Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
  • H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
  • H01H33/02—Details
  • H01H33/53—Cases; Reservoirs, tanks, piping or valves, for arc-extinguishing fluid; Accessories therefor, e.g. safety arrangements, pressure relief devices
  • H01H33/56—Gas reservoirs
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/56—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances gases
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
  • H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
  • H01H33/02—Details
  • H01H33/04—Means for extinguishing or preventing arc between current-carrying parts
  • H01H33/22—Selection of fluids for arc-extinguishing

Definitions

• the present invention relates to a gas used for the electrical insulation or extinguishing of electric arcs, as well as electrical appliances provided with an enclosure containing this gas.
• SFe has the major disadvantage of having a Global Warming Potential (GWP) of 22,800 (relative to CO 2 over 100 years) and a residence time in the atmosphere of 3,200 years, which places it among the gas with a high greenhouse effect.
• GWP Global Warming Potential
• Hybrid systems have been proposed which combine gas insulation with solid insulation (EP 1724802).
• this increases the volume of electrical appliances compared to that allowed by SF6 insulation; and the cut in the oil or vacuum requires a redesign of the equipment.
• Perfluorocarbons generally have interesting dielectric strength properties, but their GWP is typically in a range of 5,000 to 10,000.
• SFe and other gases such as nitrogen or nitrogen dioxide are used to limit the impact of SF6 on the environment: see, for example, WO 2009/049144. Nevertheless, because of the strong SF6 GWP, the GWP of these mixtures remains very high.
• a mixture of SFe and nitrogen in a volume ratio of 10/90 has a dielectric strength in alternating voltage (50 Hz) equal to 59% of that of SFe but its GWP is of the order of 8 000 to 8 650.
• Such mixtures can not therefore be used as a low environmental impact gas.
• the document FR 2955970 proposes the use of fluoroketones in the gaseous state for electrical insulation.
• the fluoroketones can be combined with a carrier gas or dilution gas (for example nitrogen, air, nitrous oxide, carbon dioxide, oxygen, helium, etc.).
• Document FR 2975818 proposes a mixture of octofluorobutan-2-one and carrier gas as isolation medium.
• the document FR 2983341 proposes the use of polyfluorinated oxiranes as electric insulation gas and / or electric arc extinguishing.
• Document FR 2986192 proposes the use of a combination of polyfluorinated oxirane and hydrofluoroolefin as an electrical insulating gas.
• the hydrofluoroolefins mentioned are 1, 3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,2,3,3,3-pentafluoropropene (HFO -1225ye).
• WO 2012/160158 proposes the use of a mixture of decafluoro-2-methylbutan-3-one and a carrier gas as an electrical insulating gas.
• Hydrofluoroolefins more particularly proposed are 1, 3,3,3-tetrafluoropropene (HFO-1234ze) and 2,3,3,3-tetrafluoropropene (HFO-1234yf).
• the document WO 2013/041695 proposes the use of a mixture of hydrofluoroolefin and of fluoroketone as electrical insulation gas.
• the hydrofluoroolefins more particularly proposed are 1, 3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,2,3,3,3-pentafluoropropene (HFO-1225ye).
• the document WO 2013/136015 proposes the use of a mixture of hydrofluoroolefin and hydrofluorocarbon as electrical insulation gas.
• the hydrofluoroolefins more particularly proposed are 1, 3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,2,3,3,3-pentafluoropropene (HFO-1225ye).
• the hydrofluorocarbons more particularly proposed are 1, 1, 1, 2,3,3, 3-heptafluoropropane (HFC-227ea), pentafluoroethane (HFC-125) and 1,1,1,2-tetrafluoroethane (HFC-134a).
• the invention firstly relates to the use of a gas as an electrical isolation medium and / or electric arc extinguishing, wherein the gas comprises 1-chloro-3,3,3-trifluoropropene.
• the 1-chloro-3,3,3-trifluoropropene is in trans form.
• the gas also comprises a diluent, preferably selected from air, nitrogen, methane, oxygen, carbon dioxide or a mixture thereof.
• said use is a use as an electrical isolation medium and / or electric arc extinguishing in a medium voltage substation electrical apparatus.
• the gas further comprises a fluoroketone, said fluoroketone being preferably decafluoro-2-methylbutan-3-one.
• the gas contains from 1 to 100 mol% of 1-chloro-3,3,3-trifluoropropene, preferably from 2 to 50 mol%, more particularly from 4 to 30 mol%, and especially from 6 to 25 mol%.
