preferably an HFC, which has less influence on the ozone layer and which has less influence on global warming.
    [00034] HFC preferably has 1 to 5 carbon atoms and can be straight or branched.
    [00035] HFC can, for example, be specifically difluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane or heptafluorocyclopentane. Among them, particularly preferred is difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC - 134a) or pentafluorethane (HFC-125), which has less influence on the ozone layer and which has less influence on global warming.
    [00036] HFC can be used alone or in combination with two more.
    [00037] The content of HFC in the working medium (100% by mass) is preferably 1 to 99% by mass, more preferably from 1 to 60% by mass. For example, in a case where the HFC is HFC -32, the coefficient of performance and the cooling capacity will be improved within a content range of 1 to 99% by mass. In the case of HFC -134a, the coefficient of performance will be improved within a content range of 1 to 99% by mass. In the case of HFC-125, the coefficient of performance and the cooling capacity can be reduced, but the reduction is not so noticeable. The HFC content can be controlled depending on the properties required for the working medium. (HCFO, CFO)
    [00038] HCFO and CFO are components of the work environment that suppress combustibility of the work environment. In addition, they are components that improve the solubility of the lubricating oil in the work material.
    [00039] Like HCFO and CFO, preferred is an HCFO that has less influence on the ozone layer and which has less influence on global warming.
    [00040] HCFO preferably has 2 to 5 carbon atoms and can be straight or branched.
    [00041] HCFO can, for example, be specifically hydrochlorofluoropropene or hydrochlorofluoroethylene. Among them, particularly preferred is 1-chloro-2,3,3,3-tetrafluoropropene (HCFO 1224yd-) or 1-chloro -1,2-difluoroethylene (HCFO-1122), with a view to sufficiently suppressing combustibility of the work of the culture medium without substantially reducing the cycle performance (capacity) of the heat cycle system.
    [00042] HCFOs can be used alone or in combination of two or more.
    [00043] The CFO preferably has 2 to 5 carbon atoms and can be straight or branched.
    [00044] The CFO can, for example, be specifically chlorofluoropropene or chlorofluoroethylene. Among them, particularly preferred is 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) or 1,2-dichloro-1,2-difluoroethylene (CFO -1112), in order to suppress the sufficiently combustibility of the working environment, without substantially decreasing the cycle performance (capacity) of the heat cycle system.
    [00045] The total content of HCFO and CFO is preferably 1 to 60% of the mass of the working medium (100% by mass). Chlorine atoms have the effect of suppressing combustibility, and through the addition of HCFO and CFO, it is possible to sufficiently suppress the combustibility of the working material, without substantially decreasing the cycle performance (capacity) of the heat cycle system. (Lubricant)
    [00046] As the lubricating oil to be used for the composition containing the working medium, a known lubricating oil used for the heat cycle system can be used.
    [00047] The lubricating oil can be, for example, a synthetic oil containing oxygen (such as an ester lubricating oil or an ether lubricating oil), a fluorinated lubricating oil, a mineral oil or a synthetic hydrocarbon oil.
    [00048] The ester lubricating oil can be, for example, a dibasic acid ester oil, a polyol ester oil, an ester oil or an ester oil complex or a polyol carbonate oil.
    [00049] Dibasic acid ester oil is preferably an ester of a C5-10 dibasic acid (such as glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid or sebacic acid) with a C1 -15 mono alcohol -hydric, which is linear or has a branched alkyl group (such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol or pentadecanol). Specifically, ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate or di (3-ethylhexyl) sebacate can, for example, be mentioned.
    [00050] Polyol ester oil is preferably an ester of a diol (such as ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5 -pentadiol, neopentyl glycol, 1,7-heptanediol, or 1,12-dodecanediol), or a polyol with 3 to 20 hydroxyl groups (such as trimethylalethane, trimethylalpropane, trimethylalbutane, pentaerythritol, glycerol, sorbitol, sorbitan or sorbitol / glycerin condensed) with a C6-20 fatty acid (such as a straight or branched chain fatty acid, such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, eicosanoic acid or oleic acid, or a so-called neo acid having a quaternary carbon atom α).
    [00051] Polyol ester oil may have a free hydroxyl group.
    [00052] Polyol ester oil is preferably an ester (such as trimethylalpropane tripelargonate, pentaerythritol 2-ethylhexanoate or pentaerythritol tetrapelargonate) of an alcohol hindered (such as neopentyl glycol, trimethylolpropane, trimethylolpropane , pentaerythritol or trimethylolbutane).
