EP2989702A1 - Procédé pour fournir un composant de réduction de contamination à un appareil électrique - Google Patents

Procédé pour fournir un composant de réduction de contamination à un appareil électrique

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Publication number
EP2989702A1
EP2989702A1 EP14718095.4A EP14718095A EP2989702A1 EP 2989702 A1 EP2989702 A1 EP 2989702A1 EP 14718095 A EP14718095 A EP 14718095A EP 2989702 A1 EP2989702 A1 EP 2989702A1
Authority
EP
European Patent Office
Prior art keywords
contamination
electrical apparatus
reducing component
carbon dioxide
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14718095.4A
Other languages
German (de)
English (en)
Inventor
Denis Tehlar
Navid Mahdizadeh
Patrick Stoller
Thomas Alfred Paul
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ABB Technology AG
Original Assignee
ABB Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ABB Technology AG filed Critical ABB Technology AG
Priority to EP14718095.4A priority Critical patent/EP2989702A1/fr
Priority claimed from PCT/EP2014/057803 external-priority patent/WO2014173776A1/fr
Publication of EP2989702A1 publication Critical patent/EP2989702A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02B—BOARDS, SUBSTATIONS OR SWITCHING ARRANGEMENTS FOR THE SUPPLY OR DISTRIBUTION OF ELECTRIC POWER
    • H02B13/00—Arrangement of switchgear in which switches are enclosed in, or structurally associated with, a casing, e.g. cubicle
    • H02B13/02—Arrangement of switchgear in which switches are enclosed in, or structurally associated with, a casing, e.g. cubicle with metal casing
    • H02B13/035—Gas-insulated switchgear
    • H02B13/055—Features relating to the gas
    • 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
    • H01H2033/566—Avoiding the use of SF6
    • 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
    • H01H2033/567—Detection of decomposition products of the gas
    • 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
    • H01H33/561—Gas reservoirs composed of different independent pressurised compartments put in communication only after their assemblage
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02B—BOARDS, SUBSTATIONS OR SWITCHING ARRANGEMENTS FOR THE SUPPLY OR DISTRIBUTION OF ELECTRIC POWER
    • H02B3/00—Apparatus specially adapted for the manufacture, assembly, or maintenance of boards or switchgear

Definitions

  • the present invention relates to a process for providing a contamination-reducing component in an electrical apparatus, according to the preamble of claim 1.
  • the present invention relates to an electrical apparatus, according to the preamble of claim 22, as well as to a process for determining a change in the sorption capacity, particularly adsorption capacity, of a contamina- tion-reducing component in an electrical apparatus.
  • the present invention relates to a process according to claim 32, particularly claims 33 and 34.
  • Dielectric insulation media in liquid or gaseous state are conventionally applied for the insulation of an electrical component in a wide variety of electrical apparatuses, such as for example switchgears, gas-insulated substations (GIS) , gas- insulated lines (GIL), transformers, or other.
  • switchgears gas-insulated substations (GIS)
  • GIS gas-insulated substations
  • GIL gas- insulated lines
  • transformers or other.
  • the electrical component is arranged in a gas-tight housing, which defines an insulating space, said insulating space comprising an insulation medium and separating the housing from the electrical component without letting electrical current to pass through the insulating space.
  • the insulating medium For interrupting the current in high voltage switchgear, the insulating medium further functions as an arc extinction medium.
  • an insulation medium comprising or consisting of carbon dioxide (C0 2 ) has been shown to be highly advantageous, due its high arc extinction capability. Further, carbon dioxide has a fairly low impact on the environment. Considering environmental friendliness, it is, thus, a suitable substitute for SF 6 (sulphur hexafluoride) , which has commonly been used as a dielectric insulation medium, but which is known to have a high Global Warming Potential (GWP) .
  • SF 6 sulfur hexafluoride
  • the known adsorbers have the disadvantage that not only moisture and - as the case may be - decomposition products are adsorbed, but also carbon dioxide and - in case of a carbon dioxide comprising mixture - potentially other constituents of the insulation medium.
  • an initial adsorption of constituents of the insulation medium thus takes place, which has an unwanted effect on the total pressure and on the composition of the insulation medium, affecting both the insulation and arc- extinguishing performance of the medium.
  • the gas compartment is refilled after initial adsorption has taken place.
  • This has the disadvantage of a relatively long waiting period, namely the period between the placing of the adsorber into the insulating space and the time until when initial adsorption is complete, before refilling can be performed.
  • both of the above described possible strategies require knowledge of the adsorption behaviour of the adsorber towards the constituents of the mixture in order to attain the desired composition of the insulation medium.
  • carbon dioxide has higher adsorption energy towards the adsorber than the other constituents of the gas mixture.
  • the relative amount of carbon dioxide in proximity to the adsorber is reduced immediately after the placing of the adsorber into the insulating space.
  • the amount of adsorber placed in the insulating space can be reduced to a minimum.
  • the deter ⁇ mination of the required minimum for each separate insulating space is not only time-consuming. It also bears the risk that during assembly of the electrical apparatus the respective adsorbers are not correctly attributed to their compartments and are thus placed in the wrong insulating space.
  • EP-A-2 445 068 describes a process in which a high-voltage unit and a zeolite case are arranged at predetermined positions inside the closed vessel of an electrical apparatus, and the closed vessel is evacuated. Subsequently, C0 2 gas is enclosed with high pressure in the closed vessel to adsorb C0 2 gas to the zeolite. After that, the predetermined insulation gas is filled into the closed vessel.
