巴西专利BR112012005350B1 Use of ternary composition as heat transfer fluid and heat transfer process

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专利摘要:
use of ternary composition as a heat transfer fluid and heat transfer process the present invention relates to a heat transfer process, in which ternary compositions of 2,3,3,3 tetrafluoro propene, of 1, 1 – difluoro ethane and difluoro methane are particularly interesting as heat transfer fluid in compression refrigeration systems with exchangers operating in countercurrent mode or in cross current mode with a countercurrent tendency.
公开号:BR112012005350B1
申请号:R112012005350-7
申请日:2010-08-18
公开日:2020-02-18
发明作者:Wissam Rached
申请人:Arkema France；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for USE OF TERNARY COMPOSITION AS HEAT TRANSFER FLUID AND HEAT TRANSFER PROCESS.
[0001] The present invention relates to the use of 2,3,3,3-tetrafluoroprene ternary compositions as heat transfer fluids. [0002] The problems presented by substances that deplete the atmospheric ozone layer (ODP: potential ozone depletion) were dealt with in Montreal where the protocol was signed, imposing a reduction in the production and use of chlorofluoro carbides (CFC). This protocol constitutes the object of fines that imposed the abandonment of CFCs and extended the regulation to other products, including hydrochloride fluoro carbon (HCFC).
[0003] The refrigeration and air conditioning industry has invested a lot in replacing these refrigerants and this is how hydrofluoro carbides (HFCs) were commercialized.
[0004] The (hydro) chloro fluoro carbides used as blowing agents or solvents have been replaced by HFCs.
[0005] In the automobile industry, the air conditioning systems of vehicles sold in many countries are passed from a refrigerant to chlorofluoro carbide (CFC-12) to that of hydrofluoro carbide (1,1,1,2 tetrafluoro ethane: HFC-134a) , less harmful to the ozone layer. However, in relation to the objectives set by the Kyoto protocol, HFC-134a (GWP = 1300) is considered to have a high heating power. The contribution to the greenhouse effect of a fluid is quantified by a criterion, the GWP (Global Warming Potentials) that summarizes the heating power, considering a reference value of 1 for carbon dioxide.
[0006] Carbon dioxide, being non-toxic, non-flammable and having a very low GWP, has been proposed as a refrigerant for
Petition 870190111109, of 10/31/2019, p. 7/24
2/12 the air conditioning systems, replacing the HFC-134a. However, the use of carbon dioxide presents several drawbacks, notably linked to the very high pressure of its use as a refrigerant in existing devices and technologies.
[0007] On the other hand, the R-410A mixture consisting of 44% by weight of pentafluoro ethane, 52% by weight of trifluoro ethane and 4% by weight HFC-134a is widely used as a large surface refrigerant (supermarket) and refrigerated transport. This mixture, however, has a GWP of 3900. The R-407C mixture, consisting of 52% by weight of HFC-134a, 25% by weight of pentafluoro ethane and 23% by weight of difluoro methane, is used as the transfer fluid heat in the air conditioner and heat pumps. This mix, however, has a GWP of 1800.
[0008] JP 4110388 describes the use of hydrofluoro propenes of formula C3HmFn, with m, n representing an integer between 1 and 5 including + n = 6, as heat transfer fluids, in particular tetrafluoro propene and trifluoro propene.
[0009] WO2004 / 037913 discloses the use of compositions comprising at least one fluoroalkene, having three or four carbon atoms, notably pentafluoro propene and tetrafluoro propene, preferably having a maximum GWP of 150, as fluids of heat transfer.
[00010] WO 2005/105947 teaches the addition of tetrafluoro propene, preferably 1,3,3,3 tetrafluoro propene, to a co-blowing agent, such as difluoro methane, pentafluoro ethane, tetrafluoro ethane , difluoro ethane, heptafluoro propane, hexafluoro propane, pentafluoro propane, pentafluoro butane, water and carbon dioxide.
[00011] WO 2006/094303 discloses a composition
Petition 870190111109, of 10/31/2019, p. 8/24
3/12 azeotropic containing 7.4% by weight of 2,3,3,3 tetrafluoro propene (1234yf) and 92.6% by weight of difluoro methane (HFC-32). That document also discloses an azeotropic composition containing 91% by weight of 2,3,3,3 tetrafluoro propene and 9% by weight of difluoro ethane (HFC-152a).