    [00053] The ester oil complex is an ester of a fatty acid and a dibasic acid, with an alcohol and a monohydric polyol. Fatty acid, dibasic acid, alcohol and monohydric polyol can be as defined above.
    [00054] Polyol carbonate oil is an ester of carbonic acid with a polyol.
    [00055] The polyol may be the diol described above, or the polyol described above. In addition, the polyol carbonate oil may be a polymer of an open ring cyclic alkylene carbonate.
    [00056] The lubricant can be a petroleum ether of polyvinyl ether or a lubricating oil of polyoxyalkylene.
    [00057] Polyvinyl ether oil can be obtained by polymerizing a vinyl ether monomer, such as an alkyl vinyl ether, or a copolymer obtained by copolymerizing a vinyl ether monomer and a hydrocarbon monomer having a bond double olefin.
    [00058] The vinyl ether monomers can be used alone or in combination of two or more.
    [00059] The hydrocarbon monomer with an oleophilic double bond can be, for example, ethylene, propylene, various forms of butene, various forms of pentene, various forms of hexene, various forms of heptene, various forms of octene , diisobutylene, triisobutylene, styrene, α-methyl-styrene or alkyl-substituted styrene. Hydrocarbon monomers having an oleophilic double bond can be used alone or in combination of two or more.
    [00060] The polyvinyl ether copolymer can be either a block copolymer and a random copolymer.
    [00061] Polyvinyl ethers can be used alone or in combination of two or more.
    [00062] The polyoxyalkylene lubricating oil can, for example, be a monool polyoxyalkylene, a polyoxyalkylene polyol, an alkyl ether of a polyoxyalkylene monool or a polyoxyalkylene polyol, or an ester of a polyoxyalkylene monool or a polyol of polyoxyalkylene or polyoxyalkylene. The polyoxyalkylene monool or polyoxyalkylene polyol can be obtained for example, a method of subjecting a C2-4 alkylene oxide (for example, ethylene oxide or propylene oxide) to ring opening addition polymerization with such an initiator such as water or a group containing the compound, in the presence of a catalyst, such as an alkaline hydroxide hydroxide. In addition, a polyoxyalkylene chain molecule of oxyalkylene units may contain one or two or more types of oxyalkylene units. It is preferred that at least the oxypropylene units are contained in a single molecule.
    [00063] The initiator can, for example, be water, a monohydric alcohol, such as methanel or butanel, or a polyhydric alcohol such as ethylene glycol, propylene glycol, pentaerythritol or glycerol.
    [00064] Polyoxyalkylene lubricating oil is preferably an alkyl ether or an ester of a polyoxyalkylene monool or polyoxyalkylene polyol. In addition, the polyoxyalkylene polyol is preferably a polyoxyalkylene glycol. Particularly preferred is a polyoxyalkylene glycol alkyl ether having the polyoxyalkylene glycol terminal hydroxy group capped with an alkyl group such as a methyl group, which is called a polyglycol oil.
    [00065] Fluorinated lubricating oil may, for example, be a compound with hydrogen atoms of a synthetic oil (such as mineral oil, after mentioned, poly-α-olefin, alkylbenzene or alkylnaphthalenesulfonate) replaced by fluorine atoms , a fluorinated silicone oil or perfluoropolyether.
    [00066] Mineral oil can be, for example, a mineral oil or naphthene, a paraffinic mineral oil obtained by purifying a fraction of lubricating oil obtained by atmospheric distillation or the vacuum distillation of crude oil by a purification treatment (such as as solvent de-asphalting, solvent extraction, hydro-cracking, solvent dewaxing, dewaxing, hydrotreating or catalytic treatment clay), optionally in combination.
    [00067] The synthetic hydrocarbon oil can, for example, be a poly-α-olefin, an alkylbenzene or an alkylnaphthalene.
    [00068] Lubricating oils can be used alone or in combination of two or more.
    [00069] The lubricant is preferably a polyol ester oil and / or a polyglycol oil for compatibility with the working medium, particularly preferably a polyalkylene glycol oil in order to obtain a remarkable antioxidant effect by a stabilizer .