• the gas is a binary mixture of 1-chloro-3,3,3-trifluoropropene and diluent, and preferably the proportion of 1-chloro-3,3,3-trifluoropropene is 5. at 50 mol%, more preferably from 10 to 30 mol%, and most preferably from 15 to 25 mol%.
• the gas is a ternary mixture of 1-chloro-3,3,3-trifluoropropene, fluoroketone and diluent, and preferably the proportion of 1-chloro-3,3,3-trifluoropropene is 2 to 15 mol%, more preferably 5 to 10 mol%, and preferably the proportion of fluoroketone is 2 to 15 mol%, more particularly 5 to 10 mol%.
• the invention also relates to an electrical apparatus comprising a sealed enclosure in which there are electrical components as well as an electrical insulating gas and / or electric arc extinguishing, in which the gas comprises 1-chloro 3,3,3-trifluoropropene.
• the 1-chloro-3,3,3-trifluoropropene is in trans form.
• the gas also comprises a diluent, preferably selected from air, nitrogen, methane, oxygen, carbon dioxide or a mixture thereof.
• the electrical apparatus is a medium voltage electrical appliance.
• the gas further comprises a fluoroketone, said fluoroketone being preferably decafluoro-2-methylbutan-3-one.
• the gas is at a pressure at 20 ° C. of 0.1 to 1 MPa, preferably of 0.1 to 0.5 MPa, and more particularly of 0.12 to 0.15 MPa.
• the gas has a partial pressure of 1-chloro-3,3,3-trifluoropropene at 20 ° C of 0.002 to 0.1 MPa, preferably of 0.005 to 0.05 MPa, more particularly preferred from 0.008 to 0.03 MPa.
• the gas is a binary mixture of 1-chloro-3,3,3-trifluoropropene and diluent, and preferably the partial pressure of 1-chloro-3,3,3-trifluoropropene at 20 ° C. ° C is from 0.01 to 0.05 MPa, more preferably from 0.02 to 0.04 MPa.
• the gas is a ternary mixture of 1-chloro-3,3,3-trifluoropropene, fluoroketone and diluent, and, preferably, the partial pressure of 1-chloro-3,3,3- trifluoropropene at 20 ° C is from 0.005 to 0.03 MPa, more preferably 0.008 to 0.02 MPa, and preferably the fluoroketone partial pressure at 20 ° C is 0.005 to 0.03 MPa, more preferably 0.008 to 0.02 MPa.
• the electrical apparatus is selected from a gas-insulated electrical transformer, a gas-insulated line for the transmission or distribution of electricity, and an electrical connection / disconnection apparatus.
• the present invention overcomes the disadvantages of the state of the art. More particularly, it provides electrical insulation and / or arc-extinguishing media having both low GWP and high dielectric strength.
• HCFO-1233zd 1-chloro-3,3,3-trifluoropropene-based media, commonly referred to as HCFO-1233zd, have remarkable dielectric strength properties, and especially superior to those of HFO-1234ze or HFO-1234yf depending on configurations.
• HCFO-1233zd with a fluoroketone such as decafluoro-2-methylbutan-3-one is particularly advantageous since a synergistic combination effect between the two compounds has been observed.
• FIG. 1 illustrates the liquid-vapor equilibrium curves, at -15.degree. C., of the HCFO-1233zd / CO2 mixture of example 4 which reflect the evolution of the pressure of this mixture (denoted P and expressed in bar) according to the molar percentage of CO2 (noted CO2 and expressed in% mol).
• the invention relates to a gas used as an electrical isolation medium and / or electric arc extinguishing.
• the gas according to the invention comprises at least 1-chloro-3,3,3-trifluoropropene or HCFO-1233zd.
• HCFO-1233zd can be in trans form, or in cis form, or can be a mixture of both forms. The trans form is preferred.
• the gas may also comprise additional compounds, in particular a diluent (or dilution gas, or buffer gas) and optionally one or more other halogenated compounds (especially fluorinated compounds).
• the gas according to the invention comprises (or possibly consists essentially of, or possibly consists of) a mixture of HCFO-1233zd and a diluent.
• the gas according to the invention comprises (or possibly consists essentially of, or possibly consists of) a mixture of HCFO-1233zd and another halogenated compound.
• the gas according to the invention comprises (or possibly consists essentially of, or possibly consists of) a mixture of HCFO-1233zd, another halogenated compound and a diluent.
• the halogenated compound is a hydrochlorofluoroolefin, a hydrofluoroolefin or a fluoroketone.
