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EP2346971A1 - Procédé pour éliminer des composés de soufre corrosifs d'une huile de transformateur - Google Patents

Procédé pour éliminer des composés de soufre corrosifs d'une huile de transformateur

Info

Publication number
EP2346971A1
EP2346971A1 EP08874989A EP08874989A EP2346971A1 EP 2346971 A1 EP2346971 A1 EP 2346971A1 EP 08874989 A EP08874989 A EP 08874989A EP 08874989 A EP08874989 A EP 08874989A EP 2346971 A1 EP2346971 A1 EP 2346971A1
Authority
EP
European Patent Office
Prior art keywords
rare earth
transformer
alumina
aluminum silicate
earth mixture
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Withdrawn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
EP08874989A
Other languages
German (de)
English (en)
Inventor
Ivanka ATANASOVA-HÖHLEIN
Peter Heinzig
Vladyslav Mezhvynskiy
Uwe Thiess
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.)
Siemens AG
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of EP2346971A1 publication Critical patent/EP2346971A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0008—Working-up used lubricants to recover useful products ; Cleaning with the use of adsorbentia
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/006—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents of waste oils, e.g. PCB's containing oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0058—Working-up used lubricants to recover useful products ; Cleaning by filtration and centrifugation processes; apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes

Definitions

  • the invention relates to a method for removing corrosive sulfur compounds from a transformer sol.
  • Transformers often use transformers as insulation and cooling media, which have been used to power transformers for many years because of their long-term chemical properties.
  • transformer sols the problem with the use of transformer sols is the presence of natural or added sulfur compounds, which contribute to the oleigen own oxidation stability, especially in the case of non-inhibited transformer sols.
  • conductive copper sulfide compounds are formed, which deposit preferentially in the paper insulation and impair their insulating properties. This phenomenon is favored especially at high operating and ambient temperatures.
  • transformer cores containing corrosive sulfur-containing constituents will form layers of copper sulfide on the paper insulation.
  • copper sulfide layers form inside the insulating paper layers surrounding the copper conductor.
  • the insulation properties of the paper insulation will in some cases have a lasting effect, so that partial discharges and voltage excursions between the live copper conductors due to the reduced insulation properties of the paper insulation can occur.
  • WO 2005/117031 A2 describes a method and a device for adding a passivator to a conductor. According to the aforementioned patent application, it is proposed to wrap the passivator directly around the conductor and then to electrically encase it with another layer of an electrical insulator and thus to electrically insulate the conductor with the passivator layer as a whole. Furthermore, WO 2007/096709 A2 describes a method for the permanent removal of corrosive components from a transformer sol. According to the aforementioned patent application, it is proposed to remove the transformer oil from a transformer tank and, after heating and adding an acidic liquid, to contact it by means of a sulfide radical trap and then to filter it. After filtering, the so-cleaned transformer oil is returned to the transformer tank.
  • WO 2007/144696 A2 as a method for deactivating corrosive sulfur in transformer sols.
  • a sulfide-producing chemical component be added to the transformer sol with corrosive sulfur compounds, so that this chemical component reacts with the sulfur compound and thus the corrosive sulfur compounds are removed from the transformer sol.
  • DE 10 2005 006 271 A1 describes a process for purifying transformer oil, wherein the transformer oil is first subjected to pretreatment by filtration before it is passed through a bed of an inert inorganic carrier coated with a reactive metal. Subsequently, the transformer oil is filtered through a Bleicherdebett and then fed back to the transformer.
  • a method for removing corrosive sulfur compounds from a transformer torol is proposed in which, with the addition of a mixture of alumina-aluminum silicate-containing rare earths in the transformer sol, this so enriched transformer sol up to heated to 300 degrees Celsius and then cooled by enrichment with an aqueous solution of soluble metal salts.
  • the transformant enriched with the alumina-aluminum silicate-containing rare earth mixture is again heated to 200 degrees Celsius for at least two hours and then cooled to room temperature.
  • the heating of the mixture of alumina-aluminum-silicate-containing rare earths activates the matrix adsorption centers by removing the water content. Thereafter, the heavy metal salts contained in the mixture of alumina-aluminum silicate-containing rare earths are dispersed in a little water and the mixture is slowly heated. This produces the heavy metal oxides which are insoluble and firmly bound to the fullerene matrix of the mixture of rare earths containing aluminum oxide and aluminum silicates.
  • the adsorbent is prepared.
  • the solution presented here is based on the removal of the reactive corrosive sulfur compounds present in the transformer sol through the use of a wide range of inorganic adsorbents in the range of applications. It is mainly a mixture of alumina-aluminum silicate-containing rare earths and optionally enriched with silver, copper, zinc and / or iron in metallic or oxidic form.
  • the metal oxides formed by means of the alumina-aluminum silicate-containing rare earth mixture bind the corrosive sulfur compounds and can be collected at a suitable site, with or without the simultaneous removal of oligomeric products, and removed from the transformer torol.
  • the advantage of this method is that no additional foreign substances, such as passivators, are added to the transformer sol.
  • the transformer oil is freed from aging products and from corrosive sulfur compounds. This increases the oxidation capacity and greatly reduces the proportion of corrosive sulfur compounds within the transformer sol, which sustainably increases the service life of the transformer.
