Method and facility for filling a gas-insulated electrical apparatus comprising a mixture of (CF3)2CFCN and CO2

Abstract

A method and a facility for filling a high- or medium-voltage gas-insulated electrical apparatus in which the insulating gas comprises a mixture of heptafluoroisobutyronitrile ((CF.sub.3).sub.2CFCN) and carbon dioxide. The method and the facility using a mixture of (CF.sub.3).sub.2CFCN and CO.sub.2 in pressurised liquid form which is heated to a temperature no lower than the critical temperature of the mixture.

Claims

1. A method of filling a closed casing containing at least one electrical component of equipment for a high-or medium-voltage electricity transmission line with a gas mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions, said method comprising: a) preparing, in a container, a pressurized liquid mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions; b) heating, in the container, the pressurized liquid mixture prepared in a) until it reaches a temperature that is higher than or equal to the critical temperature of the mixture whereby a gas mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions is obtained; and c) transferring said gas mixture obtained in b) from the container to the casing via a transfer circuit in which the gas mixture is decompressed and maintained at a temperature that is higher than the liquefaction temperature of heptafluoroisobutyronitrile at its partial pressure in the transfer circuit before it enters the casing to be filled.

2. The method according to claim 1, wherein heating is performed during b) by a heater member outside the container.

3. The method according to claim 1, wherein heating is performed during b) by a heater member inside the container.

4. The method according to claim 1, wherein, during c), the molar ratio between heptafluorobutyronitrile and carbon dioxide in the gas mixture is measured.

5. The method according to claim 1, wherein, during c), the temperature of the gas mixture in the container is measured.

6. The method according to claim 1, wherein the heating power during a) is adjusted and/or regulated on the basis of: a molar ratio between heptafluoroisobutyronitrile and carbon dioxide which is measured during c); a temperature of the gas mixture in the container which is measured during c); or a measured temperature of a heater members.

7. The method according to claim 1, wherein the gas mixture comprising heptafluoroisobutyronitrile and carbon dioxide further comprises oxygen.

8. An installation for filling a closed casing containing at least one electrical component of equipment for a high- or medium-voltage electricity transmission line with a gas mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions, the installation comprising: a container configured for containing a mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions; a heater member configured for heating the mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions present in the container in pressurized liquid form until it reaches a temperature that is higher than or equal to the critical temperature of the mixture whereby a gas mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions is obtained; and a transfer circuit configured for transferring the gas mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions from the container to the casing, the transfer circuit fluidly connecting said container with the casing and the transfer circuit having an expansion member configured for reducing the pressure of the gas mixture to a determined value to fill the casing for maintaining the gas mixture at a temperature that is higher than the liquefaction temperature of heptafluoroisobutyronitrile at its partial pressure in the transfer circuit, the filling installation comprising one or more temperature safety features.

9. The filling installation according to claim 8, wherein the transfer circuit has means configured for measuring the molar ratio between heptafluoroisobutyronitrile and carbon dioxide in the gas mixture.

10. The filling installation according to claim 8, being wherein the transfer circuit presents a temperature sensor configured for measuring the temperature of the gas mixture in the container.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a fragmentary diagram showing the structure and the operation of a first example of a filling installation of the invention in which the heating system is outside the container and regulation of heating power is conditioned by the measured temperature of the gas mixture in the container (2).

(2) FIG. 2 is a fragmentary diagram showing the structure and the operation of a second example of a filling installation of the invention in which the heating system is outside the container and regulation of heating power is conditioned by directly measuring the molar ratio between the heptafluoroisobutyronitrile and the carbon dioxide in the gas mixture.

(3) FIG. 3 is a fragmentary diagram showing the structure and the operation of a third example of a filling installation of the invention in which the heating system is inside the container and regulation of heating power is conditioned by the measured temperature of the gas mixture in the container (2).