  • EP-A-2 445 068 The process proposed in EP-A-2 445 068 is, however, relatively laborious, since it requires a large space to be evacuated and then filled with C0 2 for the adsorption to take place, before the predetermined insulation gas is filled in the vessel. This is not only time-consuming, but requires relatively sophisticated C0 2 storage tanks and filling means given the high amount of C0 2 to be filled in the vessel for adsorbing C0 2 to the zeolite.
  • the problem of the present invention is to provide a process for providing a contamination-reducing component to an electrical apparatus in a manner to maintain the insulating performance of the insulation medium contained therein on a high level, said process being efficient, fast and economic.
  • the problem is solved by the subject-matter of the independent claims, and in particular by the process according to claim 1.
  • Preferred embodiments of the process of the invention are given in the dependent claims and in claim combinations.
  • the present invention relates to a process for providing a contamination-reducing component to an electrical apparatus, the electrical apparatus comprising a housing enclosing an insulating space and an electrical component arranged in the insulating space, the insulating space comprising an insulation medium which comprises or consists of carbon dioxide.
  • the process comprises the steps of:
  • a pre-saturation gas comprising or consisting of carbon dioxide into the pre-saturation space such as to allow the contamination-reducing component placed in the pre-saturation space to sorb, in particular adsorb, carbon dioxide, and
  • the electrical apparatus is provided with a contamination-reducing component to reduce or eliminate the presence of contaminants, in particular moisture (i.e. water) and/or decomposition products and/or any other component the presence of which is not desired.
  • a contamination-reducing component to reduce or eliminate the presence of contaminants, in particular moisture (i.e. water) and/or decomposition products and/or any other component the presence of which is not desired.
  • the contamination-reducing component can be a moisture-reducing component.
  • the reduction or elimination of moisture is of particular relevance, since water can - apart from reducing insulation performance - also lead to corrosion of the electrical apparatus, in particular of the housing or the electrical component ( s ) . Further, water can open reaction pathways for the formation of toxic and/or corrosive decomposition products, in particular resulting from partial discharge or arcing in the presence of high moisture content. This is of particular relevance when using an insulation medium which comprises an organofluorine compound, since one decomposition product of the organofluorine compound is hydrogen fluoride (HF) , which is highly corrosive and extremely toxic.
  • HF hydrogen fluoride
  • housing as used in the context of the present invention is to be understood broadly as any at least approximately closed system.
  • the term “housing” can encompass a plurality of chambers interconnected with each other. More particularly in embodiments, “housing” can encompass a chamber, which encloses the insulating space, and a recycling system, the chamber being interconnected with the recycling system through which the insulation medium is removed, processed (e.g. cleaned) and reintroduced into the insulating space.
  • housing can comprise a chamber, which encloses the insulating space, and a pre-treatment room, the chamber being interconnected with the pre-treatment room for pre-treating the insulation medium prior to introduction into the insulating space of the chamber.
  • the "pre-saturation vessel" is separate from the “housing", i.e. the pre-saturation space is a different enclosed space than the insulating space.
  • sorption as used in the context of the present invention is to be interpreted broadly and encompasses any physical or chemical process by which a first substance, i.e. the sorbate, is attached to a second substance, i.e. the sorbent.
  • “sorption” encompasses any binding, capturing or generally immobilization of the sorbate by any mechanism, such as e.g. by physisorption and/or chemisorption.
  • the term “sorption” relates to "adsorption”.
  • the contamination-reducing component is allowed to adsorb carbon dioxide in step c) and the contamination-reducing component with the adsorbed carbon dioxide is transferred to the electrical apparatus in step d) .
  • adsorption or "adsorbed” as used in the context of the present invention shall encompass any type of adsorption, such as, e.g., physisorption and/or chemisorption. According to an embodiment, the steps of the process are consecutive steps.
  • the contamination-reducing component is in step d) transferred into the insulating space of the electrical apparatus.
  • the contamination-reducing component in particular the adsorber, might also be placed elsewhere in the electrical apparatus, e.g. as part of a filter of a recycling system through which the insulation medium is removed from the insulating space, processed (e.g. cleaned) and reintroduced into the insulating space.
  • the placing of the contamination-reducing component into the insulating space interferes with the composition of the insulation medium only to a minor degree or not at all. This is explained by the fact that after pre-saturation, generally, most of the sorption sites, specifically the adsorption sites, of the contamination-reducing component are occupied by the constituents of the pre-saturation gas, and particularly by carbon dioxide.
  • the contamination-reducing component when placing the contamination-reducing component into the insulating space in the manner according to the present invention, there is no significant change in the total pressure of the insulation medium or no change at all. Also - in case of the insulation medium being a gas mixture - there is no significant change in the gas mixture composition (and, thus, in the ratio of the respective constituents) or no change at all.
  • the placing of the contamination-reducing component into the insulating space does not interfere with the dielectric performance and - in the respective applications - the switching capabilities of the electrical apparatus.
  • a contamination-reducing component of relatively large size and/or amount can be used which is able to adsorb large amounts of moisture and/or decomposition products.
  • a long operating time of the apparatus can be achieved before replacement of the contamination-reducing component becomes necessary.
  • the size and/or amount of the contamination- reducing components to be used for the different insulating spaces can be standardized to the largest insulating space, thus contributing to a simple and safe assembly of the electrical apparatus.
  • pre-saturation of the contamination-reducing component in a vessel other than the insulating space of the electrical apparatus can be performed in a simple manner without the risk of release of the adsorbed carbon dioxide during the transfer into the insulating space. This is due to a strong hysteresis between adsorption and release of carbon dioxide.
  • carbon dioxide can remain adsorbed even in the case that during the transfer according to step d) the contamination-reducing component is exposed to an environment having a number density of carbon dioxide lower than in the pre-saturation space. This is in particular the case, when a low temperature is maintained during the transfer.