    [00070] The content of the lubricating oil is not limited within an interval, not notably diminishing the effects of the present invention, for example, it varies depending on the application and the form of a compressor, and is preferably from 10 to 100 parts by mass, more preferably 20 to 50 parts by mass based on working medium (100 parts by mass). (Stabilizer)
    [00071] The stabilizer to be used for the composition containing the working medium is a component that improves the stability of the working medium against heat and oxidation.
    [00072] The stabilizer can be, for example, an oxidation resistance improving agent, a heat resistance improving agent or a metal deactivator.
    [00073] The oxidation resistance improving agent and heat resistance improving agent can, for example, be N, N'-diphenylphenylenediamine, p-octyldiphenylamine, p, p'-dioctyldiphenylamine, N-phenyl-1-naphthiamine , N-phenyl-2-naphthylamine, N - (p -dodecyl) phenyl-2-naphthylamine, di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazine, 6- (t-butyl) phenol, 2,6 -di- (t-butyl) phenol, 4-methyl-2,6-di- (t-butyl) phenol, or 4,4'-methylenebis (2,6-di-t-butylphenol). Oxidation resistance improving agents and heat resistance improving agents can be used alone or in combination of two or more.
    [00074] The deactivating metal can, for example, be imidazole, benzimidazole, 2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole, salicylisine-propylene diamine, pyrazole, benzotriazole, tritriazole, 2-methylbenzamidazole, 3,5-dimethylpyrazole, 3,5-dimethylpyrazole benzotriazole, an organic acid or ester, of aliphatic primary, secondary or tertiary amines, an amine salt of an organic acid or an inorganic acid, a nitrogen-containing heterocyclic compound, an amine salt of an alkyl phosphate, or a derivative of the same.
    [00075] The content of the stabilizer is not limited within a range notably not diminishing the effects of the present invention, and is preferably at most 5% by weight, more preferably at most 1% by weight of the composition containing the medium of work (100% by mass). (Leak detection substance)
    [00076] The leak detection of substances to be used for the composition-containing composition operation may, for example, be an ultraviolet fluorescent dye, with an odor gas or an odor masking agent.
    [00077] The fluorescent ultraviolet dye can be known as fluorescent ultraviolet dyes as described for example, in U.S. Patent No. 4,249,412, JP-A-10-502737, JP-A- 2007-511645, JP-A - 2008-500,437 and JP-A-2008-531836.
    [00078] The odor masking agent can be known as perfumes as described in, for example, JP-A-2008-500437 and JP-A-2008-531836.
    [00079] In a case where the leak detection substance is used, a solubilizing agent can be used, which improves the solubility of leak detection of substances in the work environment.
    [00080] The solubilizing agent can be as described in, for example, JP-A-2007-511645, JP-A-2008-500437 and JP-A-2008- 531836.
    [00081] The leakage content of substances is not particularly limited within a range notably not diminishing the effects of the present invention, and is preferably at most 2% by weight, more preferably at most 0.5% by weight at work the composition containing the support (100% by mass). (Other compound)
    [00082] The working medium of the present invention and the composition containing the working medium may contain a C1-4 alcohol or a compound used as a conventional working medium, cooling liquid or heat transfer medium (hereinafter the alcohol and the compound will generally be referred to as another compound).
    [00083] As such another compound, the following compounds can be mentioned.
    [00084] Fluorinated ether: Perfluoropropyl methyl ether (C3F7OCH3), perfluorobutyl methyl ether (C4F9OCH3), perfluorobutyl ethyl ether (C4F9OC2H5), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF2) manufactured by Asahi Glass Compani, Limited, AE-3000), etc.
    [00085] The content of such other compounds is not limited within a range notably not lessening the effects of the present invention, and is preferably at most 30% by weight, more preferably at most 20% by weight, particularly and preferably, at most, 15% by weight in the work composition containing medium (100% by mass). Heat cycle system
    [00086] The heat cycle system of the present invention is a system that employs the working method of the present invention.
    [00087] The heat cycle system can, for example, be a Rankine cycle system, a heat pump cycle system, a refrigeration cycle system or a heat transport system. (Cooling cycle system)
    [00088] As an example of the heat cycle system, a refrigeration cycle system will be described.
    [00089] The refrigeration cycle system is a system in which an evaporator, a working medium removes thermal energy from a fluid charge to cool the charging fluid, thereby performing the cooling to a lower temperature.