(4) FIG. 4 is a fragmentary diagram showing the structure and the operation of a fourth example of a filling installation of the invention in which the heating system is inside the container and regulation of heating power is conditioned by directly measuring the molar ratio between the heptafluoroisobutyronitrile and the carbon dioxide in the gas mixture.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS

(5) Above and below, the expression high voltage is used in the conventionally accepted manner, i.e. the expression high voltage refers to a voltage that is strictly greater than 52,000 volts (V) for alternating current (AC) and 75,000 volts for direct current (DC).

(6) In the context of the invention, the expression medium voltage is used in the conventionally accepted manner, i.e. the term medium voltage refers to a voltage that is greater than 1000 V for AC or greater than 1500 V for DC, but that does not exceed 52,000 V for AC, or 75,000 V for DC.

(7) An electrical apparatus mainly comprises a longitudinal outer casing or enclosure (1), defining a hollow volume and one or more electrical component(s) that is/are arranged inside the casing.

(8) The inside volume of the casing is closed in gastight manner and is filled with a gas for electrical insulation and for electric arc extinction, which gas comprises a mixture of heptafluoroisobutyronitrile and carbon dioxide.

(9) Thus, the gas insulation implements a gas mixture comprising heptafluoroisobutyronitrile and carbon dioxide.

(10) Heptafluoroisobutyronitrile having the formula (I): (CF.sub.3).sub.2CFCN (I), also written iso-C.sub.3F.sub.7CN, or i-C.sub.3F.sub.7CN, corresponds to 2,3,3,3-tetrafluoro-2-trifluoromethyl propanenitrile, having CAS registry number: 42532-60-5, presenting a boiling point of 4.7 C. at 1013 hectopascals (hPa) (boiling point as measured by ASTM standard D1120-94 Standard Test Method for Boiling Point of Engine Coolants).

(11) The relative dielectric strength of heptafluoroisobutyronitrile having formula (I), that is normalized relative to SF.sub.6, is 2.2, said dielectric strength being measured at atmospheric pressure, with a DC voltage, between two steel electrodes having a diameter of 2.54 centimeters (cm) and spaced apart by 0.1 cm.

(12) Thus, heptafluoroisobutyronitrile having the formula (I) as described above, that is non-toxic, non-corrosive, non-flammable, and that presents a GWP that is low relative to that of SF.sub.6, is endowed with electrical insulation or electric arc extinction properties suitable for enabling it to replace SF.sub.6 as an insulation gas and/or arc-extinction gas in high-voltage equipment, in combination with a dilution gas.

(13) The liquid or gas mixture used within the context of the present invention comprises heptafluoroisobutyronitrile and carbon dioxide in predefined proportions.

(14) In the gas mixture used to fill the casing, the carbon dioxide is a dilution gas also known as mixture gas or carrier gas.

(15) Under the conditions of use of the equipment, the pressure inside the casing is of the order of 6 bars to 10 bars for high-voltage equipment and of the order of 0.3 bars to 1.5 bars for medium-voltage equipment. Under such pressure or at low temperatures, heptafluoroisobutyronitrile liquefies and that limits the effectiveness of the electric insulation. That is why a dilution gas such as carbon dioxide is used in a mixture with the heptafluoroisobutyronitrile gas, so as to lower the partial pressure to below the saturated vapor pressure at the minimum service temperature of the equipment.

(16) The liquid or gas mixture used within the context of the present invention may contain nothing other than heptafluoroisobutyronitrile and carbon dioxide and thus be made up of these two components only. In this event, the liquid or gas mixture comprises 2 molar percent (mol %) to 15 mol % of heptafluoroisobutyronitrile and 85 mol % to 98 mol % of carbon dioxide and, in particular, 4 mol % to 10 mol % of heptafluoroisobutyronitrile and 90 mol % to 96 mol % of carbon dioxide.

(17) In a variant, this liquid or gas mixture may contain at least one other element in addition to heptafluoroisobutyronitrile and carbon dioxide. This other element may be any component that is used conventionally in electrical insulation of high- or medium-voltage equipment. Advantageously, such a compound presents a GWP that is equal to 1 or even zero. More particularly, the element for use in the context of the present invention in a mixture with heptafluoroisobutyronitrile and carbon dioxide is selected from among nitrogen, oxygen, air, advantageously dry air, and any mixture thereof. Typically, the other element is oxygen.

