• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to the use of a mixture, as a dielectric fluid, comprising a composition A comprising dibenzyltoluene and benzyltoluene, to improve the life of a transformer.
    公开号:FR3078711A1
    申请号:FR1852028
    申请日:2018-03-08
    公开日:2019-09-13
    发明作者:Jeremie WALKER；Bernard Monguillon
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    Use of a mixture as a dielectric fluid
    The present invention relates to the use of a mixture comprising benzyltoluene and dibenzyltoluene as dielectric fluid, to improve the life of a transformer.
    Dielectric fluids are insulating materials conventionally used in electrical equipment, such as high voltage cables and transformers, in which they are impregnated on a solid material serving as insulator, such as a polypropylene film, of paper, possibly a combination of the two called “mixed film-paper”.
    The dielectric fluids market is booming with energy demand and population growth.
    The most commonly used dielectric fluids in transformers are mineral oils on the one hand for their physico-chemical properties and on the other hand for their low cost and availability. Mineral oils have the particular advantage of being good thermal conductors and of being able to efficiently dissipate the heat produced by the current and through the windings and the magnetic circuit of a transformer, in particular of a power transformer. A power transformer is called a transformer having an apparent power strictly greater than 3 MVA (in three-phase). Transformers with a power less than or equal to 3 MVA are distribution transformers.
    However, the use of mineral oils poses environmental problems, in particular in the event of a leak, and safety in the event of a fire due to a flash point and an ignition point which can be too low depending on the operating temperature of the transformer. In other words, mineral oils have good dielectric and thermal performance, but their use requires specific precautions in terms of safety and treatment of waste occurring at the end of the oil and / or transformer life.
    In order to overcome these drawbacks, alternative fluids, in particular based on silicone oils or on synthetic and natural esters, such as vegetable oils and fatty acid esters, have been developed. Indeed, the esters are biodegradable and the silicone oils are inert. In addition, alternative fluids generally have flash and ignition points twice as high as mineral oil, which reduces the potential risk of ignition, or even explosion, of the transformer.
    To this end, document WO 2016/167176 discloses a dielectric fluid comprising at least one fatty acid ester.
    However, their use is still too often limited because of their high cost and their poor dielectric and thermal performance. In particular, alternative fluids have a low capacity for evacuating calories when the transformer heats up, which can in some cases lead to a change in the design of the fluid circulation channels inside the transformer, leading in particular to to their widening. In addition, their low chemical stability and resistance to oxidation generally require the systematic presence of numerous additives.
    In other words, these fluids are found to be more environmentally friendly than mineral oils but have lower thermal performance which tends to lead to an increase in the size of transformers, and therefore in their cost.
    In addition, the service life of transformers used with such fluids does not exceed that of transformers used with mineral oils.
    In fact, the fluids generally used as insulating materials in transformers, especially power transformers, gradually lose their dielectric properties with aging, caused by operating conditions, and above all by temperature. In addition, the use of fluids with better heat exchange characteristics allows transformers to operate at lower temperatures, which could increase their service life.
    With this in mind, other dielectric fluids were then placed on the market, for example, complex mixtures of hydrocarbons obtained by refining mineral oils obtained from petroleum.
    Thus, the document US Pat. No. 4,523,044 discloses dielectric fluids mainly consisting of oligomers of benzyltoluene and a small proportion of oligomers of ditolyl phenyl methane.
    In addition, the replacement of transformers at the end of their life with new transformers is a source of high expense. Manufacturers generally choose the refill solution because it is economically interesting even if it could be a source of problems linked for example to a draining of the old fluid not necessarily correctly carried out. In addition, the transformer design is not always suitable for the new fluid.
    In addition, cellulose insulation (called paper insulation) has also been designed to have an insulating material with better dielectric and thermal performance. Such insulation can be carried out using layers of paper and / or polymeric films, such as polypropylene films, superimposed and dried, then impregnated with dielectric fluids.
    However, a paper-based insulating material has more affinity for water. The thermal degradation of the paper produces water which preferentially remains in the paper, which most often results in a deterioration of the dielectric properties of the insulating material.