    [00090] Figure 1 is a schematic construction view illustrating an example of a refrigeration cycle system of the present invention. A refrigeration cycle system 10 is generally a system comprising a compressor 11 compressing the steam from a working medium A for the purpose of forming a high temperature / high steam pressure from working medium B, a condenser 12, to cool and liquefy the working medium of steam B discharged from the compressor 11 in order to form a low temperature / high working pressure medium C, an expansion valve 13, to allow the working medium C discharged from condenser 12 it will expand with the purpose of forming a low medium temperature / low working pressure D, an evaporator 14 to heat the working medium D discharged from the expansion valve 13 in order to form a high temperature / low vapor pressure of a working medium, a pump 15 to supply a fluid charge E to the evaporator 14, and a pump 16 to supply a fluid F to the condenser 12.
    [00091] In the cyclic cooling system 10, the following cycle is repeated. (i) A steam working medium discharged from an evaporator 14 is compressed by means of a compressor 11 so as to form a high temperature / high steam pressure from working medium B. (ii) The working medium of steam B discharged from the compressor 11 is cooled and liquefied by means of a fluid F from a condenser 12 in order to form a low temperature / high average working pressure C. At that time, fluid F is heated with the purpose of forming a fluid F ', which is discharged from condenser 12. (iii) the working medium C discharged from condenser 12, is expanded in an expansion valve 13 in order to form a low temperature / low pressure of working medium D. (iv) working medium D discharged from expansion valve 13 is heated by means of a charging fluid and in an evaporator 14 in order to form a high temperature / low vapor pressure of medium A. At that time, the fluid charge o is cooled and becomes a charging fluid E ', which is discharged from the evaporator 14.
    [00092] The refrigeration cycle system 10 is a cycle that comprises an isentropic adiabatic change, an isentalpical change and an isobaric change, and the change of working fluid state can be presented as in figure 2, when it is represented on a temperature-entropy graph.
    [00093] In figure 2, the AB process is a process in which adiabatic compression is performed by means of compressor 11 in order to change the high temperature / low vapor pressure from medium A to a high temperature / high vapor pressure medium B. The BC process is a process in which isobaric cooling is performed on condenser 12 to change the high temperature / high vapor pressure of working medium B to a low temperature / high medium working pressure C. O CD process is a process in which the isentalpic expansion is performed by means of expansion valve 13 to change the low temperature / high working pressure medium C, to a low temperature / low working pressure medium D. The DA process is a process in which isobaric heating is carried out on the evaporator 14 to have the medium low temperature / low working pressure D returned to a medium high temperature / low vapor pressure A.
    [00094] In the same way, the change of state of the working environment can be shown as in figure 3, when it is represented in a pressure-enthalpy graph. (Moisture concentration)
    [00095] There is a problem with the inclusion of moisture in the heat cycle system. The inclusion of moisture can cause freezing in a capillary tube, hydrolysis of the working medium or lubricating oil, deterioration of materials through an acid component formed in the thermal cycle, the formation of contaminants, etc. In particular, the ether lubricating oil described above, ester lubricating oil and the like have extremely high moisture content absorption properties and are susceptible to hydrolysis, and the inclusion of moisture decreases the lubricant properties and can be a major cause impair the long-term reliability of a compressor. In addition, in a car air conditioner, moisture tends to be included from a coolant hose or a compressor bearing used for the purpose of absorbing vibrations. Therefore, in order to suppress the hydrolysis of the lubricating oil, it is necessary to suppress the moisture concentration in the heat cycle system. The moisture concentration of the working medium in the heat cycle system is preferably at most 100 ppm, more preferably at most 20 ppm.
    [00096] As a method of suppressing the concentration of moisture in the thermal cycle system, a method of using a drying agent (such as silica gel, activated aluminum or zeolite) can be mentioned. The drying agent is preferably a zeolite drying agent, taking into account the chemical reactivity of the drying agent and the working medium, and the moisture absorbing capacity of the drying agent.
    [00097] The drying agent is zeolite, in a case where a lubricating oil that has a high moisture absorption, in comparison with a conventional mineral lubricating oil, preferably a zeolite drying agent containing a compound represented by the following general formula (1) as the main component in view of an excellent moisture absorption capacity. M2 / nO AI2O3 • xSiO2 yH2O (1)
    [00098] where M is an element of a group such as Na or K, and an element of group 2, such as Ca, the symbol n represents the valence of M, and x and y are the values determined by means of the crystalline structure. The pore size can be adjusted by changing M.
    [00099] To select the drying agent, the pore size and resistance to fracture are important.