(18) In this variant, the liquid or gas mixture comprises 2 mol % to 15 mol % heptafluoroisobutyronitrile, 70 mol % to 97 mol % carbon dioxide and 1 mol % to 15 mol % of at least one other element as described above and in particular 1 mol % to 15 mol % oxygen. In particular, the liquid or gas mixture comprises 4 mol % to 10 mol % heptafluoroisobutyronitrile, 80 mol % to 94 mol % carbon dioxide and 2 mol % to 10 mol % of at least one other element as described above and in particular 2 mol % to 10 mol % oxygen.

(19) The first step of the method of the present invention consists in preparing, in a container (2), a pressurized liquid mixture comprising heptafluoroisobutyronitrile and carbon dioxide in predefined proportions.

(20) The container (2) implemented within the context of the present invention is a container adapted for filling and transporting CO.sub.2 in the liquid, gaseous, or even supercritical state. This container may be in the form of a bottle, a cylinder, or some other container, typically being suitable for containing 1 L to 1000 L of liquid, 50 L bottles of the B50 type being most commonly used. This type of container is well known to the person skilled in the art and available from nearly all manufacturers and retailers of liquefied CO.sub.2.

(21) Calculating the densities for the liquid mixtures as opposed to the gas mixtures makes it possible to come close to the advantages of step a) of preparing a mixture of components in liquid form.

(22) The density of pure CO.sub.2 in the gaseous state is, at atmospheric pressure, 1.87 kg/m.sup.3 and 1256 kg/m.sup.3 once liquefied. There is therefore a compression ratio of the order of 500. Within the context of gas mixtures implemented within the context of the present invention advantageously comprising CO.sub.2 and between 4 mol % and 10 mol % of i-C.sub.3F.sub.7CN, this compression ratio between liquid and gas remains similar (see Table 1 below).

(23) TABLE-US-00001 TABLE 1 Gas Liquid density density mol % weight % [kg/m.sup.3] [kg/m.sup.3] Heptafluoro- 100 100 8.11 1350 isobutyronitrile CO.sub.2 100 100 1.87 1256 Mixture at 0.04 0.15 2.1 1259.8 4 mol % Mixture at 0.06 0.22 2.2 1261.6 6 mol % Mixture at 0.10 0.33 2.5 1265.4 10 mol %

(24) Within the context of mixtures comprising CO.sub.2 and 4 mol % of i-C.sub.3F.sub.7CN, which make it possible to reach minimum service temperatures for the high- or medium-voltage equipment of the order of about 30 C., or even lower than 30 C., without liquefaction of the i-C.sub.3F.sub.7CN portion, the density of the gas is 2.1 kg/m.sup.3 and 1260 kg/m.sup.3 for the liquid phase.

(25) Considering, as a container (2), a traditional B50-type bottle with a capacity of 50 L and a test pressure of 190 bars, the filling ratio for this type of gas respecting ADR regulations for carriage by road is 0.5 kg/L. This bottle thus contains a maximum of 25 kilograms (kg) of mixture with 4 mol % of i-C.sub.3F.sub.7CN, which in an expanded phase represents approximately 12 m.sup.3 at atmospheric pressure (25/2.1).

(26) In order to compare it to storage and transport in a gas phase, it is necessary to remain at pressures that do not allow liquefaction of the phase i-C.sub.3F.sub.7CN at 30 C., and that represents a maximum partial pressure of 0.37 bars absolute. In this event, the pressure of the mixture in the container should not exceed 9.3 bars absolute (0.37/0.04), giving a density of 19.6 kg/m.sup.3, whereas the B50 bottle has a density of 500 kg/m.sup.3 which makes it possible to concentrate the gaseous medium by a factor of 25 (500/19.6).

(27) The preparation of a mixture in the form of a pressurized liquid comprising a predetermined amount of CO.sub.2 and i-C.sub.3F.sub.7CN is a conventional step for the person skilled in the art including an accurate measurement of the weights of CO.sub.2 and i-C.sub.3F.sub.7CN that may involve the use of flowmeters as well as compression and/or cooling.

