• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Use of ternary compositions The present invention relates to the use of compositions that essentially contain 2,3,3,3 tetrafluorpropene, hfc-134a and hfc-32 in the compression refrigeration systems with countercurrent heat exchangers.
    公开号:BR112012005237B1
    申请号:R112012005237-3
    申请日:2010-08-18
    公开日:2020-06-02
    发明作者:Wissam Rached
    申请人:Arkema France；
    IPC主号:
    专利说明:

    [001] The present invention relates to the use of ternary compositions containing 2,3,3,3-tetrafluoropropene as heat transfer fluids, notably for medium capacity refrigeration per unit volume swept by the compressor.
    [002] The problems posed by substances that deplete the atmospheric ozone layer (ODP: ozone depletion potential) were dealt with in Montreal where a protocol was signed imposing a reduction in the production and use of chlorofluorocarbons (CFC). This protocol was the object of amendments that imposed the abandonment of CFCs and extended the regulation to other products, among them hydrochlorofluorocarbons (HCFC).
    [003] The refrigeration and air conditioning industry has invested a lot in replacing these refrigerants and this is how hydrofluorocarbons (HFCs) were commercialized.
    [004] The (hydro) chlorofluorocarbons used as blowing agents or solvents have also been replaced by HFCs.
    [005] In the automobile industry, the air conditioning systems of vehicles sold in many countries have changed from a refrigerant to chlorofluorocarbon (CFC-12) to that of hydrofluorocarbon (1,1,1,2 tetrafluoroethane: HFC-134a), which is less harmful to the ozone layer. However, in reference to the objectives set by the Kyoto protocol, HFC-134a (GWP = 1300) is considered to have a high reheating power. The contribution to the greenhouse effect of a fluid is quantified by a criterion, the GWP (Global Warming Potentials) that summarizes the reheating power
    Petition 870200027007, of 28/02/2020, p. 4/23
    2/12 taking for this a reference value of 1 for carbon dioxide.
    [006] Carbon dioxide, being non-toxic, non-flammable and having a very low GWP, has been proposed as a refrigerant for air conditioning systems to replace HFC-134a. However, the use of carbon dioxide has several drawbacks, notably linked to the very high pressure of its use as a refrigerant in existing devices and technologies.
    [007] WO2004 / 037913 discloses the use of compositions comprising at least one fluoralkene which has three or four carbon atoms, notably pentafluoropropene and tetrafluoropropene, preferably having a maximum GWP of 150, as transfer fluids of heat.
    [008] WO 2005/105947 teaches the addition to tetrafluoropropene, preferably 1,3,3,3 tetrafluoropropene, of an expansion coagent such as difluoromethane, pentafluoroethane, tetrafluoroethane, difluoroethane, heptafluoropropane, hexafluoropropane, pentafluoropropane, pentafluorobutane, water and carbon dioxide.
    [009] WO 2006/094303 discloses binary compositions of 2,3,3,3-tetrafluoropropene (HFO-1234yf) with difluoromethane (HFC-32), and 2,3,3,3-tetrafluoropropene with 1.1 , 1.2 tetrafluoroethane (HFC-134a).
    [0010] Quaternary mixtures comprising 1,1,1,2,3 pentafluoropropene (HFO-1225ye) in combination with difluoromethane,
    2,3,3,3-tetrafluoropropene and HFC-134a were disclosed in that document. However, 1,1,1,2,3 pentafluoropropene is toxic.
    [0011] Quaternary mixtures comprising 2,3,3,3 tetrafluoropropene in combination with iodotrifluoromethane (CF3I), HFC-32 and HFC-134a have also been disclosed in WO
    Petition 870200027007, of 28/02/2020, p. 5/23
    12/3
    2006/094303. However, the CF3I has a non-zero ODP and has stability and corrosion problems.
    [0012] A heat exchanger is a device that allows to transfer thermal energy from one fluid to another, without mixing them. The thermal flow passes through the exchange surface that separates the fluids. Most of the time this method is used to cool or reheat a liquid or gas that is impossible to cool or heat directly.
    [0013] In compression systems, the thermal exchange between the refrigerant fluid and the heat sources is carried out through the fluids that carry heat. These heat-carrying fluids are either gaseous (air in the air conditioner, and direct expansion refrigeration), liquid (water in domestic heat pumps, glycolated water) or diphasic.
    [0014] There are different transfer modes:
    - the two fluids are arranged in parallel and go in the same direction: co-current mode (antimethodic);
    - the two fluids are arranged in parallel but go in the opposite direction: countercurrent mode (methodical);
    - the two fluids are positioned perpendicularly: cross current mode. The cross current can be of a co-current or counter-current tendency;
    - one of the two fluids makes a half turn in a wider duct, which the second fluid passes through. This configuration is comparable to a half-length co-current changer, and for the other half to a counter-current changer: pinhead mode.