[00012] A heat exchanger is a device that allows the transfer of 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 applied to cool or heat a liquid or a gas that is impossible to cool or heat directly. [00013] In compression systems, the thermal exchange between the refrigerant fluid and the heat sources is done through the fluids that carry heat. These heat-carrying fluids are either gaseous (air in the air conditioner and refrigeration with direct expansion), liquid (water in domestic heat pumps, glycolated water) or diphasic. [00014] There are different transfer modes:
- the two fluids are arranged in parallel and go in the same direction: co-current mode (anti-method);
- the two fluids are arranged in parallel, but go in the opposite direction: countercurrent mode (methodical);
- the two fluids are positioned perpendicularly: cross-flow mode. The cross current may be of a co-current or counter-current tendency;
- one of the two fluids makes a half-turn in a wider conduit, which the second fluid passes through. This configuration is comparable to a co-current exchanger about half the length, and for the other half to a countercurrent exchanger: pinhead mode. [00015] The applicant then discovered that ternary compositions of 2,3,3,3 tetrafluoro propene, 1,1-difluoro ethane and difluoro methane are particularly interesting, as heat transfer fluid
Petition 870190111109, of 10/31/2019, p. 9/24
4/12 in compression refrigeration systems with exchangers that operate in counter-current mode or in cross-current mode with a counter-current trend.
[00016] 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 refrigeration of refrigerated vehicles, using compression systems with exchangers in countercurrent mode or in cross current mode with a countercurrent tendency.
[00017] These compositions have at the same time a null ODP and a GWP lower than that of the existing heat transfer fluids with R-404A or R-407C ..
[00018] In addition, their performances (COP: defined performance coefficient, as the useful power supplied by the system over the power supplied or consumed by the system; and CAPSULE: volume capacity (kJ / m ³ )) are superior to those of fluids heat transfer systems such as the R-404A or R-407C.
[00019] The compositions used as heat transfer fluid in the present invention have a critical temperature above 93 ° C (Critical temperature of the R-404A is 72 ° C). These compositions can be used in heat pumps to provide heat at temperatures up to 65 ° C, but also at higher temperatures up to 90 ° C (temperature domain in which R-404A cannot be used).
[00020] The compositions used as heat transfer fluid in the present invention have lower condenser pressures than R-404A pressures and also lower compression rates. These compositions can use the same compressor technology applied by the R-404A. The compositions used as a transfer fluid
Petition 870190111109, of 10/31/2019, p. 10/24
5/12 heat sources in the present invention have vapor saturation density lower than the vapor saturated density of R-404A. The volume capacities given by these compositions are equivalent to or greater than the volume capacity of the R404A (between 97 and 110%). Thanks to these properties, these compositions work with smaller pipe diameters and, therefore, less pressure loss in the steam pipes, which increases the performances of the installations.
[00021] The present invention therefore has as its object the use of the ternary compositions of 2,3,3,3 tetrafluoro propene, 1,1difluoro ethane and difluoro methane are particularly interesting as heat transfer fluid in refrigeration systems compression with exchangers that operate in countercurrent or cross current mode with a countercurrent tendency.
[00022] Preferably, the compositions used in the present invention contain essentially 20 to 80% by weight of 2,3,3,3tetrafluoro propene and 15 to 40% by weight of difluoro methane and 5 to 40% by weight of difluoro ethane.
[00023] Advantageously, the compositions used contain essentially 20 to 70% by weight of 2,3,3,3 tetrafluoro propene and 20 to 40% by weight of difluoro ethane and 10 to 40% by weight of difluoro ethane.
[00024] Particularly preferred compositions contain essentially 35 to 70% by weight of 2,3,3,3 tetrafluoro propene, 20 to 25% by weight of difluoro methane and 10 to 40% by weight of 1,1difluoro ethane.
[00025] The compositions used in the present invention can be stabilized. The stabilizer preferably represents a maximum of 5% by weight in relation to the total composition.
[00026] As stabilizers, nitro methane, ascorbic acid, terephthalic acid, azoles, such as
Petition 870190111109, of 10/31/2019, p. 11/24
6/12 tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methyl phenol, epoxides (possibly fluorinated or perfluorinated alkyl or alkenyl or aromatic), such as n-butyl glycidyl ether, hexane diol diglycidyl ether, allyl glycidyl ether, butyl phenyl glycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones.
