EP0417980A1 - Procédé de préparation d'huiles de production à basse teneur en aromatiques polycycliques - Google Patents

Procédé de préparation d'huiles de production à basse teneur en aromatiques polycycliques Download PDF

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Publication number
EP0417980A1
EP0417980A1 EP90309772A EP90309772A EP0417980A1 EP 0417980 A1 EP0417980 A1 EP 0417980A1 EP 90309772 A EP90309772 A EP 90309772A EP 90309772 A EP90309772 A EP 90309772A EP 0417980 A1 EP0417980 A1 EP 0417980A1
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Prior art keywords
weight
content
column
temperature
counter current
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EP90309772A
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German (de)
English (en)
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EP0417980B1 (fr
Inventor
Wolf-Dietrich Heinz BP Oiltech GmbH Glenz
Joachim Bp Oiltech Gmbh Holst
Horst Dieter BP Oiltech GmbH Müller
Reinhard Bp Oiltech Gmbh Wommelsdorff
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BP OIL DEUTSCHLAND GMBH
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BP Oil Deutschland GmbH
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G21/00Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents

Definitions

  • the invention relates to a process for the production of process oils with an aromatic content of more than 50 weight %, in particular more than 55 weight %, according to ASTM D 2007 and with a content of polycyclic aromatics (PCA) of less than 3 weight % according to IP346.
  • PCA polycyclic aromatics
  • Process oils are hydrocarbon mixtures boiling in the lubricating oil range which are not used as, or in connection with, lubricating oils but are used in other technological areas, e.g. as plasticisers or extenders.
  • aromatic types frequently show undesirably high contents in polycyclic compounds, i.e. compounds containing more than 2 condensed, aromatic nuclei.
  • plasticisers in natural and synthetic rubber types, e.g. for rubber mixtures for the running surfaces of vehicle tires, they give an improvement in the physical properties of the rubber vulcanisate, especially with reference to the elasticity and the related property of wet grip of the running surface mixture.
  • Other technical rubber articles plasticised with the above mentioned process oils show improved vibration damping properties.
  • the process oils of the above named type are described in German patent specification DE-A 23 43 238. They are there described as pseudo raffinate and are obtained as follows. A petroleum distillate boiling in the lubricating oil range is subjected to a counter current extraction with furfural, the resulting primary extract is freed from furfural and is again subjected to a second counter current extraction with furfural. The aromatic rich pseudo raffinate obtained in the second extraction step is freed from furfural and then treated with suitable solvents, e.g. methyl ethyl ketone and toluene, to remove wax and paraffin and finally catalytically hydrogenated. In the second extraction step the temperature at the head of the extraction column is in the range 40-100°C and that in the bottom of the column is 35-80°C. The volume ratio of the primary extract feed to the extraction solvent is in the range 1:0.5 to 1:2.5.
  • German patent specification DE-B 37 17 820 relates to a multi-stage extraction process with two counter current extraction columns and three or four separators.
  • the process of DE-B 37 17 820 however is directed to the removal of aromatic components from the lubricating oil fraction fed to the process with optimisation of the yield of raffinate.
  • process oils with a relatively low content in aromatic compounds, as a consequence of the required hydrogenation step.
  • process oils used as plasticisers or extenders for natural and synthetic rubber types frequently are required to have a high content in aromatic compounds.
  • content in polycyclic aromatic compounds should be as low as possible, in particular under 3 weight %.
  • a process for the production of process oils with an aromatic content of more than 50 weight % according to ASTM D 2007 and a content of polycyclic aromatic compounds of less than 3 weight % according to IP 346 characterised in that primary extract, obtained by treatment of a lubricating oil distillate originating from a mineral oil, is extracted in a counter current extraction cola with a polar solvent wherein the volume ratio of the primary extract feed to the polar solvent is in the range 1:1 to 1:1.8 and the head temperature in the counter current extraction column is 50-90°C and the bottom temperature in the column is 20-60°C and wherein the head temperature is higher than the bottom temperature.
  • the head temperature is to be understood as the temperature established in the uppermost part of the column (substantially depending on the feed temperature of the solvent and the primary extract stream) by which this can be controlled. It is practically identical with the temperature at which the product is taken off from the head of the column.
  • bottom temperature of the column is to be understood the lowest temperature in the extraction process; it is principally dependent on the temperature of the two process feed streams mentioned above, but is however normally influenced or regulated by additional cooling installations in the bottom region of the column.
  • the cooling installations can also be located outside the column and can be combined in this position with a separate separator, in which the product taken from the bottom of the column is separated into a heavier extract phase and a lighter phase, which is fed back into the bottom region of the column.