• the halogenated compound is a fluorinated compound, which is preferably chosen from fluoroketones, fluoethers, fluonitriles, fluorinated peroxides, fluoroamides and fluoro ether oxides.
• Decafluoro-2-methylbutan-3-one is a preferred halogenated compound. Therefore, according to one embodiment, the gas according to the invention comprises (or possibly consists essentially of, or possibly consists of) a mixture of HCFO-1233zd and decafluoro-2-methylbutan-3-one; or a mixture of HCFO-1233zd, decafluoro-2-methylbutan-3-one and a diluent.
• the diluent may be for example selected from air, nitrogen, methane, oxygen, nitrous oxide, helium and carbon dioxide. Mixtures of these are also possible.
• the gas according to the invention does not undergo condensation for the entire range of projected use temperature. It is also desired to use this gas at a sufficiently high pressure, in principle greater than 10 5 Pa. Under these conditions, the use of a diluent makes it possible to avoid reaching the saturation vapor pressure of the HCFO-1233zd or other halogenated compounds that may be present throughout the projected use temperature range.
• a diluent is generally a compound having a boiling point lower than that of HCFO-1233zd and also having a lower electrical rigidity (at a reference temperature of, for example, 20 ° C).
• the absolute operating pressure of the gas according to the invention is preferably from 1 to 1.5 bar in medium voltage devices and from 4 to 7 bar in high voltage devices.
• medium voltage and “high voltage” are used herein in their usual acceptance that the term “medium voltage” refers to a voltage that is greater than 1000 volts AC and 1500 volts DC but that does not does not exceed 52000 volts AC and 75000 volts DC, while the term “high voltage” means a voltage that is strictly greater than 52000 volts AC and 75000 volts DC.
• the minimum temperature of use Tmin of the high and medium voltage equipment varies according to the countries and the standards in force. So that the dielectric strength of the device at this minimum temperature meets the country and normative requirements, it is necessary that the amount of gas (which is expressed here in terms of number of molecules or partial pressures brought to the same temperature, usually 20 ° C) inside the apparatus at Tmin is greater than or equal to the minimum amount of gas defined to have a dielectric strength greater than or equal to the normative value.
• the minimum use temperatures Tmin are generally -40 ° C, -30 ° C, -25 ° C, -15 ° C, -5 ° C, 0 ° C, + 5 ° C.
• Ptot represents the operating pressure of the gas according to the invention
• P represents the partial pressure of HCFO-1233zd and other halogenated compounds
• PVS represents the saturation vapor pressure of HCFO-1233zd and other compounds halogenated.
• the pressures are given at the filling temperature, in general about 20 ° C.
• the gas according to the invention has a GWP of less than or equal to 20, more particularly less than or equal to 15 or to 10, or to 7, or to 5, or to 4, or to 3.
• the GWP is defined relative to carbon dioxide and compared to a duration of 100 years, according to the method indicated in "The scientific assessment of ozone depletion, 2002, report of the World Meteorological Association's Global Ozone Research and Monitoring Project".
• the (molar) proportion of HCFO-1233zd in the gas may in some embodiments be 1 to 2%; or 2 to 3%; or 3-4%, or 4-5%; or from 5 to 6%; or 6-7%; or 7 to 8%; or from 8 to 9%; or from 9 to 10%; or from 10 to 12%; or from 12 to 14%; or from 14 to 16%; or from 16 to 18%; or 18 to 20%; or 20 to 22%; or 22 to 24%; or 24 to 26%; or from 26 to 28%; or from 28 to 30%; or from 30 to 35%; or 35 to 40%; or 40 to 45%; or 45 to 50%; or 50 to 55%; or 55 to 60%; or 60 to 70%; or 70 to 80%; or 80 to 90%; or 90 to 100%.
• the partial pressure of HCFO-1233zd in the gas at 20 ° C may in some embodiments be 0.002 to 0.004 MPa; or from 0.004 to 0.006 MPa; or from 0.006 to 0.008 MPa; or from 0.008 to 0.01 MPa; or from 0.01 to 0.012 MPa; or from 0.012 to 0.014 MPa; or from 0.014 to 0.016 MPa; or from 0.016 to 0.018 MPa; or from 0.018 to 0.02 MPa; or from 0.02 to 0.022 MPa; or from 0.022 to 0.024 MPa; or from 0.024 to 0.026 MPa; or from 0.026 to 0.028 MPa; or from 0.028 to 0.03 MPa; or from 0.03 to 0.032 MPa; or from 0.032 to 0.034 MPa; or from 0.034 to 0.036 MPa; or from 0.036 to 0.038 MPa; or from 0.04 to 0.045 MPa;
• electrical appliances contain a relatively high amount of HCFO-1233zd (and possibly other halogenated and especially fluorinated gases), so that the dielectric, thermal and gas-off characteristics are sufficient over the normative or desired temperature range.