    Thus, one of the objectives of the present invention is to use dielectric fluids having increased thermal stability, improved heat exchange characteristics, in particular greater than those of mineral oils, as well as optimized electrical performance in order to improve the service life of transformers.
    In other words, there is a real need to provide dielectric fluids capable of improving the life of the transformers without impacting their performance and their size, that is to say while maintaining an improvement in the reduction of their size.
    In view of the above, the invention more particularly aims to provide dielectric fluids with properties suitable for improving the life of transformers.
    The Applicant has discovered that this need can be met by the use of a particular mixture as a dielectric fluid.
    The present invention relates to the use of a mixture, as a dielectric fluid, comprising a composition A comprising dibenzyltoluene and benzyltoluene, to improve the life of a transformer, preferably a power transformer.
    In other words, the invention relates to the use of a mixture as described above to increase the life of a transformer. In other words, the invention relates to a dielectric fluid comprising a composition A as described above to increase the life of a transformer.
    The use of such a mixture makes it possible to improve the thermal performance, the heat exchange characteristics, in particular thanks to a better efficiency with regard to the evacuation of calories during the heating of the transformer. In fact, this removal of calories is rapid thanks to the use of such a mixture, which also makes it possible to reduce the temperature of the transformer, in particular at full load. In particular, the mixture allows more calories to be evacuated in free convection and in forced convection.
    The use of such a mixture also makes it possible to slow down the aging of the paper. In fact, when the insulator is paper-based, the fluid advantageously solubilizes water, especially more than mineral oils.
    Thanks to such a mixture, a gain in power of the transformer can be obtained for the same load of materials. Thus, the size of the transformer can be reduced while keeping the same power.
    The use of such a mixture makes it possible to improve the electrical performance, in particular thanks to an improved permittivity and dielectric rigidity. Within the meaning of the invention, the dielectric strength, expressed in V / m, is the minimum electric field which causes the breakdown of a material, as mentioned in "Engineering techniques d2470: Insulating liquids in electrical engineering, presentation general ”, by Noëlle Berger, May 2002.
    The mixture thus has thermal and electrical advantages while meeting the requirements in terms of environmental protection and safety.
    It is specified that the expressions "from ... to ..." used in the present description must be understood as including each of the limits mentioned.
    Other advantages and characteristics of the invention will appear more clearly on examination of the detailed description.
    As mentioned above, composition A comprises dibenzyltoluene and benzyltoluene.
    Composition A can optionally comprise water within the meaning of the present invention. The water is nevertheless present in trace amounts when the composition A comprises it, such as in a content less than or equal to 100 ppm relative to the total content of the composition A. The water possibly present is not not added during the preparation of composition A but may correspond to the residual water provided by the mixed ingredients.
    This composition A can be produced from the commercial compounds taken separately or also obtained according to a process for the condensation of benzyl chloride on toluene in the presence of a Friedel and Crafts catalyst, then distillation.
    Preferably, it is prepared according to a process such as that described in document EP 0 435 737, which uses ferric chloride as catalyst. The reaction can be carried out at a temperature of 50 to 150 ° C. The reaction mixture obtained is generally treated to remove, on the one hand, the excess toluene by distillation, and, on the other hand, the organic chlorinated products formed (for example by contacting, hot and with stirring, with an alcoholate ).
    Benzyltoluene can be in the form of any isomer, in particular chosen from ortho- (CAS 713-36-0), para- (CAS 62083-7), metabenzyltoluene and their mixtures (in particular CAS 2777601-8). Any isomer of dibenzyltoluene and their mixtures can be used (CAS 26898-17-9).
    According to a preferred embodiment, composition A comprises:
    - from 2 to 30% by weight of dibenzyltoluene, relative to the total weight of composition A;
    - from 70 to 98% by weight of benzyltoluene, relative to the total weight of composition A;
    Advantageously, composition A comprises from 10 to 30% by weight of dibenzyltoluene, preferably from 12 to 28% by weight, more preferably from 22 to 25% by weight, relative to the total weight of composition A.