  • This lighter phase is frequently designated as "pseudo raffinate".
  • the temperature ruling in the separator vessel and which is practically identical with that of the recirculated light phase represents the bottom temperature in accordance with the claims.
  • the content of residual solvent in the feed material is preferably not higher than 20 volume %.
  • a primary extract is fed which has an aromatic content of 65-85 weight % according to ASTM D 2007.
  • the primary extract resulting from the extraction of lubricant distillate fractions contains 15-35 weight % of polycyclic aromatic compounds (PCA) according to IP 346; the content can however be above or below this range.
  • PCA polycyclic aromatic compounds
  • the preferred primary extracts for use in the process of the present invention have PCA contents of not more than 25 weight % according to IP 346.
  • the lower limit of PCA-content of the primary extract for the process of the invention lies above the target PCA-content of the product of the process of the invention.
  • the head temperature in the counter current extraction column is at least 10°C higher than the bottom temperature.
  • polar solvents is to be understood as covering the usual solvents used in the extraction of lubricating oil distillates, e.g. furfural, N-methylpyrrolidone and phenol; preferably furfural is used.
  • the process oil taken from the head of the counter current extraction colum is freed, in particular by distillation, from quantities of polar solvent. Further processing of the process oil obtained in accordance with the invention by dewaxing and deparaffining is possible. However subsequent processing by hydrogenation is excluded from the process of the present invention, as the content in polycyclic aromatics in the process oil of the invention already lies under 3 weight % and hydrogenation would reduce the desired high content in non polycyclic, aromatic compounds.
  • the process oils obtained by the process of the invention may be used in the technological areas in which aromatic rich mineral oil extracts have been used up to now.
  • they are preferably used as plasticisers or extenders for natural or synthetic rubber types, and as base oils for printing oil formulations.
  • the process of the invention will be further described below, with reference to the drawing.
  • the drawing shows a flow sheet for a preferred installation for carrying out the process of the present invention.
  • an installation for carrying out the process of the invention comprises a counter current extraction column of usual type (1).
  • Column (1) is connected by line (2) to a heat exchanger (3).
  • a polar solvent is fed through heat exchanger (3) via line (2) into column (1).
  • the process oil obtained according to the invention hereinafter designated as "mesoraffinate", is taken off at the head of the column by line (6).
  • the polar solvent containing the extracted constituents is taken off from the base of the extraction column through line (7) and fed through heat exchanger (8) to a separator (9), where the extract separates into two phases.
  • the upper phase frequently designated as pseudo raffinate, is returned by line (10) to the base of the extraction column; the lower phase, containing the polar solvent and enriched in the undesired polycyclic aromatic compounds, is removed from the installation by line (11).
  • the equipment for the removal and recovery of polar solvents from the process oil taken from the head of the column and from the base product containing the undesirable aromatic compounds are not shown.
  • the spatial separation of the extraction column (1) and the separator (9) is not essential; it is possible to integrate the separator (9) with the base of column (1).
  • the starting material was an extract obtained as a by-product of the preparation of a normal solvent-neutral oil by distillation of North Sea crude oil and subsequent extraction with furfural. It had the following chacteristics: TABLE 1 Density at 70°C (DIN 51557; kg/m2) 956 Viscosity at 40°C (DIN 51562; mm2/s) 1530 Viscosity at 100°C (DIN 51562; mm2/s) 30.5 Refractive index n D 20 (DIN 51423/T2) 1.560 Flashpoint COC (°C; DIN ISO 2592) 255 Pourpoint (°C; DIN ISO 3016) + 18 Aromatic content (weight %; ASTM D 2007) 74 Polycyclic aromatics (weight %; IP 346) 19
  • Examples 1 to 3 of the invention as well as Comparative Tests A and B were carried out with the above starting material.
  • the process conditions temperature at the head of the column and at the base of the column and the volume ratio extract: furfural
  • the experimental results yield in mesoraffinate in weight %, calculated on the starting material, aromatic content of the meso raffinate in weight % according to ASTM D 2007 and content of polycyclic aromatic compounds (PCA-content) in weight % according to IP 346) are set out in Table 2.
  • the Comparative Test A shows that a column head temperature outside the claimed temperature range reduces the PCA-content but at the same time also reduces the aromatic content of the final product to below 50 weight %.
  • the Comparative Test B shows that the use of a volume ratio of raffinate to furfural below that required by the claims leaves the aromatic content substantially unaffected but leaves the PCA content however at an undesirably high level.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP90309772A 1989-09-12 1990-09-06 Procédé de préparation d'huiles de production à basse teneur en aromatiques polycycliques Expired - Lifetime EP0417980B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3930422 1989-09-12
DE3930422A DE3930422A1 (de) 1989-09-12 1989-09-12 Verfahren zur herstellung von prozessoelen mit niedrigem gehalt an polycyclischen aromaten