    [000100] In a case where a drying agent having a pore size larger than the molecular size of the working medium is used, the working medium is adsorbed on the drying agent and, as a result, the chemical reaction between the working material and the drying agent will occur, thereby leading to undesirable phenomena, such as the formation of non-condensing gas, a decrease in the strength of the drying agent, and a decrease in the adsorption capacity.
    [000101] Therefore, it is preferred to use as a drying agent a zeolite drying agent with a small pore size. Particularly preferred is type A sodium / potassium synthetic zeolite with a pore size of at most 3.5 µm. When using a synthetic sodium / potassium zeolite type A with a pore size smaller than the molecular size of the work material, it is possible to selectively adsorb and remove only the moisture in the heat cycle system without the adsorption of the work material . In other words, the working medium is less likely to be adsorbed on the drying agent, whereby thermal decomposition is less likely to occur and, as a result, the deterioration of the materials that make up the heat cycle system and the formation contaminants can be suppressed.
    [000102] The size of the zeolite desiccant is preferably about 0.5 to about 5 mm, since if it is too small, a valve or a thin portion in pipelines can be blocked, and if it is too large , the drying capacity will be decreased. Its shape is preferably granular or cylindrical.
    [000103] The zeolite desiccant can be formed in an optional form by solidifying zeolite powder using a bonding agent (such as bentonite). In this way, since the drying agent is composed mainly of the zeolite drying agent, another desiccant (such as silica gel or activated alumina) can be used in combination.
    [000104] The proportion of the zeolite drying agent based on the working medium is not particularly limited. (Chlorine concentration)
    [000105] If chlorine is present in the heat cycle system, it has adverse effects, such as the formation of a reaction deposit with a metal, the abrasion of the bearing, and the decomposition of the working medium or lubricating oil .
    [000106] The concentration of chlorine in the heat cycle system is preferably at most 100 ppm, especially preferably at most 50 ppm, by means of the mass ratio based on the working medium. (Concentration of non-condensing gas)
    [000107] If non-condensed gas is included in the heat cycle system, it has adverse effects, such as failure of heat transfer in the condenser or evaporator and an increase in working pressure, which is necessary to suppress the their inclusion as much as possible. In particular, oxygen, which is one of the non-condensing gases, reacts with the working medium or lubricating oil and promotes its decomposition.
    [000108] The concentration of non-condensed gas is preferably at most 1.5% by volume, especially preferably at most 0.5% by volume through the volume ratio based on the working medium, at a gas phase of working medium. EXAMPLES
    [000109] Now, the present invention will be described in more detail with reference to the Examples. However, it is to be understood that the present invention is in no way limited to those specific Examples. (Refrigeration cycle performance assessment)
    [000110] The performance of the refrigeration cycle (the cooling capacity and the coefficient of performance) was assessed as the performance of the cycle (the capacity and efficiency) in a case where a medium was applied to a system refrigeration cycle 10, shown in figure 1.
    [000111] The evaluation was carried out by adjusting the average temperature, the evaporation of the working medium in an evaporator 14, the average condensing temperature of the working medium in a condenser 12, the degree of overcooling of the working fluid in the condenser 12 , and the degree of elevation of the working medium in the evaporator 14, respectively. In addition, it was assumed that there was no pressure loss in the efficiency of the equipment and in the pipes and in the heat exchange.
    [000112] The cooling capacity Q and the coefficient of performance n are obtained from the following formulas (2) and (3) using the enthalpy h in each state (provided that the suffix attached to ah indicates the state of the job). Q = hA- hD (2) n = cooling capacity / compression work = (hA- hD) / (hB- hA) (3)
    [000113] The performance coefficient means efficiency in the refrigeration cycle system, and a higher throughput means that a higher output (cooling capacity) can be obtained by means of a smaller input (the electrical energy required to operate compressor).
    [000114] Furthermore, the cooling capacity means an ability to cool a cargo fluid, and a higher cooling capacity means that more work can be done on the same system. In other words, this means that with a medium of work which has a greater cooling capacity, the desired performance can be obtained with a smaller amount, in which the system can be reduced.