  • the contamination-reducing component with the carbon dioxide sorbed, specifically adsorbed is, prior to or during step d) , taken out of the pre-saturation space.
  • the contamination-reducing component is taken out of the pre- saturation space before being placed into the insulating space of the electrical apparatus.
  • the contamination-reducing component is packaged into a container, in particular a bag, prior to being taken out of the pre- saturation space, said container being moveable with regard to the pre-saturation vessel and the electrical apparatus.
  • the contamination-reducing component can be stored over a long period of time without losing carbon dioxide adsorbed thereto and thus its desired quality.
  • the container is closeable in a gas- tight manner.
  • a well-defined gas composition and pressure can be provided in the container, which allows to avoid the risk of the contamination-reducing component adsorbing unwanted contaminants and/or releasing carbon dioxide during the transfer.
  • the packaging into a container is, however, not essential due to the hysteresis between carbon dioxide adsorption and release described above. This holds true especially in the case where the placing of the contamination-reducing component into the insulating space is performed shortly after it has been taken out of the pre- saturation space.
  • the contamination-reducing component with the carbon dioxide adsorbed is, prior or during step d) , taken out of the pre- saturation space, it can - depending on the circumstances - also be preferred to transfer the pre-saturation vessel together with the contamination-reducing component placed in the pre-saturation space to the electrical apparatus and to open the pre-saturation vessel after step d) .
  • the contamination-reducing component is only exposed to the pre- saturation space and the insulating space, the gas composition and pressure in both spaces being well defined. There is thus no risk of the contamination-reducing component adsorbing unwanted contaminants and/or releasing carbon dioxide in this embodiment .
  • the contamination-reducing component is a molecular sieve, more preferably a zeolite, i.e. a micro-porous aluminosilicate mineral that has undergone cation exchange to achieve a desired pore size.
  • a zeolite i.e. a micro-porous aluminosilicate mineral that has undergone cation exchange to achieve a desired pore size.
  • the molecular sieve has an average pore size greater than 2 A, preferably greater than 4 A, more preferably greater than 5 A, even more preferably greater than 6 A, and most preferably greater than 8 A.
  • the molecular sieve has a pore size from 3 A to 13 A, preferably from 5 A to 13 A, more preferably from 6 A to 13 A or from 6 A to 12 A, even more preferably from 7 A to 11 A, most preferably from 9 A to 11 A.
  • a respective molecular sieve has been found to have a particularly high adsorption capacity not only for water, but also for e.g. hydrogen fluoride, a potential decomposition product of an insulation medium comprising an organofluorine compound .
  • Suitable zeolites include e.g. ZEOCHEM® molecular sieve 5A (having a pore size of 5 A) and ZEOCHEM® molecular sieve 13X (having a pore size of 9 A) .
  • the term "adsorption” or “adsorbed” encompasses both physisorption and/or chemisorption .
  • Physisorption can, in particular, be determined or be influenced by the relationship between the size of molecules of the insulation medium and the pore size of the molecular sieve.
  • Chemisorption can, in parti- cular, be determined or influenced by chemical interactions between molecules of the insulation medium and the molecular sieve .
  • adsorption capacity refers to the number of molecules adsorbed (in mole) to the mass of the contamination-reducing component, particularly the molecular sieve, more particularly the zeolite (in kg) .
  • sorption capacity refers to the number of molecules sorbed (in mole) to the mass of the contamination-reducing component, particularly the molecular sieve, more particularly the zeolite (in kg) .
  • the contamination- reducing component is cooled prior to step c) and/or during step c) and/or prior to step d) and/or during step d) , preferably to a temperature below 10°C, more preferably below 0°C, most preferably below -20°C.
  • the contamination-reducing component is preferably cooled, prior to step c) and/or during step c) and/or prior to step d) and/or during step d) , to a temperature which is at most 5°C above, in particular equal to or lower than, the minimum operating temperature of the electrical apparatus which is to be provided with the contamination-reducing component .
  • the number density of carbon dioxide in the pre- saturation space is higher than the number density of carbon dioxide in air at atmospheric pressure.
  • the number density of carbon dioxide in the pre- saturation space is at least approximately equal to the maximum expected number density of carbon dioxide in the insulating space of the electrical apparatus.
  • the partial pressure of carbon dioxide in the pre-saturation space at room temperature is higher than 1 bar, preferably higher than 3 bar, more preferably higher than 5 bar, and most preferably higher than 7 bar.
  • the volume of the pre-saturation space is slightly greater than the volume of the molecular sieve.
  • the insulation medium and the pre-saturation gas have at least approximately the same composition.
  • the insulation medium and the pre-saturation gas have at least approximately the same composition.
  • the insulation medium can consist or essentially consist of carbon dioxide.
  • carbon dioxide is thus the sole component of the insulation medium.
  • the insulation medium can comprise carbon dioxide apart from other constituents, and, thus, form a gas mixture, which is an often preferred embodiment. It is particularly preferred that the insulation medium comprises air or at least one air component, in particular oxygen and/or nitrogen, apart from carbon dioxide.
  • the insulation medium is a gas mixture comprising carbon dioxide and oxygen.
  • the ratio of the amount of carbon dioxide to the amount of oxygen thereby can range from 50:50 to 100:1.
  • the ratio of the amount of carbon dioxide to the amount of oxygen ranges from 80:20 to 95:5, more preferably from 85:15 to 92:8, even more preferably from 87:13 to less than 90:10, and in particular is about 89:11.
  • oxygen being present in a molar fraction of at least 5% allows soot formation to be prevented even after repeated current interruption events with high current arcing.
  • oxygen being present in a molar fraction of at most 20%, more particularly of at most 15% reduces the risk of degradation of the material of the electrical apparatus by oxidation.