Publications (2)

Publication Number Publication Date
EP0417980A1 true EP0417980A1 (fr) 1991-03-20
EP0417980B1 EP0417980B1 (fr) 1997-06-25

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EP90309772A Expired - Lifetime EP0417980B1 (fr) 1989-09-12 1990-09-06 Procédé de préparation d'huiles de production à basse teneur en aromatiques polycycliques

Country Status (5)

Country Link
EP (1) EP0417980B1 (fr)
DD (1) DD297660A5 (fr)
DE (2) DE3930422A1 (fr)
ES (1) ES2104589T3 (fr)
PT (1) PT95270B (fr)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0489371A1 (fr) * 1990-12-03 1992-06-10 Tudapetrol Mineralölerzeugnisse Nils Hansen Kg Mélanges d'hydrocarbures à haute teneur en arômes monocycliques et bicycliques
EP0839891A2 (fr) * 1996-10-31 1998-05-06 Repsol Petroleo S.A. Procédé pour l'obtention d'huiles à teneur en aromatiques polycycliques de moins que 3% utilisables comme huiles de production
ES2122917A1 (es) * 1996-10-31 1998-12-16 Repsol Petroleo Sa Proceso para la obtencion de aceites aromaticos con un contenido en compuestos aromaticos policiclicos inferior al 3 utiles como extensoresde cauchos.
EP0940462A2 (fr) * 1997-06-27 1999-09-08 Bridgestone Corporation Amelioration apportee a une huile a forte teneur en composes aromatiques, composition de caoutchouc et caoutchouc synthetique etendu a l'huile, prepares au moyen de ladite huile
EP0950703A2 (fr) * 1998-04-17 1999-10-20 Idemitsu Petrochemical Co., Ltd. Huile de traitement et son procédé de fabrication
EP0933418A3 (fr) * 1998-01-22 2000-01-05 Japan Energy Corporation Huile de processus pour caoutchouc et procédé pour sa production
EP1031621A2 (fr) * 1999-02-26 2000-08-30 Idemitsu Kosan Co., Ltd. Huile de processus, procédé pour sa production et compositions de caoutchouc
WO2000052115A1 (fr) * 1999-03-02 2000-09-08 Bp Oil International Limited Procede de traitement d'huile
US6146520A (en) * 1997-04-02 2000-11-14 Mobil Oil Corporation Selective re-extraction of lube extracts to reduce mutagenicity index
WO2001077257A1 (fr) * 2000-04-10 2001-10-18 Shell Internationale Research Maatschappij B.V. Procede de preparation d'une huile plastifiante
EP1177269A1 (fr) * 1999-03-10 2002-02-06 Miami University Procede d'extraction de contaminants de distillats de petrole
KR20020076626A (ko) * 2001-03-29 2002-10-11 금호산업 주식회사 저독성 연화제를 사용하여 내커팅/내칩핑 특성이 우수한트럭버스용 레디얼타이어 트래드고무조성물
KR20020076627A (ko) * 2001-03-29 2002-10-11 금호산업 주식회사 저독성 연화제를 사용하여 내열특성이 우수한 트럭버스용레디얼타이어 트래드고무조성물
