US3714021A - Thermally stable insulating oil - Google Patents

Thermally stable insulating oil Download PDF

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Publication number
US3714021A
US3714021A US00083232A US3714021DA US3714021A US 3714021 A US3714021 A US 3714021A US 00083232 A US00083232 A US 00083232A US 3714021D A US3714021D A US 3714021DA US 3714021 A US3714021 A US 3714021A
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United States
Prior art keywords
thermally stable
insulating oil
polycyclic
hydrocarbons
oil
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Expired - Lifetime
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US00083232A
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English (en)
Inventor
M Takahashi
A Ito
T Yamauchi
K Okuda
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Kureha Corp
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Kureha Corp
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/12—Electrical isolation oil

Definitions

  • .i member eected from the group consisting of a polya r 208/ cyclic aromatic hydrocarbon, its lower alkyl derivative Int. Cl. ..Cl0g 37/06 and a mixture thereof 1 Field of Search ..208/l4, l9
  • the present invention relates to an insulating oil having superior thermal stability, and more particularly, it relates to a novel electrical insulating oil comprising a mixture of a polycyclic naphthenic hydrocarbon having two or more rings in the molecule and a polycyclic aromatic hydrocarbon having two or more rings in the molecule.
  • the present invention is based on the discovery that the gas absorption'performanceof an insulating oil is unexpectedly improved, more so than any other electrical characteristic, and thethermal stability in the presence of oxygen is also greatly enhanced by admixing a polycyclic aromatic hydrocarbon, having two or more rings in the molecule, to a'particular hydrocarbon mixture comprising polycyclic naphthenes having two or more rings in the molecule.
  • the primary object of the present invention is to provide an electrical insulating oil having improved properties.
  • the present invention provides an electrical insulating oil comprising a mixture of from 95- to 20 percent, by volume, of a polycyclic naphthenic hydrocarbonof two or more rings or alkyl derivatives thereof or a mixture thereof, and 5 to 80 percent, by volume, of a polycyclic aromatic hydrocarbon of two or more rings or alkyl derivatives thereof or a mixture thereof.
  • polycyclic naphthenic hydrocarbons which may be used in this invention include, for example, decaline, perhydrophenanthrene, perhydropyrene, perhydrofluorene, perhydroanthracene, perhydrochrysene, and like cyclic naphthenes having two i to five rings, or C or lower, preferably C or lower,
  • Viscosity (30C) cst 10-40 Hydrogen/carbon atomic ratio (hereinafter indicated by H/C) 1.75-2.00 Ignition point 1 25C Pour point 30 to 60C Dielectric constant (a) (C) Dielectric tangent tan 8 (80C) 0.00l
  • this conventional oil has an inferior gas absorptivity.
  • this disadvantage has been overcome by the addition of certain polycyclic aromatic compounds to the polycyclic naphthenic hydrocarbon without adversely affecting its inherent electrical properties.
  • the polycyclic aromatic hydrocarbon employed as the other component in the oil of the present invention includes polycyclic aromatics having from 2 to 4 rings such as, for example, naphthalene, diphenyl, acenaphthene, fluorene, terphenyl, pyrene, chrysene, and C or lower, alkyl derivatives thereof, and mixtures of two or more such compounds.
  • an arc matic hydrocarbon in which a portion of the ring is saturated with hydrogen such as acenaphthene, can be used without departing from the scope of the present invention.
  • the oil of the present invention has an excellent gas absorptivity as well as excellent electrical properties.
  • polycyclic naphthenic hydrocarbons and the polycyclic aromatic hydrocarbons used in the present invention are easily obtainable by desulfurizing and alkylating (with lower olefins) and/or nuclear hydrogenating bottom oils or tarry materials rich in aromatic compounds, the latter type of material is, for example, formed during the thermal cracking of petroleum hydrocarbons (crude oil, heavy oil, light oil, kerosene, naphtha and the like petroleum fractions) at a temperature of above 700C but below 2,300C for a period of time of 1-0.001 second to produce ethylene and/or acetylene, or an oil tar from the gasification of heavy or crude oil at a high temperature, or coal tar, or bottom oil from the dealkylation of alkylaromatics (e.g., the bottom oil from toluene dealkylation during benzene production).
  • petroleum hydrocarbons crude oil, heavy oil, light oil, kerosene, naphtha and the like petroleum fractions
  • the desulfurization is conducted employing conventional reaction conditions and conventional catalysts at a temperature of 350-450C, a pressure of 20-100 Kg/cm a hydrogen/high aromatic oil molar ratio of 5-20, and an LHSV of 0.5-2.0.
  • the catalyst which may be employed includes cobalt-molybdenum, nickelmolybdenum, nickel-cobalt-molybdenum, etc., which may be supported on alumina or silica-alumina.