  • the advantageous effects of a contamination-reducing component are particularly pronounced in embodiments in which the insulation medium comprises an organofluorine compound, since thereby the generation of harmful decomposition products, such as hydrogen fluoride, which in the absence of a contamination-reducing component might occur, can efficiently be avoided.
  • the organofluorine compound is selected from the group consisting of fluoroethers , in particular hydrofluoro- monoethers, fluoroketones , in particular perfluoroketones , and fluoroolefins , in particular hydrofluoroolefins , and mixtures thereof .
  • fluoroethers in particular hydrofluoro- monoethers
  • fluoroketones in particular perfluoroketones
  • fluoroolefins in particular hydrofluoroolefins
  • These classes of compounds have been found to have very high insulation capabilities, in particular a high dielectric strength (or breakdown field strength) , and at the same time a low GWP and low
  • the sorption of organofluorine compounds due to the pre-saturation of the contamination-reducing component, i.e. the sorbing of carbon dioxide in the pre- saturation space, the sorption of organofluorine compounds, particularly of a fluoroketone containing from 4 to 12 carbon atoms, specifically exactly 5 carbon atoms, can be efficiently avoided by the process of the present invention. There is thus no loss in the partial pressure of the organofluorine compound due to the transfer of the contamination-reducing component to the electrical apparatus according to step d) .
  • the invention encompasses both embodiments in which the dielectric insulation gas comprises either one of a fluoro- ether, in particular a hydrofluoromonoether, a fluoroketone and a fluoroolefin, in particular a hydrofluoroolefin, as well as embodiments in which it comprises a mixture of at least two of these compounds.
  • fluoroether as used in the context of the present invention encompasses both fluoropolyethers (e.g. galden) and fluoromonoethers and encompasses both perfluoroethers , i.e. fully fluorinated ethers, and hydrofluoroethers , i.e. ethers that are only partially fluorinated.
  • fluoroether further encompasses saturated compounds as well as unsaturated compounds, i.e. compounds including double and/or triple bonds between carbon atoms.
  • the at least partially fluorinated alkyl chains attached to the oxygen atom of the fluoroether can, independently of each other, be linear or branched.
  • fluoroether further encompasses both non-cyclic and cyclic ethers.
  • the two alkyl chains attached to the oxygen atom can optionally form a ring.
  • the term encompasses fluorooxiranes .
  • the organofluorine compound according to the present invention is a perfluorooxirane or a hydrofluorooxirane, more specifically a perfluorooxirane or hydrofluorooxirane comprising from three to fifteen carbon atoms.
  • the dielectric insulation gas comprises a hydrofluoromonoether containing at least three carbon atoms.
  • these hydrofluoromonoethers are chemically and thermally stable up to temperatures above 140°C. They are further non-toxic or have a low toxicity level. In addition, they are non-corrosive and non-explosive.
  • hydrofluoromonoether refers to a compound having one and only one ether group, said ether group linking two alkyl groups, which can be, independently from each other, linear or branched, and which can optionally form a ring.
  • the compound is thus in clear contrast to the compounds disclosed in e.g. US-B-7128133, which relates to the use of compounds containing two ether groups, i.e. hydrofluorodiethers , in heat-transfer fluids.
  • hydrofluoromonoether as used herein is further to be understood such that the monoether is partially hydrogenated and partially fluorinated. It is further to be understood such that it may comprise a mixture of differently structured hydrofluoromonoethers .
  • structurally different shall broadly encompass any difference in sum formula or structural formula of the hydrofluoromonoether .
  • hydrofluoromonoethers containing at least three carbon atoms have been found to have a relatively high dielectric strength. Specifically, the ratio of the dielectric strength of the hydrofluoromonoethers according to the present invention to the dielectric strength of SF 6 is greater than about 0.4.
  • the GWP of the hydrofluoromonoethers is low. Preferably, the GWP is less than l'OOO over 100 years, more specifically less than 700 over 100 years.
  • the hydrofluoromonoethers mentioned herein have a relatively low atmospheric lifetime and in addition are devoid of halogen atoms that play a role in the ozone destruction catalytic cycle, namely CI, Br or I.
  • ODP Ozone Depletion Potential
  • the hydrofluoromonoether contains exactly three or four or five or six carbon atoms, in particular exactly three or four carbon atoms, most preferably exactly three carbon atoms.
  • the hydrofluoromonoether is thus at least one compound selected from the group consisting of the compounds defined by the following structural formulae in which a part of the hydrogen atoms is each substituted by a fluorine atom:
  • the ratio of the number of fluorine atoms to the total number of fluorine and hydrogen atoms, here briefly called "F-rate", of the hydrofluoromonoether is at least 5:8. It has been found that compounds falling within this definition are generally non-flammable and thus result in an insulation medium complying with highest safety requirements. Thus, safety requirements of the electrical insulator and the method of its production can readily be fulfilled by using a corresponding hydrofluoromonoether .
  • the ratio of the number of fluorine atoms to the number of carbon atoms ranges from 1.5:1 to 2:1.
  • Such compounds generally have a GWP of less than l'OOO over 100 years and are thus very environment-friendly. It is particularly preferred that the hydrofluoromonoether has a GWP of less than 700 over 100 years.
  • exactly one of c and f in the general structure (0) is 0.
  • the corresponding grouping of fluorines on one side of the ether linkage, with the other side remaining unsubstituted, is called "segregation". Segregation has been found to reduce the boiling point compared to unsegregated compounds of the same chain length. This feature is thus of particular interest, because compounds with longer chain lengths allowing for higher dielectric strength can be used without risk of liquefaction under operational conditions.