EA010590B1 (ru) * 2005-03-14 2008-10-30 Закрытое Акционерное Общество «Торговый Дом "Оргхим"» Способ селективной очистки масляных фракций нефти от полициклических ароматических соединений
WO2011125042A1 (fr) 2010-04-09 2011-10-13 Total Raffinage Marketing Procede de purification des extraits aromatiques contenant des composes polycycliques aromatiques
WO2011145086A2 (fr) 2010-05-17 2011-11-24 Pt Pertamina (Persero) Procédé de production d'une huile de traitement à faible teneur en hydrocarbures polyaromatiques
CN102952570A (zh) * 2011-08-19 2013-03-06 中国石油天然气股份有限公司 两段逆流溶剂抽提制备环保橡胶油的方法
RU2520096C1 (ru) * 2013-04-23 2014-06-20 Закрытое акционерное общество "Торговый дом "Оргхим" Способ получения неканцерогенного ароматического технологического масла
US8864981B2 (en) 2011-01-14 2014-10-21 Cpc Corporation, Taiwan Feed mixtures for extraction process to produce rubber processing oil
TWI464252B (zh) * 2010-02-17 2014-12-11 Dahleke Klaus Kg 利用氫化製備環烷工藝油之方法
RU2550823C1 (ru) * 2014-05-21 2015-05-20 Александр Николаевич Волков Способ получения неканцерогенного ароматического технологического масла
US9567532B2 (en) 2012-10-09 2017-02-14 Orgkhim Biochemical Holding Management Company, Joint Stock Company (Orgkhim Bch Management Company, Jsc) Method for producing non-carcinogenic aromatic process oil
US11028332B2 (en) 2011-07-29 2021-06-08 Saudi Arabian Oil Company Integrated selective hydrocracking and fluid catalytic cracking process

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2557143A1 (fr) 2011-08-11 2013-02-13 Klaus Dahleke KG Procédé de fabrication d'huiles ramollissantes hautement naphténiques par hydrogénation
US20220251460A1 (en) 2021-02-08 2022-08-11 HollyFrontier LSP Brand Strategies LLC Methods of preparing naphthenic process oil via extraction and separation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2343238A1 (de) * 1972-08-30 1974-03-14 British Petroleum Co Verfahren zur behandlung von mineralschmieroel-ausgangsmaterialien

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3717820C1 (en) * 1987-05-27 1989-01-19 Schindler Oelwerke Gmbh Process for producing mineral oil cuts of lubricating oil quality by extraction with polar solvents

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2343238A1 (de) * 1972-08-30 1974-03-14 British Petroleum Co Verfahren zur behandlung von mineralschmieroel-ausgangsmaterialien