  • the alkylation is carried out in the presence of a catalyst by admixing a tarry fraction with an olefin gas.
  • reaction conditions to be employed are as follows:
  • Reaction temperature 250 380C Pressure 1 50 Kg/crn Olefin/tar (molar ratio) 0.2 Liquid hourly space velocity (LHSV) 0.1 -3.0
  • the catalyst employed in the alkylation may be an acidic catalyst such as silica-alumina, zeolite, etc., but the use of a catalyst in which a Group lll-B metal, such as lanthanum, cerium or thorium, is supported on zeolite is especially effective. Under these conditions, the alkylation proceeds smoothly to give the desired product in a good yield.
  • the degree of alkylation can be controlled to the desired extent by modifying the olefin/tar mixing ratio or liquid hourly space velocity (LHSV).
  • LHSV liquid hourly space velocity
  • the electrical properties of the product are not sig nificantly influenced by the type of alkyl group introduced as long as it is not larger than C
  • the specific alkyl group employed is determined based on economics, considering the availability of the material.
  • the degree of alkylation is suitably controlled, in
  • the hydrogenation reaction is conducted under conventional conditions employed in the art.
  • Preferred hydrogenation catalysts to be used are exemplified by the oxides, sulfides, etc., of Group VI, VII and VIII metals of the Periodic Table. These catalysts may be supported on carriers such as activated carbon fullers earth, diatomaceous earth, bauxite, pumice stone, silica-alumina, etc.
  • the reaction is ordinarily conducted at a temperature of 100-450C, under a pressure of 10-300 kglcm at a liquid hourly space velocity (LHSV) of 0.5-2.0, and at a hydrogen/alkylated high aromatic oil molar ratio of 5-20.
  • LHSV liquid hourly space velocity
  • polycyclic naphthen s and polycyclic aromatics should be mixed, according to the present invention, in most cases within a range of -20 percent, by volume, of the former to 5-80 percent, by volume, of the latter, although this ratio varies to some extent depending upon the type of electrical equipment to be used.
  • An increased proportion of polycyclic naphthenes beyond the above stated range will result in a decrease in gas absorptivity, and a proportion less than the stated range will cause poorer electrical properties.
  • the insulating oil obtained according to this invention has demonstrated outstanding and excellent results, especially when used as a transformer oil, a cable oil and a condenser oil having thermal resistance.
  • EXAMPLE 1 A tarry material obtained by treating Seria crude oil at 1250C for a contact time of 0.005 second was determined by analysis to have an aromatic distribution comprising 47 percent dicyclic compounds, 33 percent tricyclic compounds, 19 percent tetracyclic compounds and 1 percent pentacyclic compounds, and determined by NMR to have a total of 7 percent side chain hydrogen comprising 4 percent CH and 3 percent CH
  • This tarry material was desulfurized in a hydrogen gas stream by using an ordinary desulfurization catalyst consisting of cobalt-molybdenum-alumina, then alkylated with ethylene using silicaalumina as a catalyst to give a polycyclic aromatic hydrocarbon
  • a bottom oil material was obtained as a by-product in the production of ethylene-propylene by the thermal cracking of Kuwait naphtha at 800C for the contact 5 mlxture time of 0.5 second.
  • This bottom oil had an aromatic
  • the mixture had bolhong P (calfillllated at ring distribution comprising 76 percent dicyclic comnormal P 280 pQ l P after pounds, 21 percent tricyclic compounds and 3 percent type analysis by silica gel absorption comprising 99.1 tetracyclic compounds, and total side chain hydrogen weight percent aromatics and 0.9 weight percent nonof 20 percent comprising 5% CH 5% CH and 10% aromatics, and, by Mass spectrometry analysis, com- CH --Cl-l by NMR analysis, which was an aromatic oil prising 60.1 percent dicyclic rings, 35.4 percent comalniflg relatively y Side Chaiflstricyclic rings and 4.5 percent tetracyclic rings.
  • This oil was desulfurized in a manner similar to that A portion of (B) was completely nuclearshown in Example 1 to prepare a polycyclic aromatic hydrogenated using a conventional nickel-alumina type hydrocarbon t ,7 catalyst to form a polycyclic naphthenic hydrocarbon had the followmg Propemesi bollmg P l' mixture culated at normal pressure) 280-380C, a composi- (A) had the following properties: boiling point (cal- P 9?
  • tyPehanalyss by 5 wfw culated at normal pressure 290-370C
  • a composi- L 6 P :5 i a t tion after type analysis by silica gel absorption comprise mma a y Spe.c tome ry ana in 2 6 Wei ht cream aromatics and 97 4 Wei ht er comprising 70.5 percent dicyclic rings, 26.8 percent g g M g tricyclic rings and 2.7 tetracyclic rings.
  • the material oil used in this example was a byproduct bottom oil formed in a process for the production of ethylene and propylene were Kuwait naphtha was thermally cracked in a tubular furnace at a reaction temperature of 830C for the contact time of 0.4 second.