(28) Within the context of the step b) of the method of the invention, transfer from the pressurized liquid phase contained in the container (2) is performed by causing the mixture to pass into a supercritical state. For pure CO.sub.2, this occurs at a critical temperature of 31 C. and at a critical pressure of 73.8 bars. For mixtures based on i-C.sub.3F.sub.7CN and CO.sub.2, the critical temperatures of the mixtures are calculated using equations (1) and (2) combined.

(29) By way of example, for a mixture with 4 mol % of i-C.sub.3F.sub.7CN in CO.sub.2, the critical temperature of said mixture is as follows:

(30) $T_{{\mathrm{cri}}_{\mathrm{mix}}}=\frac{0.04*378.5*\left(273.15+109\right)}{0.04*378.5+0.96*94}+\frac{0.96*94*\left(273.15+31\right)}{0.04*378.5+0.96*94}=315K$

(31) The critical temperature of the mixture with 4 mol % of i-C.sub.3F.sub.7CN in CO.sub.2 is of 315 kelvin (K), i.e. 42 C. A similar calculation was performed for the various mixtures and the values obtained are shown in Table 2 below:

(32) TABLE-US-00002 TABLE 2 i-C.sub.3F.sub.7CN T.sub.c P.sub.c mole fraction ( C.) (bar) 0 31.0 73.77 0.04 42 74 0.06 47 73 0.08 51 72 0.10 55 71

(33) Step b) of the method of the invention thus consists in heating the pressurized liquid mixture contained in the container (2) to a temperature that is higher than or equal to the temperature for bringing the contained mixture to the supercritical state. In such a state, CO.sub.2 and heptafluoroisobutyronitrile mix perfectly, pass into the gaseous state with the density of the liquid and occupy the entire volume of the container in homogeneous manner so as to form just one gas.

(34) To achieve this object, a heater member (4) outside the container (2) and/or a heater member (5) inside the container (2) is/are used.

(35) In a first implementation, heating is performed by a member (4) located outside the container (2) i.e. mounted on the walls of the container (2) or positioned in the proximity thereof. Such a member may be in the form of a heater belt or a heater cable of the resistive or inductive type or that is heated by passing a fluid heated to a temperature that is adapted to heat the mixture contained in the container (2) to the desired temperature. In a variant, this outer heater member (4) may be in the form of a temperature-stabilized box arranged around the container (2).

(36) In a second implementation, this heating is performed by a heater member (5) inside the container (2). Such a member is typically presented in the form of a heater resistor positioned in the inside volume defined by the container (2). When heating is performed by means of an inside heater member (5), the container may further present, mounted on its walls or positioned in the proximity thereof, a thermal insulation system (10) of the thermally insulating housing type.

(37) In a third implementation, heating is performed at the same time by a heater member (4) outside the container (2) and a heater member (5) inside the container (2).

(38) The heating power of the container (2) is calculated as a function of the vaporization enthalpy of the gas mixture, the required mass flow, and the heat losses of the entire system. For a mixture comprising CO.sub.2 and 4 mol % of i-C.sub.3F.sub.7CN, the vaporization enthalpy is of approximately 15.7 kJ/mol. For a transfer rate of the order of 50 kg/h, a heating power of approximately 5 kW is therefore necessary.

(39) In a first implementation, the heating power of the container (2) may be adjusted and/or regulated on the basis of the measured molar ratio between i-C.sub.3F.sub.7CN and CO.sub.2 present in the gas mixture while said gas is transferred between the container (2) and the casing (1). To this end, the transfer circuit (3) may present means (8) for measuring the molar ratio between i-C.sub.3F.sub.7CN and CO.sub.2 in the gas mixture, typically, downstream from the expansion member (6) and upstream of the casing (1) to be filled. Any means suitable for measuring a molar ratio in a gas mixture with several components can be used within the context of the present invention. By way of illustrative and non-limiting examples, mention may be made of an in-line gas chromatograph, a gas analyzer, an infra-red spectrometer, an analyzer based on the measurement of the speed of sound in the gas, a densitometer, a mass spectrometer, or any combination thereof. If the measured molar ratio is different from the predetermined value of the molar ratio, a tap or a valve (11) such as a solenoid valve placed upstream from the casing (2) to be filled is closed, manually or automatically, in order to prevent filling of the casing, and the heating power of the container (I) is regulated so that the measured molar ratio reaches the value of the predetermined molar ratio.