    [0015] The applicant has now discovered that ternary compositions of 2,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane and difluoromethane are especially interesting as heat transfer fluid in compression refrigeration systems with exchanged
    Petition 870200027007, of 28/02/2020, p. 6/23
    4/12 res that operate in countercurrent mode or in crosscurrent mode with countercurrent tendency.
    [0016] Thus, these compositions can be used as heat transfer fluid in heat pumps, possibly reversible, in air conditioning, industrial air conditioning (paper, server room), in mobile domestic air conditioning, in domestic refrigeration and freezing, in low and medium temperature refrigeration and in the refrigeration of refrigerated vehicles that use compression systems with exchangers in countercurrent mode or in cross current mode with a tendency against current.
    [0017] Thus, a first object of the present invention refers to the use of the ternary compositions of 2,3,3,3-tetrafluoropropene, of
    1.1.1.2- tetrafluoroethane and difluoromethane as heat transfer fluid in compression refrigeration systems with countercurrent or crosscurrent mode heat exchangers.
    [0018] Preferably, the compositions contain essentially from 80% by weight of 2,3,3,3-tetrafluoropropene, from 2 to 80% by weight of HFC-134a and from 2 to 80% by weight of HFC-32 .
    [0019] Advantageously, the compositions contain essentially 45 to 80% by weight, preferably 65 to 80% by weight of
    2.3.3.3- tetrafluoropropene, from 5 to 25% by weight, preferably from 5 to 10% by weight of HFC-134a and from 15 to 30% by weight of HFC-32. The compositions used as heat transfer fluid in the present invention do not present the mentioned drawbacks and at the same time have a zero ODP and a GWP lower than that of existing heat transfer fluids such as R404A (ternary mixture of pentafluoroethane (44% by weight) ), trifluoroethane (52% by weight) and HFC134a (4% by weight)) and R407C (ternary mixture of HFC-134a (52% by weight), pentafluoroethane (25% by weight) and HFC-32 (23% by weight) )).
    Petition 870200027007, of 28/02/2020, p. 7/23
    5/12 [0020] On the other hand, compositions containing essentially 5 to 25% by weight of 2,3,3,3-tetrafluoropropene, 60 to 80% by weight of HFC-134a and 15 to 25% by weight of the HFC-32 are not flammable.
    [0021] The compositions used as heat transfer fluid in the present invention have a critical temperature greater than 90 ° C (Critical temperature of R404A is 72 ° C). These compositions can be used in heat pumps to provide heat at average temperatures between 40 and 65 ° C and also at higher temperatures between 72 ° C and 90 ° C (temperature range where R404A cannot be used).
    [0022] The compositions used as heat transfer fluid in the present invention have densities in vapor saturation lower than the saturated vapor density of R404A. The volumetric capacities given by these compositions are equivalent or superior to the volumetric capacity of R-404A (between 90 and 131% depending on the applications. Thanks to these properties, these compositions can work with smaller pipe diameters and therefore less pressure loss in the steam pipes, which increases the performances of the installations.
    [0023] The compositions used as a heat transfer agent according to the present invention can be stabilized. The stabilizer preferably represents a maximum of 5% by weight in relation to the ternary composition.
    [0024] As stabilizers, nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2 , 6-di-ter-butyl-4methylphenol, epoxides (possibly fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol
    Petition 870200027007, of 28/02/2020, p. 8/23
    6/12 diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones.
    [0025] A second object of the present invention relates to a heat transfer process in which the ternary compositions of 2,3,3,3-tetrafluoropropene, 1,1,1,2tetrafluoroethane and difluoromethane are used, such as defined above, as refrigerant in compression systems that use countercurrent or crosscurrent changers with countercurrent tendency.
    [0026] The process according to the second object can be carried out in the presence of lubricants such as mineral oil, alkylbenzene, polyalkylene glycol and polyvinyl ether.
    EXPERIMENTAL PART
    Calculation tools [0027] The RK-Soave equation is used to calculate the densities, enthalpies, entropies and the liquid vapor balance data of the mixtures. The use of this equation requires knowledge of the properties of the pure bodies used in the mixtures in question and also of the interaction coefficients for each torque.
    [0028] The necessary data for each pure body are:
    [0029] Boiling temperature, Temperature and critical pressure, the pressure curve as a function of temperature from the boiling point to the critical point, the saturated liquid and saturated vapor densities as a function of temperature.
