EP1130077A2 - Brai d'huile de pétrole à forte teneur en composés aromatiques, sa préparation et son utilisation dans la fabricage d'électrodes - Google Patents

Brai d'huile de pétrole à forte teneur en composés aromatiques, sa préparation et son utilisation dans la fabricage d'électrodes Download PDF

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Publication number
EP1130077A2
EP1130077A2 EP01500047A EP01500047A EP1130077A2 EP 1130077 A2 EP1130077 A2 EP 1130077A2 EP 01500047 A EP01500047 A EP 01500047A EP 01500047 A EP01500047 A EP 01500047A EP 1130077 A2 EP1130077 A2 EP 1130077A2
Authority
EP
European Patent Office
Prior art keywords
petroleum
pitches
procedure
carbon
less
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Withdrawn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
EP01500047A
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German (de)
English (en)
Other versions
EP1130077A3 (fr
Inventor
Eduardo Romero Palazon
Carlos Gomez De Salazar Fernandez
Andres Castillo Azuaga
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.)
Repsol Petroleo SA
Original Assignee
Repsol Petroleo SA
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 Repsol Petroleo SA filed Critical Repsol Petroleo SA
Publication of EP1130077A2 publication Critical patent/EP1130077A2/fr
Publication of EP1130077A3 publication Critical patent/EP1130077A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means