    Advantageously, composition A comprises from 70 to 90% by weight of benzyltoluene, preferably from 72 to 88% by weight, more preferably from 75 to 78% by weight, relative to the total weight of composition A.
    In a particularly preferred manner, composition A consists of 25% by weight of dibenzyltoluene and 75% by weight of benzyltoluene.
    An example of composition A is in particular commercially available from the company ARKEMA under the trade name Jarythem® BT06.
    Preferably, the mixture also comprises at least one ester.
    Said ester can be chosen from the group consisting of the esters of formula (I) below: R 1 -C (O) OR 2 (I), in which:
    - R 1 denotes a carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms;
    - R 2 denotes a carbon chain, linear or branched, saturated or unsaturated, comprising from 1 to 10 carbon atoms, and the esters of formula (II) below: R 3 -C (O) -O-CH2CH (OC (O ) R 4 ) -CH2-OC (O) -R 5 (II), in which:
    - R 3 , R 4 and R 5 denote, independently of each other, a carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms.
    Preferably, R 1 comprises from 7 to 20 carbon atoms.
    Preferably, R 2 comprises from 1 to 5 carbon atoms.
    Preferably, R 3 , R 4 and R 5 denote an identical carbon chain.
    Advantageously, said esters are chosen from the group consisting of plant esters, vegetable oils and their mixtures.
    Said esters can be plant esters, such as methyl glutarate, ethyl glutarate, methyl oleate, butyl oleate, methyl succinate, 1-methyl propyl succinate, methyl esters of castor oil, animal fat esters such as tallow methyl esters.
    Said esters can also be vegetable oils, such as olive oil, rapeseed oil, cocoa oil, peanut, mustard, castor oil, cotton, sunflower, corn, safflower, palm, coconut, sesame, rice, flax, seed grapes and soy.
    Preferably, said esters have a viscosity of less than or equal to 0.1 Pa.s at 20 ° C, more preferably less than or equal to 0.06 Pa.s at 20 ° C, even more preferably less than or equal to 0, 04 Pa.s at 20 ° C.
    The viscosity is measured using a Ubbelholde type glass capillary viscometer according to ISO standard 3104.
    An example of such an ester is commercially available from the company ARKEMA under the trade name Esterol® F.
    Advantageously, when the ester is present, the mixture comprises from 72 to 96% by weight of composition A, preferably from 72 to 85% by weight, relative to the total weight of the mixture.
    Advantageously, the content by weight of ester ranges from 2 to 26% by weight, preferably from 10 to 20% by weight, relative to the total weight of the mixture.
    According to a preferred embodiment, the mixture comprises at least one additive chosen from the group consisting of an antioxidant, a passivator, a pour point depressor, a decomposition inhibitor and their mixtures, preferably a decomposition inhibitor.
    Said antioxidants can be phenolic antioxidants, such as dibutylhydroxytoluene, butylhydroxyanisole, phenyl-a-naphthylamine, N, N-di (2naphthyl) -p-phenylene, antioxidants of amine type, for example diamine, such as tocopherol, d-tocopherol, dl-alphatocopherol, acetate -a- tocopherol, acetate dl-alpha-tocopherol, tocopherol acetate, alpha-tocopherol, ascorbic acid or its salts, esters of ascorbic acid, green tea extract, coffee extract.
    An example of such an antioxidant is commercially available from the company BRENNTAG under the trade name Ionol.
    Said passivators can be derivatives of triazole, benzimidazoles, imidazoles, thiazole, benzothiazole. By way of example and without limitation, dioctyl amino methyl-2,3benzotriazolele and 2-dodecyldithio imidazole can be mentioned.
    Said pour point reducers can be sucrose fatty acid esters, acrylic polymers such as polyalkyl methacrylate or polyalkyl acrylate.
    The acrylic polymers preferably have a molecular weight of between 50,000 and 500,000 g / mol.
    Examples of these acrylic polymers include polymers which may contain linear alkyl groups comprising from 1 to 20 carbon atoms.