• a heating device in combination with an electrical appliance, said heating device being triggered according to the temperature of the gas mixture, its pressure or its density.
• a heating resistor ideally placed at the lowest point of the apparatus (point of convergence of the condensed liquids on the various parts inside the apparatus, by gravitation) can be used.
• the dielectric tests are conducted in models of epoxy resin filled with silica, between two electrodes.
• the diameter of the electrodes and the distance between them makes it possible to have two electric field configurations representative of what is encountered in medium voltage switchgear:
• the models are initially filled with ambient air.
• a moisture adsorber (CaSO 4 , CaC, molecular sieve or activated carbon) compatible with the gases tested is placed in the model. Evacuate at room temperature (to a pressure below 200 Pa) before injecting the halogenated compounds until their saturation vapor pressure at -15 ° C, calculated at room temperature. The dilution gas is then added.
• the total (absolute) pressure of the gas or gas mixture inside the models is set at 0.13 MPa (at 20 ° C).
• Each model is placed in a climatic chamber at a set temperature for at least 16 hours so that the gas reaches this temperature.
• the dielectric tests (lightning shock with a wave 1, 2-50 and frequency test at 50 Hz - 1 min) are done inside the enclosure.
• Example 1 tests at -15 ° C., binary mixture
• pure SFe reference gas
• E-HFO-1233zd 0.104 MPa of dry air
• E-HFO-1233ze alone at 0.13 MPa
• MPa, HFO-12234yf alone at 0.13 MPa and dry air alone at 0.13 MPa The pressures are given at 20 ° C.
• the tests were made in positive and negative polarity in both electric field configurations.
• the value selected for each gas is the lowest dielectric withstand value in positive and negative polarity.
• the HCFO-1233zd / dry air mixture has a better dielectric strength than those of the two other pure olefins, although its partial pressure is five times lower than that of these latter.
• the HFO-1234yf has the disadvantage that, in case of internal arc, a relatively high concentration of HF is generated around the cell; and HCFO -1233zd also has the advantage of not being flammable.
• E-HCFO-1233zd is used at a pressure of 0.08 MPa.
• the other gases are used at a pressure of 0.13 MPa.
• E-HCFO-1233zd has a better dielectric strength in lightning shock than HFO-1234ze or HFO-1234yf, although it is used at a lower pressure. Its dielectric strength is also about twice that of dry air and equivalent to that of the reference product, SF6.
• Example 3 tests at -15 ° C., binary mixture and ternary mixture
• a direct line test is performed on a C5K / air binary mixture (with 0.016 MPa of C5K and 0.114 MPa of air), a binary E-HCFO-1233zd / air mixture (with 0.0266 MPa of E-HCFO-1233zd and 0.1034 MPa of air) and a ternary mixture E-HCFO-1233zd / C5K / air (with 0.01 MPa of E-HCFO-1233zd, 0.01 MPa of C5K and 0 , 1 1 MPa of air) at 20 ° C.
• C5K refers to decafluoro-2-methylbutan-3-one.
• Example 4 tests at -15 ° C., binary mixture
• Liquid-vapor equilibrium measurements were performed with the analytical static cell method.
• the balance cell used includes a sapphire tube and is equipped with two electromagnetic ROLSITM samplers. It is immersed in a cryothermostat bath (HUBER HS40). Variable speed rotary field driving magnetic stirring is used to accelerate equilibrium attainment.
• the analysis of the samples is carried out by gas chromatography (HP5890 series II) using a katharometer (TCD). The values thus measured are reported as points in Figure 1.
• the dielectric tests were conducted in a homogeneous electric field.
• the filling pressure at 20 ° C of HCFO-1233zd is 0.0365 MPa.
• CO2 is added to have a total pressure of 0.13 MPa.

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• Spectroscopy & Molecular Physics (AREA)
• Organic Insulating Materials (AREA)
• Gas-Insulated Switchgears (AREA)

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• 2014
  • 2014-10-14 FR FR1459852A patent/FR3027154B1/fr active Active
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  • 2015-10-13 WO PCT/EP2015/073716 patent/WO2016059075A1/fr active Application Filing
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