    HFC-32, HFC-134a:
    [0030] The data on these products are published in the
    ASHRAE Handbook 2005 chapter 20, and are also available under Refrop (Software developed by NIST for calculating the properties of refrigerants).
    HFO-1234yf:
    Petition 870200027007, of 28/02/2020, p. 9/23
    7/12 [0031] The HFO-1234yf temperature-pressure curve data is measured by the static method. The temperature and critical pressure are measured by a C80 calorimeter sold by Setaram. The densities, with saturation as a function of temperature, are measured by the technology of the vibrating tube densimeter developed by the laboratories of the school of the Mines of Paris.
    Binary interaction coefficient [0032] The RK-Soave equation uses binary interaction coefficients to represent the behavior of products in mixtures. The coefficients are calculated according to the experimental data of liquid vapor balance.
    [0033] The technique used for the liquid vapor balance measurements is the analytical static cell method. The balance cell comprises a sapphire tube and is equipped with two electromagnetic ROLSITM sample selectors. It is immersed in a cryothermostat bath (HUBER HS40). A magnetic stirrer with field drive that rotates at variable speed is used to accelerate the achievement of equilibrium. The analysis of the samples is carried out by gas chromatography (HP5890 series II) using a catarometer (TCD).
    [0034] HFC-32 / HFO-1234yf, HFC-134a / HFO-1234yf:
    [0035] Liquid vapor balance measurements in torque HFC-32 /
    HFO-1234yf are performed for the following isotherms: - 10 ° C, 30 ° C and 70 ° C [0036] The liquid vapor balance measurements in the HFC134a / HFO-1234yf torque are performed for the following isotherms: 20 ° C HFC- 32 / HFO-134a:
    [0037] The liquid vapor balance data for torque HFC134a / HFC-32 are available under Refprop. Two isotherms (-20 ° C and 20 ° C) and one isobaric (30 bars) are used to calculate the
    Petition 870200027007, of 28/02/2020, p. 10/23
    8/12 interaction coefficients for that binary.
    Compression system [0038] A compression system equipped with a countercurrent evaporator and condenser, a screw compressor and a pressure reducer will be considered.
    [0039] The system works with 15 ° C of superheat and 5 ° C of subcooling. The minimum temperature difference between the secondary fluid and the refrigerant is considered to be around 5 ° C.
    [0040] The isentropic performance of the compressors is a function of the compression rate. This yield is calculated according to the following equation:
    = ab (T-ef-r- e (1) [0041] For a screw compressor, the constants a, b, c, d, and e of equation (1) of the isentropic yield are calculated according to the published data types in the Handbook “Handbook of air conditioning and refrigeration, page 11.52”.
    [0042]% CAP is the percentage of the ratio of the volumetric capacity provided by each product to the capacity of R-404A.
    [0043] The performance coefficient (COP) is defined as the useful power supplied by the system over the power brought or consumed by the system.
    [0044] The Lorenz performance coefficient (COPLorenz) is a reference performance coefficient. It is a function of temperatures and is used to compare the COP of different fluids.
    [0045] The Lorenz performance coefficient is defined as follows:
    (T temperatures are in K) average condenser i condenser input condenser output (2)
    Petition 870200027007, of 28/02/2020, p. 11/23
    9/12 rp medium evaporator evaporator outlet evaporation inlet (3) [0046]
    Lorenz COP for air conditioning and refrigeration:
    j ^ evaponadon '
    COPlorenz = ----------- j ^ condenser _ 'r evaporator 1 average average (4) [0047]
    Lorenz's COP in case of heating:
    condensation
    COPlorenz = ------------ j 7 condensation _ y ^ evaponadon average mean (5) [0048]
    For each composition, the performance coefficient of the
    Lorenz is calculated as a function of the corresponding temperatures.
    [0049]
    % COP / COPLorenz is the ratio of the system's COP to the corresponding Lorenz cycle COP.
    Heating mode results [0050] In heating mode, the compression system works between an inlet temperature of the refrigerant in the evaporator of -5 ° C and an inlet temperature of the refrigerant in the condenser of 50 ° C. The system provides heat at 45 ° C.
    [0051] The performances of the compositions according to the invention under the operating conditions in heating mode are given in Table 1. The values of the constituents (HFO-1234yf, HFC32, HFC-134a) for each composition are given in percentage by weight.