    [000115] The thermodynamic properties necessary for calculating the refrigeration cycle performance were calculated based on the generalized State equation (Soave-Redlich-Kwong equation) based on the corresponding State law and various thermodynamic equations. If a characteristic value was not available, it was calculated using an estimation technique based on a group contribution method. Example 1
    [000116] The performance of the refrigeration recycler (the cooling capacity and the coefficient of performance) was evaluated in a case where a working medium comprising HFO -1123 and an HFC, as identified in Table 1, was applied to a refrigeration cycle system 10, shown in figure 1.
    [000117] The evaluation was carried out by adjusting the average temperature the evaporation of the working medium in an evaluator 14 to be 0 ° C, the average condensing temperature of the working medium in a condenser 12, to be 50 ° C , the degree of overcooling of the working fluid in the condenser 12 to be 5 ° C, and the degree of overheating of the working fluid in the evaporator 14 to be 5 ° C.
    [000118] Based on the HFC -134a refrigeration recycler performance, the relative performance (each working medium / HFC-134a working) of the cooling cycle performance (the cooling capacity and the performance coefficient) of each medium HFC-134a-based work was obtained. The results of each of the means of work are shown in Table 1.

    [000119] From the results in Table 1, it was confirmed that the performance coefficient and the cooling capacity of HFO -1123 were improved by adding HFC-32 to HFO-1123. Through the addition of HFC -134a, the performance coefficient has improved. Through the addition of HFC-125, the coefficient of performance and the cooling capacity were reduced, but a cooling capacity of at least 1.0 was maintained. HFC-125, which has an excellent effect of suppressing combustibility and can sufficiently suppress the combustibility of a working medium, is considered to be effective when the working medium is necessary to suppress combustibility. Example 2
    [000120] The performance of the refrigeration cycle (the cooling capacity and the coefficient of performance) was evaluated in a case where a working medium comprising HFO -1123 and an HFC as identified in Table 2 or 3, was applied to a refrigeration cycle system 10, shown in figure 1.
    [000121] The evaluation was carried out by adjusting the average temperature the evaporation of the working medium in an evaporator 14 to be 0 ° C, the average condensing temperature of the working medium in a condenser 12, to be 50 ° C, the degree of overcooling of the working fluid in the condenser 12 to be 5 ° C, and the degree of overheating of the working fluid in the evaporator 14 to be 5 ° C.
    [000122] Based on the performance of the HFC -134a refrigeration cycle in Example 1, the relative performance (each working medium / HFC-134a) of the refrigeration cycle performance (the cooling capacity and the performance coefficient ) of each working medium based on HFC-134a was obtained. The results of each of the means of work are presented in Tables 2 and 3.Table 2
    Table3

    [000123] From the results of Tables 2 and 3, it was confirmed that HFO -1123 has a high cooling capacity as compared to a conventional HFO. In addition, it has been confirmed that through the addition of HFO the performance coefficient can be improved without a noticeable decrease in cooling capacity. Example 3
    [000124] The performance of the refrigeration cycle (the cooling capacity and the coefficient of performance) was evaluated in a case in which a working medium comprising HFO -1123 and a hydrocarbon as identified in Table 4 was applied to a refrigeration cycle system 10, shown in figure 1.
    [000125] The evaluation was carried out by adjusting the average temperature to evaporation of the working medium in an evaporator 14 to be 0 ° C, the average condensing temperature of the working medium in a condenser 12, to be 50 ° C, the degree of overcooling of the working fluid in the condenser 12 to be 5 ° C, and the degree of overheating of the working fluid in the evaporator 14 to be 5 ° C.
    [000126] Based on the performance of the HFC -134a refrigeration cycle in Example 1, the relative performance (each working medium / HFC-134a) of the refrigeration cycle performance (the cooling capacity and the performance coefficient ) of each working medium based on HFC-134a was obtained. The results of each of the means of work are shown in Table 4. Table 4

    [000127] From the results presented in Table 4, it was confirmed that the performance coefficient of HFO -1123 can be improved without a noticeable decrease in the cooling capacity by adding an HFO-1123 hydrocarbon. Example 4
    [000128] The performance of the refrigeration cycle (the cooling capacity and the coefficient of performance) was evaluated in a case where a working medium comprising HFO -1123 and an HCFO as identified in Table 5, was applied to a system refrigeration cycle 10, shown in figure 1.
    [000129] The evaluation was carried out by adjusting the average temperature to evaporation of the working medium in an evaporator 14 to be 0 ° C, the average condensing temperature of the working medium in a condenser 12, to be 50 ° C, the degree of overcooling of the working fluid in the condenser 12 to be 5 ° C, and the degree of overheating of the working fluid in the evaporator 14 to be 5 ° C.