Definitions

  • the present invention relates to a procedure for producing petroleum pitches of the type termed commercially as " binding” or “ impregnating” , to the pitch so obtained and to its use in the fabrication of anodes for the Aluminium industry, electrographites for steel production, and also the conforming, agglomeration and impregnation of carbon compounds and ceramic (refractory) materials, and in the production of general purpose carbon fibres.
  • the pitches that constitute the purpose of the present invention are produced from petroleum fractions and residues and have the advantage, when compared to those presently in use and obtained from the distillation of coal tar, of being much less toxic and less polluting in terms of poly-aromatic hydrocarbons (benzo(a)pyrene, crysene, dibenzo-anthracene, etc.).
  • the materials employed for binding or impregnating must fulfil different characteristics among which are:
  • the petroleum pitches obtained according to the procedure claimed herein have the exceptional virtue of being environmentally clean: they produce practically no polluting gaseous emissions, like carcinogenic polyaromatics of the benzo(a)pyrene, crysene, dibenzoanthracene, etc. types.
  • the objective of this invention is to define the process and operating conditions in order that through the heat treatment of petroleum fractions or residues selected for this purpose, they evolve; and by combining cracking, dehydrogenation and polymerisation reactions it is possible to obtain a petroleum pitch with suitable properties to be used for binding or impregnating in the production of anodes for the production of Aluminium, electrographites for producing steel, in the manufacture of whatever composition or conglomerate of a carbonaceous nature and in the production of carbon fibres.
  • this petroleum pitch is environmentally " cleaner" than that of coal tar.
  • the equivalent content in benzo(a)pyrene is below 4000 ppm; the emission of PAHs in gases being less than 6 mg/m 3 . In both cases these contents imply a reduction of 85-95% in comparison with those encountered in coal tar pitches.
  • the present invention provides a procedure for obtaining non-polluting petroleum pitches, of the binding or impregnating type, said procedure comprising the subjecting of a petroleum fraction or residue to a heat treatment at temperatures lying between 350° and 470° C, preferably between 370° and 430° C, for a time less than 120 minutes, preferably less than 60 minutes and under a pressure under 20 atmospheres absolute, preferably under 10 atmospheres absolute.
  • the input material for producing petroleum pitches according to the invention includes industrial petroleum residues, such as atmospheric petroleum residues, residues obtained under reduced pressure conditions, or heavy petroleum oils coming from thermal or catalytic cracking of petroleum-derived products.
  • the feed selected is held in a tank (A) at between 100° and 150° C, is extracted by pump (B) and heated in an oven (C) up to a minimum temperature of 300° C without undergoing any change in chemical composition.
  • a flash distillation column (D) in order to remove the light distillates and then to a stirred reaction chamber (E), or else directly without passing through the distillation column (D), to the said stirred reaction chamber.
  • the distillates are sent to a fractioning column (F) in order to be used later.
  • the reaction chamber (E) the product is treated thermally with the provision of external heat in order maintain the temperature constant. This temperature shall be maintained between 350° and 470° C, preferably between 370° and 430° C, for a dwelling time less than 120 minutes, preferably less than 60 minutes and under a pressure under 20 atmospheres absolute, and preferably under 10 atmospheres absolute.
  • the product so obtained proves to be a highly aromatic pitch, with anisotropy contents variable in the range 0-70% (measured as a mesophase percentage observed in a polarised light optical microscope over a total of 5000 points), at the will of the producer, and insoluble in Toluene and Quinoline within the range 0-50% and 0-30% respectively, also at the will of the producer, through the control of the variables in this new process.
  • These new petroleum pitches can replace those currently being used by manufacturers of electrodes, electrographites and carbon compositions with no need to alter any stage of their productive system since they adapt to the latter and satisfy the specifications set by the user in each case. Likewise they can be used as agglomerating agent in refractory products and a base material for producing general purpose carbon fibre.
  • the present invention provides a highly aromatic petroleum pitch, which has the following properties:
  • the present invention provides for the use of highly aromatic petroleum pitches which have the properties aforementioned and obtained by the procedure described above, in the manufacture of anodes, in particular anodes for the aluminium industry, electrographites for steel production, as well as in the conforming, agglomerating and impregnating of carbon compositions and graphitic materials and in the fabrication of carbon fibres.
  • the resulting product termed petroleum pitch, has the following properties: Matter insoluble in Toluene(% by weight) 31.2 Matter insoluble in Quinoline(% by weight) 13.1 Viscosity at 177° C (cP) 1210 Viscosity at 240° C (cP) 280 Ring and Ball (°C) 118 Sulphur (% by weight) 2.2 Fixed carbon yield (% by weight) 57
  • this petroleum pitch is environmentally " cleaner" than that of coal tar since its content in PAHs measured as equivalent benzo(a)pyrene is 3600 ppm with a PAH emission in gases of 6 mg/m 3 . In both cases these contents imply a reduction of 85-95% in comparison with the figures corresponding coal tar pitches presently in use.
  • This petroleum pitch can replace those in use by manufacturers of electrodes, electrographites and carbon compositions without any requirement to alter any stage in their productive system since they adapt to the latter and satisfy the specifications set by the user in each case.
  • the resulting product termed petroleum pitch, has the properties indicated in Table II, column A: Example 2 3 Column A B Matter insoluble in Toluene(% by weight) 27.6 22.01 Matter insoluble in Quinoline(% by weight) ⁇ 0.1 ⁇ 0.1 Viscosity at 177° C (cP) 7500 474 Viscosity at 204° C (cP) 1150 119 Ring and Ball (°C) 149 100 Sulphur (% by weight) ⁇ 0.1 ⁇ 0.1 Carbon yield (% by weight) 59 51 Commercial equivalent " binding " " impregnating "
  • This petroleum pitch is environmentally " cleaner” than those of coal tar for its low Sulphur content (less than 0.1% by weight) and the low PAH concentration (measured as equivalent benzo(a)pyrene) present in it (3290 ppm) and its low PAH emission in gases of (5 mg/m 3 ), but in addition it can replace the pitches presently in use by manufacturers of electrodes, electrographites and carbon compositions without any requirement to alter any stage in their productive system since they adapt to the latter and satisfy the specifications set by the user in each case, with the advantage of having, with respect to coal tar pitches, 85-95% less PAHs expressed as equivalent benzo(a)pyrene.
  • the resulting product termed petroleum pitch, has the properties indicated in Table II, column B.
  • This petroleum pitch is " cleaner" than those of coal tar for its low Sulphur content (less than 0.1% by weight) and the low equivalent benzo(a)pyrene concentration present in the pitch (1820 ppm) and PAH emission in gases (4 mg/m 3 ), but in addition it proves to be a product which can replace the pitches presently in use by manufacturers of electrodes, electrographites and carbon compositions without any requirement to alter any stage in their productive system since they adapt to the latter and satisfy the specifications set by the user in each case, with the advantage of having, with respect to coal tar pitches, 85-95% less PAHs expressed as equivalent benzo(a)pyrene.
  • This petroleum pitch is " cleaner” than those of coal tar for its low Sulphur content (less than 0.1% by weight) and the low concentration of PAHs measured as equivalent benzo(a)pyrene present in the pitch (2250 ppm) and PAH emissions in gases (4 mg/m 3 ).
  • This pitch has an important facility for extrusion, producing mono-filaments in a continuous and highly uniform manner.
  • a coal tar in order to alter determined properties of the pitches, for example the wettability, can be added to the petroleum residue or fraction before subjecting the latter to the heat treatment, said coal tar being in amounts lying between 10 and 90% by weight and preferably between 30 and 70%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Ceramic Products (AREA)
  • Working-Up Tar And Pitch (AREA)
EP01500047A 2000-03-01 2001-02-23 Brai d'huile de pétrole à forte teneur en composés aromatiques, sa préparation et son utilisation dans la fabricage d'électrodes Withdrawn EP1130077A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200000497A ES2186466B1 (es) 2000-03-01 2000-03-01 Procedimiento de obtencion de breas de petroleo no contaminantes para su uso en la fabricacion de electrodos y otros compuestos grafiticos.
ES200000497 2000-03-01