  • the hydrofluoromonoether is selected from the group consisting of pentafluoro-ethyl-methyl ether (CH 3 -0- CF 2 CF 3 ) and 2 , 2 , 2-trifluoroethyl-trifluoromethyl ether (CF 3 -0-CH 2 CF 3 ) .
  • Pentafluoro-ethyl-methyl ether has a boiling point of +5.25°C and a GWP of 697 over 100 years, the F-rate being 0.625, while 2 , 2 , 2-trifluoroethyl-trifluoromethyl ether has a boiling point of +11°C and a GWP of 487 over 100 years, the F-rate being 0.75. They both have an ODP of 0 and are thus environmentally fully acceptable.
  • pentafluoro-ethyl-methyl ether has been found to be thermally stable at a temperature of 175°C for 30 days and therefore to be fully suitable for the operational conditions given in the apparatus. Since thermal stability studies of hydrofluoromonoethers of higher molecular weight have shown that ethers containing fully hydrogenated methyl or ethyl groups have a lower thermal stability compared to those having partially hydrogenated groups, it can be assumed that the thermal stability of 2 , 2 , 2-trifluoroethyl-trifluoromethyl ether is even higher.
  • hydrofluoromonoethers and in particular pentafluoro-ethyl- methyl ether as well as 2 , 2 , 2-trifluoroethyl-trifluoromethyl ether, have a lethal concentration LC 50 of higher than 10' 000 ppm, rendering them suitable also from a toxicological point of view.
  • hydrofluoromonoethers mentioned have a higher dielectric strength than air.
  • pentafluoro-ethyl-methyl ether at 1 bar has a dielectric strength about 2.4 times higher than that of air at 1 bar.
  • the hydro- fluoromonoethers mentioned are normally in the gaseous state at operational conditions.
  • a dielectric insulation medium in which every component is in the gaseous state at operational condi ⁇ tions of the apparatus can be achieved, which is advantageous.
  • the dielectric insulation gas comprises a fluoroketone containing from four to twelve carbon atoms.
  • fluoroketone as used in this application shall be interpreted broadly and shall encompass both perfluoroketones and hydrofluoroketones , and shall further encompass both saturated compounds and unsaturated compounds, i.e. compounds including double and/or triple bonds between carbon atoms.
  • the at least partially fluorinated alkyl chain of the fluoro- ketones can be linear or branched, or can form a ring, which optionally is substituted by one or more alkyl groups.
  • the fluoroketone is a perfluoroketone .
  • the fluoroketone has a branched alkyl chain, in particular an at least partially fluorinated alkyl chain.
  • the fluoroketone is a fully saturated compound.
  • the present invention also relates to a dielectric insulation medium comprising a fluoroketone having from 4 to 12 carbon atoms, the at least partially fluorinated alkyl chain of the fluoroketone forming a ring, which is optionally substituted by one or more alkyl groups.
  • a dielectric insulation medium can comprise a background gas, in particular selected from the group consisting of: air, air component, nitrogen, oxygen, nitrogen oxides, carbon dioxide, and mixtures thereof.
  • the invention relates to an electrical apparatus comprising such a dielectric insulation medium.
  • the fluoroketone is at least one compound selected from the group consisting of the compounds defined by the following structural formulae in which at least one hydrogen atom is substituted with a fluorine atom:
  • the present invention relates to a dielectric insulation medium comprising a fluoroketone having exactly 5 carbon atoms and having a structural formula according to (la) to (Ii) .
  • dielectric insulation medium can comprise a background gas, in particular selected from the group consisting of: air, air component, nitrogen, oxygen, nitrogen oxides, carbon dioxide, and mixtures thereof.
  • an electrical apparatus comprising such a dielectric insulation medium is disclosed.
  • Fluoroketones containing five or more carbon atoms are further advantageous, because they are generally non-toxic with outstanding margins for human safety. This is in contrast to fluoroketones having less than four carbon atoms, such as hexafluoroacetone (or hexafluoropropanone) , which are toxic and very reactive.
  • fluoroketones containing exactly five carbon atoms herein briefly named fluoroketones a)
  • fluoroketones containing exactly six carbon atoms are thermally stable up to 500°C.
  • the fluoroketones in particular fluoroketones a) , having a branched alkyl chain are preferred, because their boiling points are lower than the boiling points of the corresponding compounds (i.e. compounds with same molecular formula) having a straight alkyl chain.
  • the fluoroketone a) is a perfluoroketone, in particular has the molecular formula C 5 F 10 O, i.e. is fully saturated without double or triple bonds between carbon atoms.
  • the fluoroketone a) may more preferably be selected from the group consisting of 1,1,1,3,4,4,4- heptafluoro-3- (trifluoromethyl) butan-2-one (also named decafluoro-2-methylbutan-3-one) , 1,1,1,3,3,4,4,5,5, 5-deca- fluoropentan-2-one, 1,1,1,2,2,4,4,5,5, 5-decafluoropentan-3-one and octafluorocylcopentanone, and most preferably is 1,1,1,3,4,4, 4 -heptafluoro-3- (trifluoromethyl) butan-2 -one .
  • 1,1,1,3,4,4, 4 -heptafluoro-3- (trifluoromethyl) butan-2 -one can be represented by the following structural formula (I) :
  • even higher insulation capabilities can be achieved by combining the mixture of different fluoroketone components.
  • a fluoroketone containing exactly five carbon atoms, as described above and here briefly called fluoroketone a) and a fluoroketone containing exactly six carbon atoms or exactly seven carbon atoms, here briefly named fluoroketone c) , can favourably be part of the dielectric insulation at the same time.
  • an insulation medium can be achieved having more than one fluoroketone, each contributing by itself to the dielectric strength of the insulation medium.