(40) In a second implementation, the heating power of the container (2) may be adjusted and/or regulated on the basis of the measured temperature of the gas mixture in the container (2) during transfer step c) and before its expansion. Indeed, in order to maintain the advantages related to the use of the supercritical mixture, it is necessary during the transfer step c) and before the gas expands, for the temperature of the gas mixture to remain at a value that is greater than or equal to the critical temperature of the mixture. Any means known to the person skilled in the art for measuring the temperature of a gas of the temperature sensor type may be used for this monitoring. Such a temperature sensor must be located as close as possible to the mixture in a supercritical state. Typically this temperature sensor (9) is located at the bottom of the container (2). If the measured temperature is lower than the critical temperature of the mixture, a tap or a valve (11) such as a solenoid valve placed upstream from the casing to be filled (2) is closed, manually or automatically, in order to prevent filling of the casing, and the heating power of the container (1) is regulated so that the measured temperature reaches a value that is greater than or equal to the critical temperature of the mixture.

(41) Finally, the heating power of the container (2) may be adjusted and/or regulated on the basis of the measured temperatures of the heater members (4, 5). Thus, the heater members (4, 5) within the context of the method and of the installation of the invention may present temperature sensors suitable for or intended for stopping heating in the event of a limit value defined by the operator being exceeded.

(42) In addition, the installation of the invention advantageously presents at the container (2) a rupture disk designed to avoid an overpressure in said container in the event of failure of the heat regulation system. Such a rupture disk is typically rated at 120 bars.

(43) Finally, it should be observed that the installation of the present invention contains one or more temperature safety features so that the gas mixture never reaches a temperature determined by the operator, which is typically 65 C.

(44) During step c) of the method of the invention, the gas mixture obtained during step b) is brought from the container (2) to the casing (1) via a transfer circuit (3). During said transfer, the gas mixture must be expanded until it presents a pressure value that is adapted to filling the casing (1). This expansion uses an expansion member (6) that is configured to lower the pressure of the gas mixture by a value that is greater than or equal to the critical pressure of the mixture up to a given value lying in the range 1 bar to 15 bars. Any expansion member (6) known to the person skilled in the art is suitable for use within the context of the present invention. Such a member of the pressure-reducing type presents a chamber or zone of high pressure (HP) arranged downstream from the container (2) and a chamber or zone of low pressure (LP) arranged upstream from the casing (1).

(45) At the same time, the temperature of the gas mixture must be maintained at a temperature that is higher than the liquefaction temperature of i-C.sub.3F.sub.7CN at its partial pressure in the transfer circuit (3) in order to avoid depositing liquid i-C.sub.3F.sub.7CN in the transfer circuit (3), which would lead to a modification of the molar ratio between i-C.sub.3F.sub.7CN and CO.sub.2 in the remaining gas mixture. However, when the valve or the tap (12) isolating the container (2) of the transfer circuit (3) is open, the gas mixture initially contained in the container passes through the transfer circuit (3) where it cools by Joule-Thomson (expansion) effect. In order to compensate for this cooling and maintain the gas mixture at a temperature that is higher than the liquefaction temperature of i-C.sub.3F.sub.7CN, the transfer circuit (3) presents a system (7) that is suitable for keeping the gas mixture at a temperature that is higher than the liquefaction temperature of heptafluoroisobutyronitrile, which system is of the gas heater type and in particular of the CO.sub.2 heater type. The temperature-regulating action of this system may be supplemented by using a transfer circuit (3) having all or some of its ducts or pipes being heating ducts or pipes. In the method or the installation of the invention, the heating ducts or pipes are typically at a temperature of about 30 C. (i.e. 30 C.4 C.). In a particular implementation, the transfer circuit (3) presents a gas heater (7) placed downstream from the valve or the tap (12) and upstream from the expansion member (6), and the pipes or ducts of the transfer circuit downstream from the expansion member (6) are heating pipes or ducts in order to compensate for the cooling of the gas mixture due to its expansion. In another particular implementation, the transfer circuit (3) presents a gas heater (7) placed downstream from the valve or the tap (12) and upstream from the expansion member (6) and the set of pipes or ducts forming the transfer circuit (3) are heating pipes or ducts.

