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Title:
A CIRCUIT BREAKER COMPRISING A METAL-ORGANIC FRAMEWORK MATERIAL FOR CO ADSORPTION
Document Type and Number:
WIPO Patent Application WO/2018/210938
Kind Code:
A1
Abstract:
A circuit breaker, comprising an enclosure comprising: - at least two arcing contacts that are movable axially relative to each other, between an open position of the circuit breaker in which the arcing contacts are separated from each other and a closed position of the circuit breaker in which the arcing contacts are in contact with each other; and - a gas inlet configured to blow an arc-control gas in order to interrupt an electric arc that is likely to form during movement of the arcing contacts from the closed position to the open position of the circuit breaker, wherein the arc-control gas comprises at least 80% of carbon dioxide; wherein the enclosure further comprises an adsorbing material, which adsorbs carbon monoxide that forms after ionization of the carbon dioxide during arcing, said adsorber being a metal-organic framework comprising nickel and/or iron.

Inventors:
KIEFFEL, Yannick (21 Rue Cyprian, Villeurbanne, 69100, FR)
MAKSOUD, Louis (21 Rue Cyprian, Villeurbanne, 69100, FR)
Application Number:
EP2018/062755
Publication Date:
November 22, 2018
Filing Date:
May 16, 2018
Export Citation:
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Assignee:
GENERAL ELECTRIC TECHNOLOGY GMBH (Brown Boveri Strasse 7, 5400 Baden, 5400, CH)
International Classes:
H01H33/22
Domestic Patent References:
WO2012122233A22012-09-13
Foreign References:
EP2445068A12012-04-25
JP2015073348A2015-04-16
US20120031268A12012-02-09
US20080227634A12008-09-18
US20160250618A12016-09-01
Attorney, Agent or Firm:
GENERAL ELECTRIC TECHNOLOGY GMBH (Global Patent Operation - Europe, Brown Boveri Strasse 7, 5400 Baden, 5400, CH)
Download PDF:
Claims:
CLAIMS

1. A circuit breaker, comprising an enclosure comprising:

- at least two arcing contacts that are movable axially relative to each other, between an open position of the circuit breaker in which the arcing contacts are separated from each other and a closed position of the circuit breaker in which the arcing contacts are in contact with each other;

- a gas inlet configured to blow an arc-control gas in order to interrupt an electric arc that is likely to form during movement of the arcing contacts from the closed position to the open position of the circuit breaker, wherein the arc-control gas comprises at least 80% of carbon dioxide; and

wherein the enclosure further comprises an adsorbing material, which adsorbs carbon monoxide that forms after ionization of the carbon dioxide during arcing, the adsorbing material being a metal-organic framework comprising nickel and/or iron. 2. A circuit breaker according to claim 1, wherein the metal organic framework is in the form of particles.

3. A circuit breaker according to claim 1 or 2, wherein the particles have a diameter from 1mm to 10mm, preferably from 1mm to 5mm.

4. A circuit breaker according to claim 1, wherein the adsorbing material is supported by a ceramic substrate.

5. A circuit breaker according to any one of claims 1 to 4, wherein the arc-control gas is constituted by carbon dioxide C02.

6. A circuit breaker according to any one of claims 1 to 4, wherein the arc-control gas is a gas mixture comprising C02 and at least a fluorinated compound, such as 2,3,3,3-tetrafluoro-2-(trifluoromethyl)-2-propanenitrile, 1,1,1,3,4, 4,4-heptafluoro-3- (trifluoromethyl)-2-butanone, 2,3,3,3-Tetrafluoropropene, 1,3,3,3-Tetrafluoropropene or fluorooxirane.

7. An air-insulated switchgear comprising a circuit breaker as defined in any one of claims 1 to 6.

8. A gas-insulated switchgear comprising a circuit breaker as defined in any one of claims 1 to 6.

Description:
A CIRCUIT BREAKER COMPRISING A METAL-ORGANIC FRAMEWORK MATERIAL

FOR CO ADSORPTION

DESCRIPTION

TECHNICAL FIELD AND PRIOR ART

The present invention relates to the field of electrical insulation and extinguishing of electrical arcs in medium- and high-voltage devices.

More precisely, it relates to a medium- or high-voltage circuit breaker comprising an adsorber, which adsorbs carbon monoxide that forms during arcing.

An arc-blast circuit breaker comprises at least two arcing contacts that are movable axially relative to each other, between an open position of the circuit breaker in which the arcing contacts are separated from each other and a closed position of the circuit breaker in which the arcing contacts are in contact with each other. In circuit breaker, current is typically broken by separating arcing contacts. From the closed position to the open position of the circuit breaker, an electric arc is likely to form between said contacts. In order to interrupt an electric arc, an insulating dielectric gas is blasted onto the arc, thereby making it possible to cool said arc and to extinguish it.