  • the further fluoroketone c) is at least one compound selected from the group consisting of the compounds defined by the following structural formulae in which at least one hydrogen atom is substituted with a fluorine atom:
  • any fluoroketone having exactly 6 carbon atoms in which the at least partially fluorinated alkyl chain of the fluoroketone forms a ring, which is substituted by one or more alkyl groups (Ilh); and/or is at least one compound selected from the group consisting of the compounds defined by the following structural formulae in which at least one hydrogen atom is substituted with a fluorine atom:
  • ( ⁇ ) for example dodecafluoro-cycloheptanone, as well as any fluoroketone having exactly 7 carbon atoms, in which the at least partially fluorinated alkyl chain of the fluoroketone forms a ring, which is substituted by one or more alkyl groups (IIIo) .
  • the present invention relates to a dielectric insulation medium comprising a fluoroketone having exactly 6 carbon atoms, in which the at least partially fluorinated alkyl chain of the fluoroketone forms a ring, optionally substituted by one or more alkyl groups.
  • a dielectric insulation medium can comprise a background gas, in particular selected from the group consisting of: air, air component, nitrogen, oxygen, nitrogen oxides, carbon dioxide, and mixtures thereof.
  • an electrical apparatus comprising such a dielectric insulation medium is disclosed.
  • the present invention relates to a dielectric insulation medium comprising a fluoroketone having exactly 7 carbon atoms, in which the at least partially fluorinated alkyl chain of the fluoroketone forms a ring, optionally substituted by one or more alkyl groups.
  • a dielectric insulation medium can comprise a background gas, in particular selected from the group consisting of: air, air component, nitrogen, oxygen, nitrogen oxides, carbon dioxide, and mixtures thereof.
  • an electrical apparatus comprising such a dielectric insulation medium is disclosed.
  • the present invention encompasses each compound or each combination of compounds selected from the group consisting of the compounds according to structural formulae (Oa) to (Or) , (la) to (Ii), (Ha) to (Ilh), (Ilia) to (IIIo), and mixtures thereof .
  • fluoroketone c a fluoroketone containing exactly six carbon atoms (falling under the designation “fluoroketone c) " mentioned above) may be preferred; such a fluoroketone is non ⁇ toxic, with outstanding margins for human safety.
  • fluoroketone c) alike fluoroketone a) , is a perfluoroketone, and/or has a branched alkyl chain, in particular an at least partially fluorinated alkyl chain, and/or the fluoroketone c) contains fully saturated compounds.
  • the fluoroketone c) has the molecular formula C 6 Fi 2 0, i.e. is fully saturated without double or triple bonds between carbon atoms.
  • the fluoroketone c) can be selected from the group consisting of 1,1,1,2,4,4,5,5,5- nonafluoro-2- (trifluoromethyl) pentan-3-one (also named dodecafluoro-2-methylpentan-3-one) , 1,1,1,3,3,4,5,5,5- nonafluoro-4- (trifluoromethyl) pentan-2-one (also named dodecafluoro-4-methylpentan-2-one) , 1,1,1,3,4,4,5,5,5- nonafluoro-3- (trifluoromethyl) pentan-2-one (also named dodecafluoro-3-methylpentan-2-one) , 1,1,1,4,4, 4-hexafluoro-
  • the organofluorine compound can also be a fluoroolefin, in particular a hydrofluoroolefin . More particularly, the fluoroolefin or hydrofluorolefin, respectively, contains exactly three carbon atoms.
  • the hydrofluoroolefin is, thus, selected from the group consisting of: 1 , 1 , 1 , 2-tetrafluoropropene (HFO-1234yf) , 1,2,3,3- tetrafluoro-2-propene (HFO-1234yc) , 1, 1, 3, 3-tetrafluoro-2- propene (HFO-1234zc) , 1 , 1 , 1 , 3-tetrafluoro-2-propene (HFO- 1234ze) , 1 , 1 , 2 , 3-tetrafluoro-2-propene (HFO-1234ye) ,
  • the electrical apparatus comprises a housing enclosing an insulating space and an electrical component arranged in the insulating space, said insulating space containing an insulation medium which comprises or consists of carbon dioxide .
  • a molecular sieve having an average pore size in a range from 5 A to 13 A is arranged in the insulating space.
  • the purpose of the molecular sieve is primarily to reduce or eliminate the presence of contaminants, in particular moisture (i.e. water) and/or decomposition products and/or any other component the presence of which is not desired. Since the reduction or elimination of water is of particularly high relevance, the molecular sieve is preferably a water-reducing component. Any preferred feature described with regard to the process likewise applies to the electrical apparatus and vice versa.
  • the molecular sieve is thus preferably a zeolite.
  • the molecular sieve specifically the zeolite, has preferably an average pore size greater than 5 A, more preferably greater than 6 A, and most preferably greater than 8 A.
  • the molecular sieve in particular the zeolite, according to the present invention has a very high adsorption capacity towards water and decomposition products, specifically hydrogen fluoride.
  • the molecular sieve has an average pore size from 6 A to 13 A or from 6 A to 12 A, even more preferably from 7 A to 11 A, most preferably from 9 A to 11 A.
  • the molecular sieve is preferably arranged in the pre- saturation space of a pre-saturation vessel as defined above, said pre-saturation vessel being in its open state.
  • the insulation medium comprises, apart from carbon dioxide, an additional background gas, in particular selected from the group consisting of: air, air component, nitrogen, oxygen, nitrogen oxides, and mixtures thereof.
  • the ratio of the amount of carbon dioxide to the amount of oxygen ranges from 50:50 to 100:1, preferably from 80:20 to 95:5, more preferably from 85:15 to 92:8, even more preferably from 87:13 to less than 90:10, and most preferably is about 89:11, as has already been described in the context of the process defined above.