(46) When the tap or the valve (11) of the solenoid valve type is open, the gas mixture comprising CO.sub.2 and i-C.sub.3F.sub.7CN then fills the casing (1). During this filling step, the air initially present in the casing (1) is expelled by the gas mixture. In a variant, before the filling step, void is made in the inside volume of the casing (1) (0-0.1 kPa). The system forming the object of the present invention can also be used to add additional gas into the casing (1) on site.

(47) FIGS. 1 to 4 show four installations of the invention, on the following principles: heating the container (2) of the transport container or bottle type, containing the mixture of CO.sub.2 and i-C.sub.3CF.sub.7CN in the pressurized liquefied state until it reaches the critical temperature of the mixture by using the external heater member (4) of the external heater belt type (FIGS. 1 and 2) or the internal heater member (5) of the internal heater resistor type combined with a thermal insulation system (10) of the thermally insulating housing type surrounding the container (2) (FIGS. 3 and 4); once the CO.sub.2 and i-C.sub.3F.sub.7CN mixture is in gaseous form and in a supercritical state, opening the valve or the tap (12) isolating the container (2) from the transfer circuit (3), so that the gas mixture is introduced into the transfer circuit (3); passing the gas mixture through a gas heater (7) of the CO.sub.2 heater type in order to compensate for the cooling of the gas mixture; passing the gas mixture through an expander (6); transferring the gas mixture to the transfer circuit (3) via heating pipes so as to compensate for cooling of the gas by Joule-Thomson (expansion) effect; the transfer circuit (3) contains a solenoid valve (11) controlled by measuring the critical temperature of the gas mixture at the container (2) (for FIGS. 1 and 3) or by directly measuring the ratio between i-C.sub.3F.sub.7CN and CO.sub.2 (for FIGS. 2 and 4). The solenoid valve (11) is opened to allow the casing of the equipment (1) to be filled only when the temperature of the mixture is at least equal to the critical temperature of the mixture, or the ratio is equal to the target value; and the heating power is controlled by measuring the temperature of the gas mixture in the container (2) at the measuring means (9) (for FIGS. 1 and 3) or by directly measuring the ratio between i-C.sub.3F.sub.7CN and CO.sub.2 at the measuring means (8) (for FIGS. 2 and 4).

(48) The installations of FIGS. 1 to 4 contain temperature safety features so that the gas mixture never reaches 65 C.

(49) In addition, the installations of FIGS. 1 to 4 contain a rupture disk rated at 120 bars in order to avoid an overpressure in the container (2) of the bottle or transport container type in the event of any failure of the heat regulation system.

(50) In the FIG. 1 installation, the heater system (4) is outside the container (2) (transport container or bottle). Heating power regulation is conditioned by measuring the temperature of the gas mixture in the container (2) at the measurement means (9).

(51) The FIG. 2 installation is a variant of the FIG. 1 installation in which regulation of the heating power is conditioned by directly measuring the ratio between i-C.sub.3F.sub.7CN and CO.sub.2 at the measurement means (8).

(52) In the FIG. 3 installation, the heating system (5) is inside the container (2) (transport container or bottle) that is combined with a thermal-insulation system (10) of the thermally insulating housing type surrounding the container (2). Heating power regulation is conditioned by measuring the temperature of the gas mixture in the container (2) at the measurement means (9).

(53) The FIG. 4 installation is a variant of the FIG. 3 installation in which heating power regulation is conditioned by directly measuring the ratio between i-C.sub.3F.sub.7CN and CO.sub.2 at the measurement means (8).