    By way of example, mention may be made of polymethyl acrylate, polymethyl methacrylate, Porihepuchiru acrylate, poly heptyle methacrylate, polynonyl acrylate, polynonyl methacrylate, polyundecyl acrylate, polyundecyl methacrylate, polytridecyl acrylate, polytridecyl polypentadecyl acrylate, polypentadecyl methacrylate, polyheptadecyl acrylate, or even polyheptadecyl methacrylate.
    An example of such a pour point depressor is commercially available from Sanyo Chemical Industries under the trade name ACLUBE.
    More preferably, the mixture according to the invention comprises at least one decomposition inhibitor.
    Said decomposition inhibitors can be carbodiimide derivatives such as diphenyl carbodiimide, di-tolyl carbodiimide, bis (isopropylphenyl) carbodiimide, bis (butylphenyl) carbodiimide, phenyl glycidyl ethers, or ester, alkyl glycidyl ethers, or esters , 3,4-epoxycyclohexylmethyl (3,4epoxycyclohexane) carboxylate, epoxy derivatives such as vinylcyclohexene diepoxides, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methyl-hexane) carboxylate, resins epoxy phenol novolak type, bisphenol A epoxy diglycidyl ether such as DGEBA or CEL 2021P available from the company WHYTE CHEMICAL.
    According to a particular embodiment of the invention, the mixture comprises a composition A and at least one decomposition inhibitor.
    Advantageously, the mixture comprises a composition A, at least one ester and at least one decomposition inhibitor.
    The content by weight of the additive can range from 0.0001 to 2% by weight, preferably from 0.001 to 1% by weight, more preferably from 0.01 to 0.5% by weight, relative to the total weight of the mixed.
    As mentioned above, the mixture improves the life of a transformer.
    Preferably, the mixture according to the invention is used to improve the life of power or measurement transformers, or high voltage transformers. More preferably, the mixture according to the invention is used to improve the life of power transformers.
    It has been said above that composition A could possibly comprise trace water. Other sources of trace water can also be found which are found in the dielectric fluid during its use in a transformer. For example, and in a nonlimiting manner, the water can come from the degradation of the paper and mix with the dielectric fluid.
    The present invention will be better understood from the following examples, which are given purely by way of illustration and are not intended to limit the scope of the invention.
    EXAMPLES
    1. Preparation of three dielectric fluids
    Three dielectric fluids are prepared according to the compositions as indicated in table 1 below:
    Fluid B (comp) C (inv) D (inv) Mineral oil 1 (% by weight) 100 - - Composition A 2 (% by weight) - qs 100 qs 100 CEL2021P (% by weight) - 0.2 0.2 Esterol® F (% by weight) - - 14.9
    Table 1: Nytro Libra mineral oil (uninhibited mineral oil sold by Nynas): Composition A consisting of 25% by weight of dibenzyltoluene, relative to the total weight of composition A, and 75% by weight of benzyltoluene, relative to total weight of composition A
    Thus, fluid B is a comparative fluid. The fluids C and D are fluids according to the invention.
    2, Evaluation and results
    at. Paper aging study
    The water content of fluids B and C was measured before impregnation of paper in each of these fluids. It is respectively 20.8 ppm for fluid B and 81.4 ppm for fluid C.
    Then, paper was impregnated with fluid B and fluid C. The aging of the paper in each of these fluids was studied at different temperatures and durations.
    Thus, fluids B and C are tested at 70 ° C, 100 ° C and 130 ° C for periods of 250 hours and 500 hours respectively. The water content was measured at room temperature. The degree of polymerization was measured for the experiments carried out at 100 ° C and 5,130 ° C. The results are collated in Table 2 below.