  • the ratio between the proportion of aluminum oxide and the proportion of aluminum silicate of the alumina-aluminum silicate-containing rare earth mixture is in a ratio of 20:80 to 80:20, preferably 50:50 ,
  • the catalytic effect of the alumina-aluminum silicate-containing rare earth mixture is best ensured in the preferred ratio range of fractions.
  • the aqueous solution has a proportion of up to 40% of, in particular, soluble metal salts.
  • the addition of copper and silver salts leads to improved binding of the corrosive sulfur compounds to the metal salts present in the aqueous solution.
  • the pH of the alumina-aluminosilicate-containing rare earth mixture is 6.5 to 9.0. In the above-indicated pH range, the highest possible reaction rate of the metal oxides formed with the corrosive sulfur compounds.
  • the ratio of the aluminum oxide-aluminum silicate-containing rare earth mixture to the transformer sol in relation to the respective weights in a ratio of 0.01: 100 to 40: 100, preferably 10: 100, is present.
  • the preferred weight ratio of 10: 100 of alumina silicate-containing rare earth mixture to the transformer sol the highest possible reaction rate based on the respective concentrations is made possible.
  • the rare earth metals according to the third group of the periodic table, including the lantanoides are part of the rare earth mixture containing aluminum oxide-aluminum silicate.
  • the aluminum oxide-aluminum silicate-containing rare earth mixture silver, copper, zinc and / or iron are added.
  • silver nitrate is advantageously added to the aluminum oxide-aluminum silicate-containing rare earth mixture to form silver oxides and / or copper salts for the formation of copper oxides and / or iron oxides.
  • the metal oxides within the alumina-aluminum silicate-containing rare earth mixture are highly reactive and combine with the corrosive sulfur compounds within the transformer and neutralize the corrosive sulfur compounds.
  • the alumina-aluminum silicate-containing rare earth mixture is disposed in a container, wherein the container is mounted on a transformer housing and the transformer sol is guided and cleaned in the container, sowxe in the alumina-aluminum silicate-containing rare earth mixture bound sulfides remain as reaction products of the corrosive sulfur compounds in the container.
  • the reaction of the corrosive sulfur compounds of the transformer sol within the container and the accumulation of bound sulfides in the container these waste products can be disposed of during the removal of the container.
  • further contamination of the transformer with the bound sulfides in the container is ruled out, so that almost complete removal of corrosive sulfur compounds from the transformer oil is possible with the aforementioned method.
  • the container in the case of complete consumption of the alumina-aluminum silicate-containing rare earth mixture, is removed from the transformer housing.
  • the container has a display with respect to the existing reactive alumina-aluminum silicate-containing rare earth mixture. As part of a maintenance, the display can be used to determine whether sufficient reactive alumina-aluminum silicate-containing rare earth mixture components are present. conditions and a flawless implementation of the procedure is guaranteed.
  • a filter system is introduced within the container, the filter system comprising the alumina-aluminum silicate-containing rare earth mixture and the transformer sol is introduced into the filter system.
  • the filter system comprising the alumina-aluminum silicate-containing rare earth mixture and the transformer sol is introduced into the filter system.
  • the container can be connected to a cleaning device, wherein the cleaning device with the
  • Transformer housing connectable and the Transformatorol from the Transformatorgehause for cleaning in the cleaning device is transferable and thus in the container outside the Transformatorgehauses the corrosive sulfur compounds are removed.
  • An aluminum oxide-aluminum silicate-containing rare earth mixture is present with a ratio of aluminum oxide to aluminum silicate of 50:50 with a density of 600 g / l.
  • the pH is 7.0.
  • One kilogram of the alumina silicate-containing rare earth mixture is added
  • 150 0 C activated and treated after cooling with 400 ml of a 20% aqueous solution of soluble salts of silver, copper, zinc or iron in portions.
  • the mixture is homogenized and gradually to 120 0 C within five Heated for hours. This temperature is maintained for 15 to 20 hours. After cooling, the mixture is stored in the closed vessel.
  • the ratio based on the weights of the active alumina-aluminum silicate-containing rare earth mixture to the treated transformer oil is 0.5: 100 to 10: 100, depending on the aging state and corrosivity of the transformer oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé pour éliminer des composés de soufre corrosifs d'une huile de transformateur. Les composés de soufre corrosifs dans l'huile de transformateur sont neutralisés grâce à l'ajout d'un mélange de terres rares contenant de l'oxyde d'aluminium et du silicate d'aluminium dans l'huile de transformateur et l'enrichissement avec une solution aqueuse de sels métalliques solubles par des phases de chauffage et de refroidissement définies. L'avantage de ce procédé réside dans le fait qu'aucun composant chimique supplémentaire comme, par exemple, des passivateurs, ne sont ajoutés à l'huile de transformateur. En utilisant un récipient pour recevoir le mélange de terres rares contenant de l'oxyde d'aluminium et du silicate d'aluminium, la réaction peut se dérouler dans le récipient. De cette façon, des produits de vieillissement éventuellement présents et les composés de soufre corrosifs liés peuvent être efficacement retenus à l'intérieur du récipient au moyen d'un système de filtre et évacués avec le récipient.
EP08874989A 2008-10-20 2008-10-20 Procédé pour éliminer des composés de soufre corrosifs d'une huile de transformateur Withdrawn EP2346971A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2008/008985 WO2010045958A1 (fr) 2008-10-20 2008-10-20 Procédé pour éliminer des composés de soufre corrosifs d'une huile de transformateur