  • This bottom oil was hydrogenated using a nickel-molybdenum-alumina catalyst in the presence of hydrogen at a temperature of 350C, an LHSV of 0.8 and under a pressure of 40 Kglcm G.
  • the resulting hydrogenated product was then reacted with 1.5 mole equivalents of propylene in the presence of a silica-alumina type catalyst under apressure of 10 Kg/cm, an LHSV of 1.0 and at a temperature of 200C.
  • a thermally stable electrical insulating oil with improved gas absorption performance comprising from 5 to 80 percent by volume ofa member selected from the group consisting of one or more polycyclic naphthenic hydrocarbons, lower alkyl derivatives thereof and a mixture of such naphthenic hydrocarbons and lower alkyl derivatives, and from 95 to percent by volume of a mem lle selected from the group consisting of one or more polycyclic aromatic hydrocarbons, lower alkyl derivatives thereof and a mixture of such aromatic hydrocarbons and lower alkyl derivatives, the polycyclic naphthenic hydrocarbons being obtained by hydrogenating an aromatic fraction which is obtained by the thermal cracking of petroleum hydrocarbons at a temperature above 700C.
  • the thermally stable insulating oil of claim 1 wherein the one or more polycyclic naphthenic hydrocarbons, lower alkyl derivatives thereof and mixtures thereof, have a specific gravity d of from 0.85 to 0.99, a refractive index n of from 1.45 to 1.60, a viscosity (30C.) of from 10 to 40 cst, a hydrogen/carbon atomic ratio of from 1.75 to 2.00, an ignition point of above 125C., and a pour point of from --30 to 60 C.
  • thermoly stable insulating oil of claim 1 wherein the one or more polycyclic aromatic hydrocarbons, lower alkyl derivatives thereof and mixtures thereof, have a specific gravity d of from 1.00 to 1.20, a refractive index n of from 1.50 to 1.68, a viscosity (30C.) of from 10 to 25 est, an ignition point of above 150C., and a pour point of below -40C.
  • thermoly stable insulating oil of claim 1 wherein more than one polycyclic naphthenic hydrocarbon is present as a mixture of polycyclic naphthenic hydrocarbons, each having from two to five rings, their lower alkyl derivatives or a mixture thereof.
  • the thermally stable insulating oil of claim 1 wherein the polycyclic aromatic hydrocarbon is a mixture of polycyclic hydrocarbons each having from two to four rings, their lower alkyl derivatives or a mixture thereof.
  • thermoly stable insulating oil of claim 1 wherein the polycyclic naphthenic hydrocarbons, lower alkyl derivatives thereof and mixtures thereof are obtained by desulfurization, alkylation and hydrogenation of an aromatic fraction which is obtained by the high temperature cracking of petroleum hydrocarbons.
  • thermally stable insulating oil of claim 6 wherein the alkylation is carried out with butylene, propylene or ethylene.
  • thermoly stable insulating oil of claim 1 wherein the polycyclic aromatic hydrocarbons are obtained by desulfurization and alkylation of an aromatic fraction which is obtained by the high temperature thermal cracking of the petroleum hydrocarbons.
  • thermally stable insulating oil of claim 8 wherein the alkylation is carried out with butylene, propylene or ethylene.
  • thermoly stable insulating oil of claim 1 wherein the alkyl portion of the lower alkyl derivatives contains less than eight carbon atoms.
  • the thermally stable insulating oil of claim 10 wherein the alkyl portion of the alkyl derivative contains four or less carbon atoms.
  • thermally stable insulating oil of claim I having the following properties:
  • the thermally stable insulating oil of claim 13 wherein the polycyclic hydrocarbons are obtained by desulfurization and alkylation of an aromatic fraction obtained by the high temperature cracking of the petroleum hydrocarbons at a temperature greater than 700C. to yield the polycyclic aromatic hydrocarbons, and a portion of the polycyclic aromatic hydrocarbons is thereafter hydrogenated to' yield the polycyclic naphthenic hydrocarbons, the polycyclic naphthenic and the polycyclic aromatic hydrocarbons thereafter being blended to yield the thermally stable insulating oil.
  • thermally stable insulating oil of claim 13 wherein the thermal cracking is at a temperature of above 700C but below 2,300C for a period of time above from 1 to 0.001 seconds.
  • the thermally stable insulating oil of claim 14 wherein the material cracked is selected from the group consisting of crude oil, heavy oil, light oil, kerosene, naphtha, an oil tar from the gasification of heavy or crude oil at a high temperature, a coal tar or a bottom oil from the dealkylation of alkyl aromatics.
  • the thermally stable insulating oil of claim 1 wherein the polycyclic naphthenic hydrocarbon is selected from the group consisting of decaline, perhydrophenanthrene, perhydropyrene, perhydrofluorene, perhydroanthracene and perhydrochrysene, alkyl derivatives thereof wherein the alkyl group contains eight or less carbon atoms, and mixtures thereof.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)
US00083232A 1969-10-22 1970-10-22 Thermally stable insulating oil Expired - Lifetime US3714021A (en)