    Fluid Temperature (° C) duration(H) Fluid water content (ppm) Degree of polymerization B (comp) 70 250 3.0 - C (inv) 70 250 38.8 - B (comp) 70 500 3.8 - C (inv) 70 500 22.1 - B (comp) 100 250 0.1 640 C (inv) 100 250 22.0 920 B (comp) 100 500 0.5 490 C (inv) 100 500 21.2 1000 B (comp) 130 250 0 350 C (inv) 130 250 14.4 780 B (comp) 130 500 0.5 410 C (inv) 130 500 18.4 790
    Table 2
    Before impregnating the paper, the water content in the fluids is high. Water, being more soluble in paper, will migrate into the paper during the impregnation at room temperature.
    Compared to the comparative fluid B, the water content in the fluid C according to the invention is always greater whatever the temperature and the duration of the tests. This indicates that water will migrate faster in fluid C which will keep the paper drier compared to fluid B, thanks to its greater solubility of water in fluid C, at a given temperature, compared to fluid B.
    The comparison of the degrees of polymerization clearly shows that the degradation of the paper is more pronounced with the fluid B by approximately 2 times, whatever the duration of aging compared to the fluid C.
    b. Thermal performance evaluation
    The thermal performances of fluids B, C and D are evaluated.
    In a 400 KV transformer with an oil capacity of 400 L and operating in free convection, the difference in temperature of the fluid between the inlet (or outlet) of the transformer and the outlet of the refrigerant was measured.
    The results are shown in Table 3 below:
    Fluid B (comp) C (inv) D (inv) Transformer outlet temperature (° C) 90 84 87 Refrigerant outlet temperature (° C) 40 30 35 Δ Temperature (° C) 50 54 52
    Table 3
    Table 3 clearly shows a greater temperature difference between the outlet of the transformer and the outlet of the refrigerant when fluids C and D are used compared to fluid B.
    Thus, better heat dissipation can be observed when the dielectric fluids C or D are used. The use of dielectric fluids C or D therefore allows a more efficient heat exchange.
    A more efficient heat exchange contributes to slowing the aging of the film, possibly associated with a layer of paper, in which the dielectric fluids are impregnated, consequently improving the service life of a transformer.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    1. Use of a mixture, as a dielectric fluid, comprising a composition A comprising dibenzyltoluene and benzyltoluene, to improve the life of a transformer, preferably a power transformer.
    [2" id="c-fr-0002]
    2. Use according to claim 1, characterized in that composition A comprises:
    - from 2 to 30% by weight of dibenzyltoluene, relative to the total weight of composition A;
    - from 70 to 98% by weight of benzyltoluene, relative to the total weight of composition A.
    [3" id="c-fr-0003]
    3. Use according to claim 1 or 2, characterized in that composition A comprises from 10 to 30% by weight of dibenzyltoluene, preferably from 12 to 28% by weight, relative to the total weight of composition A.
    [4" id="c-fr-0004]
    4. Use according to any one of the preceding claims, characterized in that composition A comprises from 70 to 90% by weight of benzyltoluene, preferably from 72 to 88% by weight, relative to the total weight of composition A.
    [5" id="c-fr-0005]
    5. Use according to any one of the preceding claims, characterized in that the mixture also comprises at least one ester.
    [6" id="c-fr-0006]
    6. Use according to claim 5, characterized in that the ester is chosen from the group consisting of the esters of formula (I) below: R 1 -C (O) OR 2 (I), in which:
    - R 1 denotes a carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms;
    - R 2 denotes a carbon chain, linear or branched, saturated or unsaturated, comprising from 1 to 10 carbon atoms, and the esters of formula (II) below: R 3 -C (O) -O-CH2CH (OC (O ) R 4 ) -CH2-OC (O) -R 5 (II), in which R 3 , R 4 and R 5 denote, independently of each other, a carbon chain, linear or branched, saturated or unsaturated, comprising 5 to 20 carbon atoms.
    [7" id="c-fr-0007]
    7. Use according to claim 5 or 6, characterized in that the mixture comprises from 72 to 96% by weight of composition A, preferably from 72 to 85% by weight, relative to the total weight of the mixture.
    [8" id="c-fr-0008]
    8. Use according to any one of claims 5 to 7, characterized in that the content by weight of ester ranges from 2 to 26% by weight, preferably from 10 to 20% by weight, relative to the total weight of the mixture .