    Petition 870200027007, of 28/02/2020, p. 12/23
    12/10
    Table 1
    Evap outlet temp (° C) Comp output temp (° C) T cond output (° C) evap P (bar) cond P (bar) Rate (p / p) Glide comp yield % CAP % COP / COPLorenz R404A -5 77 50 5.2 23.0 4.4 0.38 79.7 100 57.7 HFO-1234yf HFC-32 HFC-134a 80 15 5 0 77 43 4.0 16.5 4.2 4.57 80.5 90 64.7 75 20 5 0 79 43 4.4 17.7 4.1 5.19 80.8 98 64.8 70 25 5 0 82 43 4.7 19.0 4.0 5.37 80.9 106 64.755 20 25 -1 82 44 4.2 17.7 4.2 4.43 80.4 97 65.2 50 25 25 0 84 44 4.5 18.8 4.2 4.71 80.5 104 65.2 45 30 25 0 87 44 4.8 19.9 4.2 4.74 80.6 111 65.1 40 35 25 0 90 45 5.0 20.9 4.2 4.59 80.5 116 64.9 35 40 25 -1 93 45 5.2 21.9 4.2 4.34 80.4 121 64.640 20 40 -1 84 45 4.1 17.6 4.3 4.21 80.1 96 65.4 35 25 40 0 86 45 4.4 18.6 4.3 4.56 80.2 103 65.5 30 30 40 0 89 45 4.6 19.6 4.2 4.71 80.3 109 65.4 25 35 40 0 92 45 4.8 20.5 4.2 4.71 80.3 114 65.3 20 40 40 0 95 45 5.0 21.3 4.3 4.62 80.3 119 65.115 20 65 -1 87 45 3.8 17.1 4.5 4.07 79.5 94 65.7 10 25 65 -1 90 45 4.0 17.9 4.4 4.49 79.8 99 65.8
    Results in cooling or air conditioning mode [0052] In cooling mode, the compression system works between an inlet temperature of the refrigerant in the evaporator of -5 ° C and an inlet temperature of the refrigerant in the condenser of 50 ° C. The system supplies cold at 0 ° C.
    [0053] The performances of the compositions according to the invention under operating conditions in cooling mode are given
    Petition 870200027007, of 28/02/2020, p. 13/23
    11/12 in table 2. The values of the constituents (HFO-1234yf, HFC-32, HFC134a) for each composition are given in percentage by weight. Table 2
    Evap outlet temp (° C) Comp output temp (° C) T cond output (° C) evap P (bar) cond P (bar) Rate (p / p) Glide comp yield % CAP % COP / COPLorenz R404A -5 77 50 5.2 23.0 4.4 0.38 79.7 100 47.9 HFO-1234yf HFC-32 HFC-134a 75 20 5 0 79 43 4.4 17.7 4.1 5.19 80.8 106 56.6 70 25 5 0 82 43 4.7 19.0 4.0 5.37 80.9 114 56.6 65 30 5 0 85 44 5.0 20.2 4.0 5.22 80.9 121 56.460 15 25 -1 79 45 3.9 16.6 4.3 3.83 80.2 95 56.5 55 20 25 -1 82 44 4.2 17.7 4.2 4.43 80.4 104 57.0 50 25 25 0 84 44 4.5 18.8 4.2 4.71 80.5 112 57.2 45 30 25 0 87 44 4.8 19.9 4.2 4.74 80.6 119 57.2 40 35 25 0 90 45 5.0 20.9 4.2 4.59 80.5 125 57.1 35 40 25 -1 93 45 5.2 21.9 4.2 4.34 80.4 130 56.945 15 40 -1 81 45 3.8 16.6 4.4 3.59 79.8 95 56.8 40 20 40 -1 84 45 4.1 17.6 4.3 4.21 80.1 103 57.3 35 25 40 0 86 45 4.4 18.6 4.3 4.56 80.2 111 57.6 30 30 40 0 89 45 4.6 19.6 4.2 4.71 80.3 118 57.6 25 35 40 0 92 45 4.8 20.5 4.2 4.71 80.3 124 57.6 20 40 40 0 95 45 5.0 21.3 4.3 4.62 80.3 129 57.520 15 65 -2 84 46 3.5 16.3 4.6 3.43 79.2 93 57.3 15 20 65 -1 87 45 3.8 17.1 4.5 4.07 79.5 101 57.8 10 25 65 -1 90 45 4.0 17.9 4.4 4.49 79.8 107 58.15 15 80 -2 86 46 3.4 15.9 4.7 3.28 78.8 91 57.4
    Low temperature cooling mode results
    Petition 870200027007, of 28/02/2020, p. 14/23
    12/12 [0054] In low temperature refrigeration mode, the compression system works between an inlet temperature of the refrigerant in the evaporator of -30 ° C and an inlet temperature of the refrigerant in the condenser of 40 ° C. The system supplies cold at 25 ° C.