Publications (2)

Publication Number Publication Date
EP1130077A2 true EP1130077A2 (fr) 2001-09-05
EP1130077A3 EP1130077A3 (fr) 2003-04-23

Family

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EP01500047A Withdrawn EP1130077A3 (fr) 2000-03-01 2001-02-23 Brai d'huile de pétrole à forte teneur en composés aromatiques, sa préparation et son utilisation dans la fabricage d'électrodes

Country Status (4)

Country Link
EP (1) EP1130077A3 (fr)
AR (1) AR027566A1 (fr)
BR (1) BR0102355A (fr)
ES (1) ES2186466B1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100418878C (zh) * 2006-11-20 2008-09-17 彭绍权 大直径管状半石墨炭电极的生产方法
WO2011073153A1 (fr) 2009-12-16 2011-06-23 Italghisa S.P.A. Pâte à électrodes pour électrodes dans un graphite sans liant comprenant une base hydrocarbure
CN103173235A (zh) * 2013-03-27 2013-06-26 天津大学 沥青中喹啉不溶物的低能耗脱除方法
US8580105B2 (en) 2008-03-05 2013-11-12 Saint-Gobain do Brasil Produtos Industriais e para Construção Ltda. Development process of an ecological binder system for refractories mixes
CN103450694A (zh) * 2013-09-22 2013-12-18 交通运输部公路科学研究所 一种煤系与石油系混炼沥青及其制备方法
EP3272187B1 (fr) 2016-03-31 2018-08-22 Rheinfelden Carbon GmbH & Co. KG Composition pour électrodes
CN110607186A (zh) * 2014-10-17 2019-12-24 Oci有限公司 高纯度沥青的制备方法
EP4215597A1 (fr) * 2022-01-24 2023-07-26 Rain Carbon bv Matériau précurseur de carbone thermoplastique amélioré pour application dans des processus de revêtement, de liaison et d'imprégnation pour la fabrication d'électrodes de production d'acier et d'aluminium et de batteries