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0489371A1 (fr) * 1990-12-03 1992-06-10 Tudapetrol Mineralölerzeugnisse Nils Hansen Kg Mélanges d'hydrocarbures à haute teneur en arômes monocycliques et bicycliques
EP0839891A2 (fr) * 1996-10-31 1998-05-06 Repsol Petroleo S.A. Procédé pour l'obtention d'huiles à teneur en aromatiques polycycliques de moins que 3% utilisables comme huiles de production
EP0839891A3 (fr) * 1996-10-31 1998-07-29 Repsol Petroleo S.A. Procédé pour l'obtention d'huiles à teneur en aromatiques polycycliques de moins que 3% utilisables comme huiles de production
ES2122917A1 (es) * 1996-10-31 1998-12-16 Repsol Petroleo Sa Proceso para la obtencion de aceites aromaticos con un contenido en compuestos aromaticos policiclicos inferior al 3 utiles como extensoresde cauchos.
ES2137123A1 (es) * 1996-10-31 1999-12-01 Repsol Petroleo Sa Mejoras introducidas en el objeto de la patente principal 9602311, presentada el 31 de octubre de 1996, sobre: un proceso para la obtencion de aceites aromaticos con un contenido en compuestos aromaticos policiclicos inferior al 3.
US6146520A (en) * 1997-04-02 2000-11-14 Mobil Oil Corporation Selective re-extraction of lube extracts to reduce mutagenicity index
EP0940462A2 (fr) * 1997-06-27 1999-09-08 Bridgestone Corporation Amelioration apportee a une huile a forte teneur en composes aromatiques, composition de caoutchouc et caoutchouc synthetique etendu a l'huile, prepares au moyen de ladite huile
EP0940462A4 (fr) * 1997-06-27 2005-03-02 Bridgestone Corp Amelioration apportee a une huile a forte teneur en composes aromatiques, composition de caoutchouc et caoutchouc synthetique etendu a l'huile, prepares au moyen de ladite huile
EP0933418A3 (fr) * 1998-01-22 2000-01-05 Japan Energy Corporation Huile de processus pour caoutchouc et procédé pour sa production
US6878263B2 (en) 1998-01-22 2005-04-12 Japan Energy Corporation Rubber process oil and production process thereof
US6248929B1 (en) 1998-01-22 2001-06-19 Japan Energy Corporation Rubber process oil and production process thereof
EP0950703A3 (fr) * 1998-04-17 2000-01-05 Idemitsu Petrochemical Co., Ltd. Huile de traitement et son procédé de fabrication
EP0950703A2 (fr) * 1998-04-17 1999-10-20 Idemitsu Petrochemical Co., Ltd. Huile de traitement et son procédé de fabrication
US6410816B2 (en) * 1998-04-17 2002-06-25 Idemitsu Kosan Co., Ltd. Processing oil and method for producing the same
EP1031621A2 (fr) * 1999-02-26 2000-08-30 Idemitsu Kosan Co., Ltd. Huile de processus, procédé pour sa production et compositions de caoutchouc
US6605695B2 (en) 1999-02-26 2003-08-12 Idemitsu Kosan Co., Ltd. Process oil, process for producing the same and rubber composition
EP1031621A3 (fr) * 1999-02-26 2000-11-29 Idemitsu Kosan Co., Ltd. Huile de processus, procédé pour sa production et compositions de caoutchouc
US6399697B1 (en) 1999-02-26 2002-06-04 Idemitsu Kosan Co., Ltd. Process oil, process for producing the same and rubber composition
US6802960B1 (en) 1999-03-02 2004-10-12 Bp Oil International Limited Two stage extraction oil treatment process
WO2000052115A1 (fr) * 1999-03-02 2000-09-08 Bp Oil International Limited Procede de traitement d'huile
EP1177269A4 (fr) * 1999-03-10 2003-06-18 Univ Miami Procede d'extraction de contaminants de distillats de petrole