    [0055] The performances of the compositions according to the invention under operating conditions in low temperature refrigeration mode are given in table 3. The values of the constituents (HFO-1234yf, HFC-32, HFC-134a) for each composition are given in percentage by weight.
    Table 3
    Evap outlet temp (° C) Comp output temp (° C) T cond output (° C) evap P (bar) cond P (bar) Rate (p / p) Glide comp yield % CAP % COP / COPLorenz R404A -30 101 40 2.1 18.1 8.8 0.45 53.7 100 31.7 HFO-1234yf HFC-32 HFC-134a 75 20 5 -25 103 33 1.7 13.8 8.3 4.68 58.0 101 39.3 70 25 5 -25 106 33 1.8 14.8 8.1 4.94 59.2 110 40.2 65 30 5 -25 110 33 2.0 15.8 8.1 4.88 59.6 118 40.5 60 35 5 -25 115 34 2.1 16.7 8.1 4.59 59.4 125 40.4 55 40 5 -26 121 35 2.2 17.6 8.1 4.15 58.9 131 40.050 25 25 -26 113 34 1.7 14.7 8.4 4.31 57.0 108 39.4 45 30 25 -26 117 34 1.9 15.5 8.3 4.41 57.5 116 39.8 40 35 25 -26 122 34 2.0 16.3 8.3 4.34 57.6 122 39.8 35 40 25 -26 127 35 2.0 17.1 8.3 4.15 57.4 128 39.530 30 40 -25 124 34 1.8 15.2 8.6 4.52 55.7 113 38.8 25 35 40 -25 128 35 1.9 15.9 8.5 4.59 56.0 119 39.0 20 40 40 -25 134 35 1.9 16.5 8.5 4.56 56.0 124 38.9
    Petition 870200027007, of 28/02/2020, p. 15/23
    权利要求:
    Claims (9)
    [1]
    1. Use of a ternary composition of 2,3,3,3tetrafluoropropene, 1,1,1,2-tetrafluoroethane and difluoromethane, characterized by the fact that it is for use as heat transfer fluid in compression refrigeration systems with exchangers operating in countercurrent mode or in crosscurrent mode with countercurrent tendency.
    [2]
    2. Use, according to claim 1, characterized by the fact that the composition contains 2 to 80% by weight of 2,3,3,3tetrafluoropropene, 2 to 80% by weight of HFC-134a and 2 to 80% by weight of HFC-32.
    [3]
    3. Use, according to claim 1, characterized by the fact that the composition contains 5 to 25% by weight of 2,3,3,3tetrafluoropropene, 60 to 80% by weight of HFC-134a and 15 to 25% by weight of HFC-32.
    [4]
    4. Use according to claim 1, characterized by the fact that the composition contains from 45 to 80% by weight, preferably from 65 to 80% by weight of 2,3,3,3-tetrafluoropropene, from 5 to 25% by weight, preferably 5 to 10% by weight of HFC-134a and 15 to 30% by weight of HFC-32.
    [5]
    Use according to any one of claims 1 to 4, characterized in that the composition is stabilized.
    [6]
    6. Heat transfer process, characterized by the fact that a ternary composition of 2,3,3,3-tetrafluoropropene,
    1.1.1.2- tetrafluoroethane and difluoromethane is used as a refrigerant in compression systems with exchangers in countercurrent mode or in cross current mode with a countercurrent tendency.
    [7]
    7. Process according to claim 6, characterized by the fact that the composition contains from 5 to 25% by weight of the
    2.3.3.3- tetrafluoropropene, from 60 to 80% by weight of HFC-
    Petition 870200027007, of 28/02/2020, p. 16/23
    2/2
    134a and 15 to 25% by weight of HFC-32.
    [8]
    8. Process according to claim 6, characterized in that the composition contains from 45 to 80% by weight, preferably from 65 to 80% by weight of 2,3,3,3-tetrafluoropropene, from 5 to 25% by weight, preferably 5 to 10% by weight of HFC-134a and 15 to 30% by weight of HFC-32.
    [9]
    Process according to any one of claims 6 to 8, characterized in that it is carried out in the presence of lubricant.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-05| B06T| Formal requirements before examination|
    2019-08-06| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-12-31| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-04-07| B09A| Decision: intention to grant|
    2020-06-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/08/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR0956247A|FR2950069B1|2009-09-11|2009-09-11|USE OF TERNARY COMPOSITIONS|
    FR09.56247|2009-09-11|
    PCT/FR2010/051729|WO2011030030A2|2009-09-11|2010-08-18|Use of ternary compositions|
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