    [9" id="c-fr-0009]
    9. Use according to any one of the preceding claims, characterized in that the mixture comprises at least one additive chosen from the group consisting of an antioxidant, a passivator, a pour point depressor, a decomposition inhibitor and their mixtures , preferably a decomposition inhibitor.
    [10" id="c-fr-0010]
    10. Use according to claim 9, characterized in that the content by weight of the additive ranges from 0.0001 to 2% by weight, preferably from 0.001 to 1% by weight, more preferably from 0.01 to 0, 5% by weight, relative to the total weight of the mixture.
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    同族专利:
    公开号 | 公开日
    CN112088200A|2020-12-15|
    WO2019171001A1|2019-09-12|
    EP3762466A1|2021-01-13|
    FR3078711B1|2020-07-31|
    US20210005345A1|2021-01-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20160163412A1|2013-07-19|2016-06-09|Arkema France|Dielectric or heat-transfer fluid compositions and uses of same|FR3101476A1|2019-10-01|2021-04-02|Arkema France|Dielectric fluid for transformer retrofilling|
    FR3101477A1|2019-10-01|2021-04-02|Arkema France|INCREASING THE POWER OF A TRANSFORMER|FR2552423B1|1983-09-23|1985-10-25|Ugine Kuhlmann|POLYARYLALCAN OLIGOMER COMPOSITIONS AND THEIR MANUFACTURING METHOD|
    FR2656603B1|1989-12-28|1993-05-21|Atochem|METHODS OF SYNTHESIS OF BENZYLTOLUENE AND LOW CHLORINE DIBENZYLTOLUENE.|
    FR2658812B1|1990-02-27|1992-05-15|Atochem|DIELECTRIC COMPOSITIONS BASED ON BENZYLTOLUENE AND XYLENE.|
    FR2734392B1|1995-05-19|1997-06-20|Atochem Elf Sa|CROSSLINKABLE DIELETRIC COMPOSITION|
    FR2794567A1|1999-06-07|2000-12-08|Atofina|DIELECTRIC COMPOSITION HAVING IMPROVED GAS ABSORPTION|
    EP2210259A1|2007-10-18|2010-07-28|Cooper Technologies Company|Dielectric fluid for improved capacitor performance|
    CN105315969A|2014-07-07|2016-02-10|上海久星导热油股份有限公司|High temperature modified heat conduction oil and preparation method thereof|
    WO2016167176A1|2015-04-13|2016-10-20|ライオン・スペシャリティ・ケミカルズ株式会社|Electrically insulating oil base oil for oil-filled electrical device, electrically insulating oil containing same, and oil-filled electrical device|
    GB2541929B|2015-09-04|2018-05-09|M&I Mat Limited|Ester compositions for dielectric fluids|
    法律状态:
    2019-02-13| PLFP| Fee payment|Year of fee payment: 2 |
    2019-09-13| PLSC| Publication of the preliminary search report|Effective date: 20190913 |
    2020-02-14| PLFP| Fee payment|Year of fee payment: 3 |
    2021-02-10| PLFP| Fee payment|Year of fee payment: 4 |
    2022-02-09| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1852028|2018-03-08|
    FR1852028A|FR3078711B1|2018-03-08|2018-03-08|USE OF A MIXTURE AS A DIELECTRIC FLUID|FR1852028A| FR3078711B1|2018-03-08|2018-03-08|USE OF A MIXTURE AS A DIELECTRIC FLUID|
    US16/976,990| US20210005345A1|2018-03-08|2019-03-06|Use of a mixture as dielectric fluid|
    CN201980030643.1A| CN112088200A|2018-03-08|2019-03-06|Use of mixtures as dielectric fluids|
    EP19713531.2A| EP3762466A1|2018-03-08|2019-03-06|Use of a mixture as a dielectric fluid|
    PCT/FR2019/050497| WO2019171001A1|2018-03-08|2019-03-06|Use of a mixture as a dielectric fluid|
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