Currently, the most frequently-used arc-control gas for that type of circuit breakers is sulfur hexafluoride SF6 because of the exceptional physical properties of said gas. However, SF 6 presents the major drawback of being a very powerful greenhouse gas, with a particularly high global warming potential (GWP).

Among the alternatives to the use of SF 6 as an arc-control gas, various gases of global warming potential that is lower than that of SF6 are known, such as dry air or also nitrogen.

A particularly advantageous arc-control gas is carbon dioxide C0 2 because of its strong electric insulation and arc-extinction capabilities. Furthermore, C0 2 is non-toxic, non-flammable, with a very low GWP, and is also easy to obtain.

C0 2 can be used alone or in the form of a gas mixture, of which it constitutes the main gas referred to as "vector gas". For example, the gaseous medium, commonly marketed by Alstom under the name g 3 (or 'green gas for green'), a mixture of C0 2 (100- x)% with a fluorinated gas x% (x≤10%), is suitable for replacing SF6. The gas mixture presents extinction capabilities that are comparable to, or even better than those of SF 6 , has little or no effect on the environment (a global warming potential (GWP) 98% lower than the GWP of SFe), a cost that is compatible with its use in manufacturing switchgear on an industrial scale and is non-toxic for humans and animals.

But, and contrary to the SF6 which has the property of recombining after decomposition by arc discharge, C0 2 does not recombine completely and namely produces a significant amount of toxic gaseous carbon monoxide CO and carbon powder. Therefore, the neutralization of CO is a key issue. The neutralization of carbon monoxide can be performed in adsorbing (trapping) carbon monoxide on the surface of a substrate.

CO adsorption can be achieved with zeolite or with a Metal-Organic Framework (MOF) material.

The drawback of that first solution lies in the fact that a zeolite cannot sufficiently remove CO as the zeolite also adsorbs the insulating C0 2 gas.

MOFs are microporous solids, multidimensional structures of metallic atoms coordinated to organic ligands. They are structural materials with very high inner surface areas and ordered pore channels which make them highly attractive for gas- storage, especially for small gaseous molecules, such as H 2 , CH 4 . However, few existing MOFs in the market are proved to be selective to CO instead of C0 2 .

In US 2012/0031268, gaseous contaminants, such as S0 2 , NH 3 , Cl 2 , and

CO have been captured with different MOFs: a Zn 4 0(C0 2 )6 cluster linked by terephthalate, 2-aminoterephthalate, benzene-l,3,5-tris(4-benzoate), and diacetylene-l,4-bis-(4-benzoic acid); a Cu 2 (C0 2 ) 4 cluster linked by trimesate; and ID Zn 2 0 2 (C0 2 ) 2 chains linked by 2,5-dihydroxyterephthalate. However, the carbon monoxide breakthrough curves do not differ from that measured for a blank sample cell.

In document US 2008/0227634, it is mentioned that a MOF compound combined with a polymer can be used to adsorb a gas such as carbon monoxide. The framework material comprises at least one bidentate organic compound bound by coordination to at least one metal ion. The pores of the material comprise a polymer which is suitable for adsorbing the gas, so that the material has improved properties in the storage and also separation of gases.

In the document US 2016/0250618, it is indicated that a MOF comprising oxide and/or carboxylate linking clusters of 4,6-dioxido-l,3-benzenedicarboxylate based linking moieties, is suitable for storing and/or separating gas molecules such as gases including ammonia, argon, carbon dioxide, carbon monoxide, hydrogen, and methane.

These documents overall focus on the synthesis of the MOFs and the implicated ligands. Among them, there is no investigation of MOFs for selective adsorption of CO in C0 2 in the operation conditions of a medium- or high-voltage circuit breaker (i.e. at temperature lower than 105°C).

SUMMARY OF THE INVENTION

The invention aims to propose a circuit breaker comprising a material adsorbing selectively CO gas in a gas mixture formed mainly with C0 2 , at low temperature (below around 100°C).

The material shall be inert to all the other components of the gas, with a feasible cost and with a good selectivity to CO compared to the other components.