Publications (1)

Publication Number Publication Date
EP2346971A1 true EP2346971A1 (fr) 2011-07-27

Family

ID=40852296

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08874989A Withdrawn EP2346971A1 (fr) 2008-10-20 2008-10-20 Procédé pour éliminer des composés de soufre corrosifs d'une huile de transformateur

Country Status (6)

Country Link
US (1) US20110220552A1 (fr)
EP (1) EP2346971A1 (fr)
CN (1) CN102186959A (fr)
BR (1) BRPI0823168A2 (fr)
CA (1) CA2740998A1 (fr)
WO (1) WO2010045958A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102368417A (zh) * 2011-11-22 2012-03-07 虞海盈 变压器内部合成油的回收方法
CN102608194B (zh) * 2012-02-24 2014-09-10 北京盈胜泰科技术有限公司 一种液体油中腐蚀性硫的在线检测装置
CN103965951B (zh) * 2014-05-21 2015-10-21 国家电网公司 绝缘油腐蚀性硫脱除装置
CN104046422B (zh) * 2014-06-16 2016-06-01 江苏双江能源科技股份有限公司 一种高燃点变压器油及其制造方法
CN104357187A (zh) * 2014-10-15 2015-02-18 安徽蓝翔电器成套设备有限公司 一种变压器油及其制备方法和应用
CN104403740A (zh) * 2014-10-16 2015-03-11 苏州市宝玛数控设备有限公司 一种高性能电火花线切割用工作液
CN105032024B (zh) * 2015-08-17 2017-01-04 国家电网公司 一种绝缘油中二苄基二硫的脱除方法
CN108051392A (zh) * 2017-11-30 2018-05-18 广东电网有限责任公司电力科学研究院 一种变压器油泥老化组成的检测方法
US12075598B2 (en) * 2020-07-24 2024-08-27 Dell Products L.P. System and method for service life management based on corrosive material removal
US11809246B2 (en) 2020-07-24 2023-11-07 Dell Products L.P. System and method for service life management based on corrosion rate reduction

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1826140A (en) * 1929-05-08 1931-10-06 Richfield Oil Company Of Calif Process of refining hydrocarbon oils with cadmium salts
US2276526A (en) * 1939-04-03 1942-03-17 Shell Dev Process for refining hydrocarbon oils
US4170543A (en) * 1975-03-03 1979-10-09 Exxon Research & Engineering Co. Electrical insulating oil
DE2624239A1 (de) * 1976-05-29 1977-12-15 Reinhausen Maschf Scheubeck Vorrichtung zur aufbereitung des isolieroeles von hochspannungsgeraeten
US4498992A (en) * 1984-02-09 1985-02-12 Petro-Williams Service Company Process for treating contaminated transformer oil
US5208200A (en) * 1992-02-27 1993-05-04 Exxon Research And Engineering Co. Noble metal on rare earth modified silica alumina as hydrocarbon conversion catalyst
AU2001244705A1 (en) * 2000-03-31 2001-10-08 Idemitsu Kosan Co. Ltd. Desulfurizing agent for hydrocarbon derived from petroleum, method for producinghydrogen for use in fuel cell and method for producing nickel-based desulfurizi ng agent
US20040065618A1 (en) * 2001-02-16 2004-04-08 Ghaham Walter Ketley Purification process
US20050129952A1 (en) * 2003-09-29 2005-06-16 Questair Technologies Inc. High density adsorbent structures
BRPI0509337A (pt) * 2004-04-30 2007-07-24 Abb Technology Ltd método para remoção de enxofre reagente de óleo isolante

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010045958A1 *

Also Published As

Publication number Publication date
BRPI0823168A2 (pt) 2015-06-23
WO2010045958A1 (fr) 2010-04-29
CN102186959A (zh) 2011-09-14
US20110220552A1 (en) 2011-09-15
CA2740998A1 (fr) 2010-04-29

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