EP1177269A1 (fr) * 1999-03-10 2002-02-06 Miami University Procede d'extraction de contaminants de distillats de petrole
WO2001077257A1 (fr) * 2000-04-10 2001-10-18 Shell Internationale Research Maatschappij B.V. Procede de preparation d'une huile plastifiante
US7186876B2 (en) 2000-04-10 2007-03-06 Shell Oil Company Process to prepare a process oil
KR20020076627A (ko) * 2001-03-29 2002-10-11 금호산업 주식회사 저독성 연화제를 사용하여 내열특성이 우수한 트럭버스용레디얼타이어 트래드고무조성물
KR20020076626A (ko) * 2001-03-29 2002-10-11 금호산업 주식회사 저독성 연화제를 사용하여 내커팅/내칩핑 특성이 우수한트럭버스용 레디얼타이어 트래드고무조성물
EA010590B1 (ru) * 2005-03-14 2008-10-30 Закрытое Акционерное Общество «Торговый Дом "Оргхим"» Способ селективной очистки масляных фракций нефти от полициклических ароматических соединений
TWI464252B (zh) * 2010-02-17 2014-12-11 Dahleke Klaus Kg 利用氫化製備環烷工藝油之方法
WO2011125042A1 (fr) 2010-04-09 2011-10-13 Total Raffinage Marketing Procede de purification des extraits aromatiques contenant des composes polycycliques aromatiques
FR2958655A1 (fr) * 2010-04-09 2011-10-14 Total Raffinage Marketing Procede de purification des extraits aromatiques contenant des composes polycycliques aromatiques
CN102884160A (zh) * 2010-04-09 2013-01-16 道达尔炼油与销售部 纯化含芳族多环化合物的芳烃提取物的方法
CN102884160B (zh) * 2010-04-09 2016-01-20 道达尔炼油与销售部 纯化含芳族多环化合物的芳烃提取物的方法
RU2547659C2 (ru) * 2010-04-09 2015-04-10 Тоталь Маркетин Сервис Способ очистки ароматических экстрактов, содержащих ароматические полициклические соединения
WO2011145086A3 (fr) * 2010-05-17 2012-06-28 Pt Pertamina (Persero) Procédé de production d'une huile de traitement à faible teneur en hydrocarbures polyaromatiques
CN102971400A (zh) * 2010-05-17 2013-03-13 印尼国家石油和天然气公司 生产具有低含量的多环芳烃的加工油的方法
WO2011145086A2 (fr) 2010-05-17 2011-11-24 Pt Pertamina (Persero) Procédé de production d'une huile de traitement à faible teneur en hydrocarbures polyaromatiques
CN102971400B (zh) * 2010-05-17 2016-02-10 印尼国家石油和天然气公司 生产具有低含量的多环芳烃的加工油的方法
US8864981B2 (en) 2011-01-14 2014-10-21 Cpc Corporation, Taiwan Feed mixtures for extraction process to produce rubber processing oil
US11028332B2 (en) 2011-07-29 2021-06-08 Saudi Arabian Oil Company Integrated selective hydrocracking and fluid catalytic cracking process
CN102952570B (zh) * 2011-08-19 2014-12-24 中国石油天然气股份有限公司 两段逆流溶剂抽提制备环保橡胶油的方法
CN102952570A (zh) * 2011-08-19 2013-03-06 中国石油天然气股份有限公司 两段逆流溶剂抽提制备环保橡胶油的方法
US9567532B2 (en) 2012-10-09 2017-02-14 Orgkhim Biochemical Holding Management Company, Joint Stock Company (Orgkhim Bch Management Company, Jsc) Method for producing non-carcinogenic aromatic process oil
WO2014175770A1 (fr) * 2013-04-23 2014-10-30 Закрытое акционерное общество "Торговый дом "Оргхим" Procédé de production d'une huile technique aromatique non cancérigène
RU2520096C1 (ru) * 2013-04-23 2014-06-20 Закрытое акционерное общество "Торговый дом "Оргхим" Способ получения неканцерогенного ароматического технологического масла
RU2550823C1 (ru) * 2014-05-21 2015-05-20 Александр Николаевич Волков Способ получения неканцерогенного ароматического технологического масла

Also Published As

Publication number Publication date
DE69030970T2 (de) 1997-12-18
PT95270A (pt) 1991-05-22
DE69030970D1 (de) 1997-07-31
EP0417980B1 (fr) 1997-06-25
DE3930422A1 (de) 1991-03-21
DD297660A5 (de) 1992-01-16
ES2104589T3 (es) 1997-10-16
PT95270B (pt) 1997-09-30

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