These objects are achieved by the invention that provides a circuit breaker, comprising an enclosure comprising:

- at least two arcing contacts that are movable axially relative to each other, between an open position of the circuit breaker in which the arcing contacts are separated from each other and a closed position of the circuit breaker in which the arcing contacts are in contact with each other,

- a gas inlet configured to blow an arc-control gas in order to interrupt an electric arc that is likely to form during movement of the arcing contacts from the closed position to the open position of the circuit breaker, the arc-control gas comprises at least 80% of carbon dioxide,

the enclosure further comprises an adsorbing material, which adsorbs carbon monoxide that forms after ionization of the carbon dioxide during arcing, said adsorbent being a metal-organic framework comprising nickel and/or iron. A metal organic framework (MOF) is composed of two components: a metal ion or a cluster of metal ions that is linked to at least an organic ligand. The MOF can comprise several ligands to form two dimensional or three dimensional structures. The choice of metal and ligand has significant effects on the structure (porosity, size) and properties of the MOF. The inventors have highlighted that a MOF with nickel and/or iron presents remarkable adsorbing properties in the operation conditions of a medium- or high-voltage circuit breaker.

This material enables the neutralization of carbon monoxide even at low temperature (below 200°C, and preferably below 105°C).

It selectively adsorbs and retains carbon monoxide instead of carbon dioxide. The fluorinated compounds are not adsorbed onto the materials.

There is no need to add an adsorbing polymer as described in the prior art.

The successful purification of the insulating gas maintains its properties and improves its longevity.

Additionally, this material is suitable for fitting in a circuit breaker without any increase in its bulk and without any noticeable increase in costs, namely in terms of manufacturing process.

Advantageously, the metal organic framework is in the form of particles. This enables to increase the surface area.

Advantageously, the particles have a diameter from 1mm to 10mm, preferably from 1mm to 5mm. It is relatively easy to obtain such size of particles by conventional and low-cost methods.

According to another embodiment, the adsorbing material is supported by a ceramic substrate, such as a cordierite substrate or an aluminosilicate substrate. Ceramic substrates have a high thermal resistance, which is suitable for circuit breaker applications.

Advantageously, the arc-control gas is constituted by carbon dioxide C0 2 . In a second variant of the invention, the arc-control gas is a gas mixture comprising C0 2 and at least a fluorinated compound, such as 2,3,3,3-tetrafluoro-2- (trifluoromethyl)-2-propanenitrile or l,l,l,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2- butanone, 2,3,3,3-Tetrafluoropropene, 1,3,3,3-Tetrafluoropropene or fluorooxirane.

The adsorbing material can be used to neutralize carbon monoxide in different arc-control gases.

The invention also provides an air-insulated switchgear (AIS) comprising a circuit breaker as defined previously.

The invention also provides a gas-insulated switchgear (GIS) comprising a circuit breaker as defined previously.

The invention can be better understood on reading the additional description given below that relates to a circuit breaker according to the invention.

Naturally, however, this additional description is given merely by way of illustrative example of the invention and is in no way limiting on said invention.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS

The circuit breaker is a medium- or high-voltage circuit breaker

Above and below, the terms "medium voltage" and "high voltage" are used in the conventionally accepted manner, i.e. the term "medium voltage" refers to a voltage that is in the range 7,2 kV to 52 kV, whereas the term "high voltage" refers to a voltage that is in the range 52 kV to 800 kV.

The circuit breaker includes a closed enclosure having a certain number of electrical and/or mechanical components that are housed inside said enclosure. The enclosure is a leak-tight enclosure.

The volume of the enclosure can be from 50L to 1000L.

The enclosure comprises a gas inlet that is configured to blow the arc- control gas on the electric arc to extinguish it. The gas can be injected in a nozzle. The enclosure also contains a gas outlet.

The adsorbing material is disposed so as to be in contact with the gas flow containing the CO molecules. It can be located close to the arcing contacts.

According to another embodiment, it is located in the gas outlet of the circuit breaker The arc-control gas in the circuit breaker is a dielectric insulating gas.

It contains at least 80% by volume, and preferably, at least 90% by volume of carbon dioxide. For example, it can be a mixture of carbon dioxide (80-100%) and one or more fluorinated compounds (0-20%). Preferably, it is a mixture of carbon dioxide (90-97, preferably 90-96%) and one or more fluorinated compounds (3-10%, preferably 4-10%). For illustrative purpose, the fluorinated compound can be a compound commercialized by Alstom under the name Novec 4710 (2,3,3,3-tetrafluoro-2- (trifluoromethyl)-2-propanenitrile of formula (CF 3 )2CFCN) or Novec 5110 (1,1,1,3,4,4,4- heptafluoro-3-(trifluoromethyl)-2-butanone of formula CF 3 C(0)CF(CF 3 ) 2 ). It can also be 2,3,3,3-Tetrafluoropropene (HFO-1234yf), 1,3,3,3-Tetrafluoropropene (HFO-1234ze) or fluorooxirane.