    [000130] Based on the HFC -134a refrigeration cycle performance in Example 1, the relative performance (each medium / HFC-134a) of the refrigeration cycle performance (the cooling capacity and the performance coefficient ) of each working medium based on HFC-134a was obtained. The results of each of the means of work are shown in Table 5.Table 5

    [000131] From the results in Table 5, it was confirmed that the performance coefficient of HFO -1123 can be improved without a noticeable decrease in cooling capacity, by adding an HCFO of HFO-1123. Example 5
    [000132] The performance of the refrigeration cycle (the refrigeration capacity and the coefficient of performance) was evaluated in the case of HFO -1123 as a working medium was applied to a refrigeration cycle system 10, shown in figure 1.
    [000133] The evaporating temperature of the working fluid in an evaporator 14, the condensing temperature of the working fluid in a condenser 12, the degree of overcooling of the working fluid in the condenser 12 and the degree of overheating of the working fluid in the evaporator 14 had the temperatures as identified in Table 6.
    [000134] Based on the performance of the HFC -134a refrigeration cycle in Example 1, the relative performance (HFO-1123 / HFC-134a) of the HFO refrigeration cycle performance (the cooling capacity and the performance coefficient) -1123 based on HFC-134a was obtained. The results are shown in Table 6.Table 6

    [000135] The operating medium of the present invention is useful as a working medium for the heat cycle, such as a coolant in a refrigerator, a cooling in an air conditioner, a working fluid for the generation system energy sources (such as exhaust heat recovery power generation), a working medium for a latent heat apparatus (such as a heat pipe), or a secondary cooling medium.
    [000136] The complete description of Japanese Patent Application No. 2011-112417 filed on May 19, 2011, including the specification, drawings and claims and the summary is incorporated into the present invention by reference in its entirety. REFERENCE LISTING 10: refrigeration cycle system
    权利要求:
    Claims (11)
    [0001]
    1. Working medium for the heat cycle, characterized by the fact that it comprises 1,1,2-trifluoroethylene and difluoromethane.
    [0002]
    2.Method of work, according to claim 1, characterized by the fact that it also contains a hydrocarbon.
    [0003]
    3. Working method according to claim 1 or 2, characterized by the fact that it also contains a hydrochlorofluorolefin or a chlorofluorolefin.
    [0004]
    4.Method of work, according to any of the vindications 1 to 3, characterized by the fact that 1,1,2-trifluorethylene is contained in a content of at least 60% by mass of the working medium for the cycle of heat (100% by mass).
    [0005]
    5.Method of work, according to any of the vindications 2 to 4, characterized by the fact that the hydrocarbon is contained in a content of 1 to 40% by mass of the working medium for the heat cycle (100% in large scale).
    [0006]
    6.Method of work, according to any of the vindications 1 to 5, characterized by the fact that difluoromethane is contained in a content of 1 to 99% by mass of the working medium for the heat cycle (100% in large scale).
    [0007]
    7.Method of work, according to any of the vindications 3 to 6, characterized by the fact that the total content of hydrochlorofluorolefin and chlorofluorolefin is from 1 to 60% by mass of the working medium for the cycle of heat (100% by mass).
    [0008]
    8.Method of work, according to any of the vindications 2 to 7, characterized by the fact that the hydrocarbon is propane, propylene, cyclopropane, butane, isobutane, pentane or iso-pentane.
    [0009]
    9.Method of work, according to any of the vindications 3 to 8, characterized by the fact that hydrochlorofluoroolefin is 1-chloro-2,3,3,3-tetrafluoropropene or 1-chlorine -1,2- difluoroethylene.
    [0010]
    10.Method of work, according to any of the vindications 3 to 8, characterized by the fact that chlorofluoroolefin is 1,1-dichloro -2,3,3,3-tetrafluoropropene or 1,2- dichloro -1 , 2-difluoroethylene.
    [0011]
    11.Heat cycle system, characterized by the fact that it employs the working medium for the heat cycle, as defined in any one of claims 1 to 10.
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-12| B25D| Requested change of name of applicant approved|Owner name: AGC INC. (JP) |
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011112417|2011-05-19|
    JP2011-112417|2011-05-19|
    PCT/JP2012/062843|WO2012157764A1|2011-05-19|2012-05-18|Working medium and heat-cycle system|
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