  • the insulation medium further comprises an organofluorine compound, preferably an organofluorine compound selected from the group consisting of: fluoroethers including fluoropolyethers and fluoromonoethers , in particular hydro- fluoromonoethers ; fluoroketones , in particular perfluoro- ketones; fluoroolefins , in particular hydrofluoroolefins ; and mixtures thereof.
  • organofluorine compound preferably an organofluorine compound selected from the group consisting of: fluoroethers including fluoropolyethers and fluoromonoethers , in particular hydro- fluoromonoethers ; fluoroketones , in particular perfluoro- ketones; fluoroolefins , in particular hydrofluoroolefins ; and mixtures thereof.
  • the electrical component of the electrical apparatus is a high voltage or medium voltage unit, since in these the task of controlling and delimiting the moisture content is of high importance and the advantages achieved by the present invention are, thus, of particular relevance .
  • the electrical apparatus can be a switchgear, in particular a gas-insulated switchgear (GIS) or a part and/or component thereof, a busbar, a bushing, a cable, a gas- insulated cable, a cable joint, a gas-insulated line (GIL), a transformer, a current transformer, a voltage transformer, a surge arrester, an earthing switch, a disconnector, a combined disconnector and earthing switch, a load-break switch, a circuit breaker, a convertor building and/or any type of gas- insulated switch.
  • GIS gas-insulated switchgear
  • GIL gas-insulated line
  • the present invention further relates to a process for determining a change in the adsorption capacity of a contamination-reducing component in an electrical apparatus.
  • the electrical apparatus comprises a housing enclosing an insulating space and an electrical component arranged in the insulating space.
  • the insulating space comprises an insulation medium which comprises or consists of carbon dioxide.
  • the present invention also relates to a process for determining and/or monitoring the sorption capacity, in particular adsorption capacity, of a contamination-reducing component in an electrical apparatus, said electrical apparatus comprising a housing enclosing an insulating space and an electrical component arranged in the insulating space, said insulating space comprising an insulation medium which comprises or consists of carbon dioxide .
  • the process comprises the steps of:
  • step III) determining from the amount determined in step II) the amount of the remaining sorbates in the contamination- reducing component, in particular water and/or decomposition products, and thus the sorption capacity of the contamination-reducing component.
  • the present invention relates to process for determining the sorption capacity of contamination reducing component in an electrical apparatus, said electrical apparatus comprising a housing enclosing an insulating space and an electrical component arranged in the insulating space, said insulating space comprising an insulation medium which comprises or consists of carbon dioxide.
  • the process comprises the steps of:
  • a contamination-reducing component in particular a molecular sieve
  • step D) determining from the amount determined in step C) the amount of the remaining sorbates (or adsorbates) in the contamination-reducing component, in particular water and/or decomposition products, and thus the sorption capacity (or adsorption capacity, respectively) of the contamination-reducing component .
  • the term "adsorbate” as used in the context of the present invention relates to a substance adsorbed to the contamination-reducing agent.
  • at least one further substance or adsorbate can be adsorbed.
  • the expression “at least one adsorbate” is equivalent to the expression “at least one kind of adsorbate”.
  • the release according to step B) can, e.g., be induced by a temporary change in the temperature of the contamination- reducing component.
  • a heating coil can be used to temporarily heat up the contamination-reducing component to a temperature of, e.g., above 50°C.
  • a release of adsorbate can be induced by a displacement of the adsorbate from the adsorption sites using a displacement adsorbate of higher adsorption energy.
  • a release of sorbate can be induced by a displacement of the sorbate from the sorption sites using a displacement sorbate of higher sorption energy.
  • the determination of the amount of carbon dioxide can be quantitative or qualitative.
  • a qualitative determination is performed by comparing the total amount of adsorbate (or generally sorbate) released with the total amount of adsorbate (or generally sorbate) released from a "fresh" contamination-reducing component, i.e. a contamina- tion-reducing component to which - at least approximately - only carbon dioxide is adsorbed (or generally sorbed) .
  • the ratio of adsorbed (or generally sorbed) carbon dioxide to the total amount of adsorbate (or generally sorbate) can qualitatively be determined.
  • the amount of carbon dioxide released can be determined based on the determination of the total amount of adsorbate (or generally sorbate) released.
  • the process described above can thus comprise between step B) and step C) a further step ("step B'") of determining the total amount of adsorbate (or generally sorbate) released in step B) .
  • This total amount of adsorbate (or generally sorbate) released can be determined, e.g. by measuring the pressure change caused by the release of adsorbate (or generally sorbate) .
  • the change in weight of the contamination-reducing component caused by the release of adsorbate (or generally sorbate) can be determined.
  • the present invention further relates to a process for monitoring the sorption capacity, in particular adsorption capacity, of a contamination-reducing component in an electrical apparatus over time, said electrical apparatus comprising a housing enclosing an insulating space and an electrical component arranged in the insulating space, said insulating space comprising an insulation medium which comprises or consists of carbon dioxide.
  • This process comprises the steps of:
  • a contamination-reducing component in particular a moisture-reducing component, more particularly a molecular sieve, with carbon dioxide adsorbed (or generally sorbed) thereto,
  • step ⁇ ) determining from a change measured in step ⁇ ) the amount of carbon dioxide released from the contamination-reducing component, in particular the moisture-reducing component, more particularly the molecular sieve, over time, and ⁇ ) determining from the amount determined in step ⁇ ) the amount of water and/or decomposition products adsorbed (or generally sorbed) by the contamination-reducing component, in particular the moisture-reducing component, more particularly the molecular sieve, and thereby its adsorption capacity (or generally sorption capacity) over time.
  • the above defined processes are for determining and/or monitoring the sorption capacity.