Two fluorinated compounds, such as heptafluoroisobutyronitrile and tetrafluoromethane, could also be used in association.

It should be noted that the adsorbing material could be used for gases with lower C0 2 amount. As long as there is C0 2 in the gas mixture, CO can be formed due to arcing in high-voltage circuit breaker.

According to a further embodiment the gas mixture comprises oxygen. The oxygen can further facilitate the reduction of harmful byproducts. For example, the gas mixture contains at least 80 % of a mixture of carbon dioxide and oxygen. Wherein the oxygen content is preferably in the range of 1 % to 25 %.

In another embodiment, the gas could consist of carbon dioxide.

The arc-control gas is oxygen-free. By oxygen-free, it should be understood that the arc-control gas contains less than 0.1% by volume of oxygen gas, and preferably less than 0.02%.

Advantageously, the dielectric insulating gas is present in the equipment in entirely gaseous form whatever the utilization temperature of the equipment. It is therefore advisable for the pressure of the gas inside the equipment to be selected as a function of the saturated vapor pressure (SVP) presented by the gas at the lowest utilization temperature of said equipment. During arcing, carbon dioxide is ionized into carbon monoxide. The amount of formed CO depends on the physical conditions of the operation and the chemical reaction involved in the process. It varies from few ppm up to few %, from example from lppm to 5%.

Carbon monoxide neutralization is achieved using an adsorbing material. The adsorbing material is a MOF.

Every time an electric arc is extinguished and carbon monoxide is formed, the adsorbing material adsorbs it.

The performance and the application of a MOF depend on the metal and on the ligand. Selectivity can evolve between 10% (very low selectivity to CO) and 100% (exclusive adsorption of CO). In the present invention, the structure of MOFs has been modified in order to be selective to CO instead of C0 2 in the operation conditions of a medium- or high-voltage circuit breaker.

A MOF with iron and/or nickel presents adsorption selectivity to CO in a gas mixture comprises CO and C0 2

The tests consist in following during minutes/hours/days the evolution of the amount of CO (and C0 2 ) within an airtight test cell containing the sample (gas mixture) in contact with the MOF. Several MOFs materials of the invention have been successfully performed and tested using spectroscopy and gas chromatography.

The adsorbing material can be a powder of particles. The particles may a have a diameter of few millimeters, from example 1mm to 10mm, preferably from 1mm to 5mm.

The MOFs material of the present invention may be coated to the surface of any suitable substrates.

Advantageously, the substrate presents a high specific surface. For example, the substrate can be a substrate with a "honeycomb" or "monolithic" shape. The honey comb structure is also useful to trap the carbon powder.

The substrate can be a ceramic such as a cordierite substrate or an aluminosilicate substrate. Alternatively, the neutralization material can be dispersed on a particulate support, such as pellets or particles or the like.

This kind of MOFs can be used in situ in medium- or high-voltage circuit breaker.

When an electric arc is formed, a portion of the fraction of C0 2 , which is present in the gaseous state inside the enclosure, is broken down into molecular species of smaller molecular mass and, therefore, of smaller size than C0 2 . This has the effect of raising the total pressure that exists inside the enclosure, while lowering the partial pressure of the C0 2 to below its SVP. The carbon monoxide molecules thus formed in this way are trapped by the adsorbing material, and this has the effect of returning the partial pressure of C0 2 to a value equal to its SVP.

The man skilled in the art will be able to select the appropriate amount of adsorbing material according to the volume of CO gas to be treated and the inner geometry of the involved enclosure of the circuit-breaker. For example, the amount of adsorbing material is calculated as function of the potential amount of CO formed within the circuit breaker after arcing simulated over the circuit breaker lifetime. It depends on the energy of arcing and so on the circuit breaker type. For illustrative purpose, maintenance can be expected every 20 years, during which the circuit breaker is opened and the adsorbing material may then be replaced by a new one if necessary.

The circuit breaker according to the invention has a compact structure.

The concepts of the various embodiments described above can be effectively applied to various kinds of circuit breaker, such as for example circuit breakers with an interruption chamber of the axial- or transverse-blast type or of the mixed transverse-axial blast type.

For illustrative purposes, the circuit breaker can be used in any electrical device employing C02 gas electric insulation, namely an electrical transformer, an electricity transporting or distributing line, a set of busbars, a switch, a connector/disconnector (also called switchgear), a unit combining a circuit breaker with fuses, a grounding switch, or a contactor.

The circuit breaker is particularly valuable for air-insulated switchgear (AIS) or gas-insulated switchgear (GIS), and more preferably for high-voltage AIS or GIS.