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086156A (en) * 1974-12-13 1978-04-25 Exxon Research & Engineering Co. Pitch bonded carbon electrode
GB2083492A (en) * 1980-04-29 1982-03-24 British Petroleum Co Production of pitch from petroleum fractions
US4655902A (en) * 1981-08-28 1987-04-07 Toa Nenryo Kogyo Kabushiki Kaisha Optically anisotropic carbonaceous pitch
US4961837A (en) * 1989-04-28 1990-10-09 Intevep, S.A. Process for the production of petroleum tar pitch for use as a binder in the production of electrodes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR200954A1 (es) * 1973-11-19 1974-12-27 Acme Cleveland Corp Maquina de fundicion para mezclar un componente de material de molde y un componente aglomerante
JPS5512158A (en) * 1978-07-14 1980-01-28 Nippon Oil Co Ltd Preparation of petroleum binder pitch
JPS5594991A (en) * 1979-01-16 1980-07-18 Kureha Chem Ind Co Ltd Preparating pitch
CA2002828C (fr) * 1989-11-14 1999-08-03 Biswa Nath Nandi Procede de fabrication d'un liant a coke a nocivite environnementale reduite
ES2049644B1 (es) * 1992-07-10 1994-12-16 Repsol Petroleo Sa Procedimiento para producir industrialmente microesferas de mesofase carbonosa y las consiguientes piezas de carbon.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086156A (en) * 1974-12-13 1978-04-25 Exxon Research & Engineering Co. Pitch bonded carbon electrode
GB2083492A (en) * 1980-04-29 1982-03-24 British Petroleum Co Production of pitch from petroleum fractions
US4655902A (en) * 1981-08-28 1987-04-07 Toa Nenryo Kogyo Kabushiki Kaisha Optically anisotropic carbonaceous pitch
US4961837A (en) * 1989-04-28 1990-10-09 Intevep, S.A. Process for the production of petroleum tar pitch for use as a binder in the production of electrodes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ACUNA CAROLA ET AL: "Petroleum pitch, a real alternative to coal tar pitch as binder material for anode production" LIGHT MEATLS 1997: PROCEEDINGS OF THE 1997 126TH TMS ANNUAL MEETING; ORLANDO, FL, USA FEB 9-13 1997, 1997, pages 549-554, XP002228040 Warrendale, PA, USA *
MARTNEZ-ESCANDELL M ET AL: "Pyrolysis of petroleum residues: I. Yields and product analyses" CARBON, vol. 37, no. 10, 1999, pages 1567-1582, XP004179421 ISSN: 0008-6223 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100418878C (zh) * 2006-11-20 2008-09-17 彭绍权 大直径管状半石墨炭电极的生产方法
US8580105B2 (en) 2008-03-05 2013-11-12 Saint-Gobain do Brasil Produtos Industriais e para Construção Ltda. Development process of an ecological binder system for refractories mixes
WO2011073153A1 (fr) 2009-12-16 2011-06-23 Italghisa S.P.A. Pâte à électrodes pour électrodes dans un graphite sans liant comprenant une base hydrocarbure
EP2651184A1 (fr) 2009-12-16 2013-10-16 Italghisa S.p.A. Pâte d'électrode pour électrodes de graphite sans liant à base d'hydrocarbures
US9131538B2 (en) 2009-12-16 2015-09-08 Italghisa S.P.A. Electrode paste for electrodes in a graphite and/or anthracite with hydrocarbon base
CN103173235A (zh) * 2013-03-27 2013-06-26 天津大学 沥青中喹啉不溶物的低能耗脱除方法
CN103173235B (zh) * 2013-03-27 2014-06-18 天津大学 沥青中喹啉不溶物的低能耗脱除方法
CN103450694A (zh) * 2013-09-22 2013-12-18 交通运输部公路科学研究所 一种煤系与石油系混炼沥青及其制备方法
CN110607186A (zh) * 2014-10-17 2019-12-24 Oci有限公司 高纯度沥青的制备方法
EP3272187B1 (fr) 2016-03-31 2018-08-22 Rheinfelden Carbon GmbH & Co. KG Composition pour électrodes
EP4215597A1 (fr) * 2022-01-24 2023-07-26 Rain Carbon bv Matériau précurseur de carbone thermoplastique amélioré pour application dans des processus de revêtement, de liaison et d'imprégnation pour la fabrication d'électrodes de production d'acier et d'aluminium et de batteries
WO2023139287A1 (fr) * 2022-01-24 2023-07-27 Rain Carbon Bv Matériau précurseur de carbone thermoplastique amélioré pour application dans des procédés de revêtement, de liaison et d'imprégnation pour la fabrication d'électrodes pour la production d'acier et d'aluminium et batteries

Also Published As

Publication number Publication date
ES2186466B1 (es) 2004-08-01
AR027566A1 (es) 2003-04-02
BR0102355A (pt) 2001-10-30
ES2186466A1 (es) 2003-05-01
EP1130077A3 (fr) 2003-04-23

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