[00027] Another object of the present invention relates to a heat transfer process, in which ternary compositions of 2,3,3,3-tetrafluoro propene, 1,1-difluoro ethane and difluoro methane are particularly used. interesting as heat transfer fluid in compression refrigeration systems with exchangers operating in countercurrent mode or in crosscurrent mode with countercurrent tendency.
[00028] The process, according to the present invention, can be applied in the presence of lubricants, such as mineral oil, alkyl benzene, polyalkylene glycol and polyvinyl ether.
[00029] The compositions used in the present invention are suitable for the replacement of R-404A in refrigeration and / or R-407C in air conditioning and heat pumps with current installations.
Experimental Part
Calculation Tools [00030] The RK-Soave equation is used to calculate the densities, enthalpies, entropies and vapor balance data for mixtures. The use of this equation requires knowledge of the properties of the pure bodies used in the mixtures in question and also the interaction coefficients for each torque.
[00031] The necessary data for each pure body are:
[00032] 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 densities and saturated vapor 870190111109, of 10/31/2019, p. 12/24
7/12, depending on the temperature.
HFC-32, HFC-152a [00033] The data on these products are published in the ASHRAE Handbook 2005, chapter 20, and are also available under Refrop (Program developed by NIST for calculating the properties of refrigerants).
HFO-1234yf [00034] The data of the temperature-pressure curve of the HFO-1234yf are measured by the static method. The temperature and critical pressure are measured by a C80 calorimeter sold by Setaram. Densities, with saturation as a function of temperature, are measured by the densimeter technology with vibrating tube developed by the laboratories of the school of Mines of Paris.
Binary Interaction Coefficient [00035] 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.
[00036] The technique applied for the liquid vapor balance measures is the analytical static cell method. The balance cell comprises a saphir tube and is equipped with two electromagnetic ROLSITM samplers. It is immersed in a cryothermostat bath (HUBER HS40). A magnetic stirring with a rotating field drive at variable speed is used to accelerate the achievement of equilibrium. The analysis of the samples is done by gas chromatography (HP5890 series !!), using a catarometer (TCD).
HFC-32 / HFO-1234yf, HFC-152a / HFO-1234yf.
[00037] The liquid vapor balance measurements on the HFC32 / HFO-1234yf torque are performed for the following isotherms: -10 ° C, 30 ° C and 70 ° C.
Petition 870190111109, of 10/31/2019, p. 13/24
8/12 [00038] The liquid vapor balance measurements on the HFC152a / HFO-1234yf torque are performed for the following isotherms: 10 ° C.
HFC-32 / HFO-152a:
[00039] Liquid vapor balance data for torque HFC152a / HFC-32 are available under Refprop. Two isotherms (-20 ° C and 20 ° C) and two isobars (1 bar and 25 bar) are used to calculate the interaction coefficients for that torque.
Compression system [00040] Consider a compression system equipped with a countercurrent evaporator and condenser, a screw compressor and a distender.
[00041] The system works with 15 ° C of superheat and 5 ° C of subcooling. The minimum temperature deviation between secondary fluid and refrigerant is considered to be around 5 ° C.
[00042] The isentropic performance of the compressors is a function of the compression rate. This yield is calculated according to the following equation:
Qisen = ab (Tc) ² - d / Te (1) [00043] For a screw compressor, the constants a, b, c, and d of equation (1) of the isentropic performance are calculated according to the standard data published in the Handbook Handbook of air conditioning and refrigeration, page 11.52. The% CAP is the percentage of the ratio of the volume capacity provided by each product to the capacity of the R-410A.
[00044] The performance coefficient (COP) e is defined as the useful power supplied by the system over the power supplied or consumed by the system.
[00045] 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.
Petition 870190111109, of 10/31/2019, p. 14/24
9/12 [00046] Lorenz's performance coefficient is defined as follows:
(T temperatures are in K) (2) rj-f evaporator _ <-p evaporator π evaporator (3)
Lorenz's COP in the case of air conditioning and refrigeration:
COPlorenz - π CD cc ¹ css dur iTTedfs
(4)
Lorenz's COP in case of heating:
cDcdscssdur
COPlorenz = (5) [00047] For each composition, the Lorenz cycle performance coefficient is calculated as a function of the corresponding temperatures.