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JP44084060A JPS4931279B1 (enrdf_load_stackoverflow) 1969-10-22 1969-10-22

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JP (1) JPS4931279B1 (enrdf_load_stackoverflow)
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844931A (en) * 1971-06-30 1974-10-29 Japan Gasoline Method of manufacturing special solvent
US4170543A (en) * 1975-03-03 1979-10-09 Exxon Research & Engineering Co. Electrical insulating oil
US4387256A (en) * 1980-09-02 1983-06-07 Imperial Oil Limited Traction fluid lubricants derived from coal tar
US4533778A (en) * 1981-01-21 1985-08-06 Imperial Oil Limited Traction fluid lubricants derived from mineral oil
US4899009A (en) * 1987-09-09 1990-02-06 Nippon Petrochemicals Co. Ltd. Method for producing m-benzyltolune
US4902841A (en) * 1987-03-11 1990-02-20 Nippon Petrochemicals Company, Ltd. Method for producing electrical insulating oil composition
US4982025A (en) * 1988-03-09 1991-01-01 Nippon Petrochemicals Company, Limited Electrical insulating oil comprising improved fraction
US20030211949A1 (en) * 2002-03-06 2003-11-13 Pierre-Yves Guyomar Hydrocarbon fluids
US20060100467A1 (en) * 2004-11-08 2006-05-11 Holmes Steven A Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same
US20060100466A1 (en) * 2004-11-08 2006-05-11 Holmes Steven A Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5164192U (enrdf_load_stackoverflow) * 1974-11-14 1976-05-20
JPS5281729U (enrdf_load_stackoverflow) * 1975-12-15 1977-06-18

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846372A (en) * 1954-07-15 1958-08-05 Sun Oil Co Stabilized petroleum oils
US3095366A (en) * 1960-03-03 1963-06-25 Standard Oil Co Insulating oil
US3252887A (en) * 1962-11-20 1966-05-24 Exxon Research Engineering Co Electrical insulating oil
US3406111A (en) * 1960-03-18 1968-10-15 Sun Oil Co Transformer oil
US3462358A (en) * 1967-03-11 1969-08-19 Sun Oil Co Clay treatment of hydrorefined cable oils

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846372A (en) * 1954-07-15 1958-08-05 Sun Oil Co Stabilized petroleum oils
US3095366A (en) * 1960-03-03 1963-06-25 Standard Oil Co Insulating oil
US3406111A (en) * 1960-03-18 1968-10-15 Sun Oil Co Transformer oil
US3252887A (en) * 1962-11-20 1966-05-24 Exxon Research Engineering Co Electrical insulating oil
US3462358A (en) * 1967-03-11 1969-08-19 Sun Oil Co Clay treatment of hydrorefined cable oils

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844931A (en) * 1971-06-30 1974-10-29 Japan Gasoline Method of manufacturing special solvent
US4170543A (en) * 1975-03-03 1979-10-09 Exxon Research & Engineering Co. Electrical insulating oil
US4387256A (en) * 1980-09-02 1983-06-07 Imperial Oil Limited Traction fluid lubricants derived from coal tar
US4533778A (en) * 1981-01-21 1985-08-06 Imperial Oil Limited Traction fluid lubricants derived from mineral oil
US4902841A (en) * 1987-03-11 1990-02-20 Nippon Petrochemicals Company, Ltd. Method for producing electrical insulating oil composition
US4899009A (en) * 1987-09-09 1990-02-06 Nippon Petrochemicals Co. Ltd. Method for producing m-benzyltolune
US4982025A (en) * 1988-03-09 1991-01-01 Nippon Petrochemicals Company, Limited Electrical insulating oil comprising improved fraction
US20030211949A1 (en) * 2002-03-06 2003-11-13 Pierre-Yves Guyomar Hydrocarbon fluids
US7056869B2 (en) * 2002-03-06 2006-06-06 Exxonmobil Chemical Patents Inc. Hydrocarbon fluids
US20060100467A1 (en) * 2004-11-08 2006-05-11 Holmes Steven A Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same
US20060100466A1 (en) * 2004-11-08 2006-05-11 Holmes Steven A Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same
US7531083B2 (en) 2004-11-08 2009-05-12 Shell Oil Company Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same

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Publication number Publication date
DE2051934B2 (de) 1972-11-16
GB1332509A (en) 1973-10-03
DE2051934A1 (de) 1971-05-13
JPS4931279B1 (enrdf_load_stackoverflow) 1974-08-20

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