  • the adsorbate is, thus, a sorbate, which is sorbed to the contamination-reducing component or moisture-reducing component, respectively, and in particular to the molecular sieve.
  • any of the above defined processes for determining and/or monitoring the sorption capacity, specifically the adsorption capacity, is carried out after the process for providing the contamination-reducing component to the electrical apparatus defined above.
  • the electrical apparatus is as defined in above. If the amount of carbon dioxide increases over time, this is a clear indication that adsorbed (generally sorbed) carbon dioxide is released due to a replacement by water adsorbing (generally sorbing) to the contamination-reducing component and that thus the contamination-reducing component is fully functional .
  • the process preferably comprises the further step of determining the amount of water in the insulating space over time, in particular in case that the amount of carbon dioxide in the insulating space remains stable or decreases over time.
  • a molecular sieve in particular a zeolite, having an average pore size in the range from 5 A to 13 A is particularly preferred for its high adsorption capacity towards water and decomposition products, such as hydrogen fluoride.
  • Table 1 listing the limit capacity, inter alia, of zeolite 5A (having an average pore size of 5 A) and zeolite 13X (having an average pore size of about 9 A) towards water and hydrogen fluoride (amongst other compounds) .
  • limit capacity means the maximum adsorption capacity of the contamination-reducing component or adsorbent, that is the maximum possible amount of the respective adsorbate (in mole) per weight of the contamination-reducing component or adsorbent (in kilogram) , at the temperature of maximum adsorption.
  • the limit capacity towards water is higher for the specific molecular sieves mentioned above than for activated alumina. Said molecular sieves also show a high adsorption capacity towards hydrogen fluoride.
  • the present invention is further illustrated by way of the following example.
  • a vessel enclosing a volume of 4.6 liter with zeolite 5A is provided.
  • the vessel is then filled with carbon dioxide to a partial pressure of 0.97 bar and the zeolite 5A is allowed to adsorb carbon dioxide, by which adsorption the carbon dioxide partial pressure drops to almost 0.7 bar.
  • water is injected.
  • the carbon dioxide partial pressure rapidly increases to 0.97 bar, i.e. the value prior to initial adsorption.
  • essentially all carbon dioxide adsorbed during initial adsorption is replaced by water adsorbing to the contamination-reducing component and is thus released .
  • FIG. 1 showing a purely schematic representation of an electrical apparatus according to the present invention, for example a switchgear, and
  • FIG. 2 showing a presaturation vessel according to embodiments of the present invention.
  • the electrical apparatus 1, more particularly the switchgear, shown in Fig. 1 comprises a housing 2 enclosing an insulating space 3 and an electrical component 4 arranged in the insulating space 3.
  • the insulating space 3 contains an insulation medium which comprises or consists of carbon dioxide.
  • Fig. 2 shows schematically a gas-tight closeable and openable presaturation vessel 6 providing a presaturation space 7 for receiving and presaturating with carbon dioxide the contamination-reducing component 5, in particular molecular sieve 5 and preferably zeolite 5.
  • the presaturation vessel 6 may be transferred into the electrical apparatus 1 and may be opened (in particular the component 5 may be removed from the vessel 6) therein in order to expose the contamination- reducing component 5 to the dielectric insulation medium of the electrical apparatus 1.
  • a container 8 or bag 8 may be present for transferring the presaturated contamination-reducing component 5 to the insulating space 3 of the electrical apparatus 1 and to bring it into gas-exchange contact with the dielectric insulation medium of the electrical apparatus 1.
  • sorption as used throughout this application is to be interpreted broadly and encompasses any physical or chemical process by which a first substance, i.e. the sorbate, is attached to a second substance, i.e. the sorbent. In particular, it encompasses any binding, capturing or immobilization of the sorbate, for example by physisorption and/or chemisorption .
  • the term “sorption” relates to “adsorption”.
  • the terms “sorbed”, “sorbate” and “sorbent” relates to the “adsorbed”, “adsorbate” and “adsorbent”, respectively.
  • sorption can also relate to “absorption”, in the context of which the terms “sorbed”, “sorbate” and “sorbent” relates to the “adsorbed”, “adsorbate” and “adsorbent”, respectively.
  • the term “contamination-reducing component” encompasses any component suitable for reducing or eliminating the presence of contaminants, in particular moisture (i.e. water) and/or decomposition products and/or any other component the presence of which is not desired.
  • the term “contamination-reducing component” relates to a water-reducing component, in particular encompassing a desiccant.

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Abstract

La présente invention concerne un procédé pour fournir un composant de réduction de contamination (5) à un appareil électrique (1), ledit appareil électrique (1) comprenant un boîtier (2) enfermant un espace isolant (3) et un composant électrique (4) placé dans l'espace isolant (3), ledit espace isolant (3) comprenant un milieu d'isolation qui comprend ou est composé de dioxyde de carbone. Le procédé comprend les étapes de saturation préalable du composant de réduction de contamination (5) avec du dioxyde de carbone avant de le placer à l'intérieur de l'appareil électrique (1).
EP14718095.4A 2013-04-22 2014-04-16 Procédé pour fournir un composant de réduction de contamination à un appareil électrique Withdrawn EP2989702A1 (fr)

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EP14718095.4A EP2989702A1 (fr) 2013-04-22 2014-04-16 Procédé pour fournir un composant de réduction de contamination à un appareil électrique

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EP2013058316 2013-04-22
EP14718095.4A EP2989702A1 (fr) 2013-04-22 2014-04-16 Procédé pour fournir un composant de réduction de contamination à un appareil électrique
PCT/EP2014/057803 WO2014173776A1 (fr) 2013-04-22 2014-04-16 Procédé pour fournir un composant de réduction de contamination à un appareil électrique

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