[00048] The% COP / COP Lorenz is the ratio of the system's COP to the COP of the corresponding Lorenz cycle.
Results in cooling mode or Air conditioning [00049] 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 provides heat at 45 ° C.
[00050] The performances of the compositions, according to the invention, under the heating operating conditions are given in Table 1. The values of the constituents (HFO-1234yf, HFC-32, HFC152a) for each composition are given in percentage by weight.
Petition 870190111109, of 10/31/2019, p. 15/24
Table 1
Temp. evap output. (° C) Temp. output comp. (° C) T outputcond (° C) Evap. P(Pub.) Cond P(Pub.) Rate(w / w) Glide Rend.Comp. % CAP % COP /COPLorenz R410A -5 77 50 5.2 23.0 4.4 0.38 79.7 100 57.7 HFO-1234yf HFC-32 HFC-152a 70 20 10 0 81 43 4.2 17.3 4.1 4.86 80.7 97 65.8 60 25 15 0 85 43 4.4 18.1 4.1 5.02 80.7 104 65.9 50 25 25 0 88 43 4.2 17.7 4.2 4.98 80.4 102 66.6 35 25 40 0 92 43 3.9 16.9 4.3 5.18 80.1 100 67.6
12/10
Petition 870190111109, of 10/31/2019, p. 16/24
12/11
Results Cooling or Air Conditioning Mode [00051] 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 provides heat at 0 ° C.
[00052] The performances of the compositions according to the invention in the operating conditions in heating mode are given in Table 2. The values of the constituents (HFO-1234yf, HFC32, HFC-152a) for each composition are given in percentage by weight .
Petition 870190111109, of 10/31/2019, p. 17/24
12/12
Table 2
Te mp. exit eva p.° C) Te mp. exit with p.(° C) T output with d (° C) Eva p.P (ba r.) Co nd P (ba r.) Rate (p / p) Gly from Ren d.Co mp. %CA P %COP / COPLo renz R41 0A -5 77 50 5.2 23, 0 4.4 0.38 79,7 100 47.9 HF O-123 4yf HFC-32 H F C-152a 70 20 10 0 81 43 4.2 17,3 4.1 4.86 80,7 105 57.8 65 20 15 0 82 43 4.1 17,1 4.2 4.68 80,6 104 58.3 60 25 15 0 85 43 4.4 18,1 4.1 5.02 80.7 113 58.2 55 20 25 0 85 43 3.9 16,7 4.2 4.52 80,3 104 59.0 50 25 25 0 88 43 4.2 17,7 4.2 4.98 80,4 112 59.2 40 20 40 0 89 43 3.7 16,1 4.4 4.58 80, 0 103 60.3 35 25 40 0 92 43 3.9 16,9 4.3 5.18 80,1 110 60.5 45 50 10 -26 140 35 2.2 18,6 8.5 3.73 56,4 93 38.9
Petition 870190111109, of 10/31/2019, p. 18/24

权利要求:
Claims (4)
[1]
1. Use of a ternary composition containing 35 to 70% by weight of 2,3,3,3-tetrafluorpropene, 20 to 25% by weight of 1,1difluorethane and 10 to 40% by weight of difluoromethane, characterized by fact that it is like heat transfer fluid in compression refrigeration systems with exchangers that operate in countercurrent mode or in cross current mode with countercurrent tendency, in which the composition is stabilized.
[2]
2. Heat transfer process, characterized by the fact that it uses 2,3,3,3-tetrafluorpropene ternary compositions,
1,1-difluorethane and difluoromethane as heat transfer fluid in compression refrigeration systems with exchangers that operate in countercurrent mode or in crosscurrent mode with a countercurrent tendency.
[3]
3. Process according to claim 2, characterized by the fact that the composition contains 35 to 70% by weight of 2,3,3,3-tetrafluorpropene and 20 to 25% by weight of difluoromethane and 10 to 40% by weight of difluorethane.
[4]
4. Process according to claim 2 or 3, characterized by the fact that it is applied in the presence of a lubricant.

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