EP0286499B1 - Elektrodenbindemittelpech und Verfahren zur Herstellung derselben - Google Patents

Elektrodenbindemittelpech und Verfahren zur Herstellung derselben Download PDF

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Publication number
EP0286499B1
EP0286499B1 EP19880400709 EP88400709A EP0286499B1 EP 0286499 B1 EP0286499 B1 EP 0286499B1 EP 19880400709 EP19880400709 EP 19880400709 EP 88400709 A EP88400709 A EP 88400709A EP 0286499 B1 EP0286499 B1 EP 0286499B1
Authority
EP
European Patent Office
Prior art keywords
pitch
weight
treatment
equal
content
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.)
Expired - Lifetime
Application number
EP19880400709
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English (en)
French (fr)
Other versions
EP0286499A1 (de
Inventor
Denis Rue Du Capitaine Hazebrouck Cottinet
Serge Buche
Jean Louis Saint-Romain
Pierre Couderc
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.)
Arkema France SA
Original Assignee
Norsolor SA
Elf Atochem 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 Norsolor SA, Elf Atochem SA filed Critical Norsolor SA
Priority to AT88400709T priority Critical patent/ATE55776T1/de
Publication of EP0286499A1 publication Critical patent/EP0286499A1/de
Application granted granted Critical
Publication of EP0286499B1 publication Critical patent/EP0286499B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C10C1/00—Working-up tar

Definitions

  • the present invention relates to pitches, in particular the pitches of coal tar, without however being limited to the latter.
  • coal tars makes it possible to obtain, in substantially equal quantities, on the one hand, oils (benzene, toluene, xylene, the corresponding phenolic and methylated products, naphthalene, medium oils, anthracene, chrysene, etc.) , and, on the other hand, the concentrate or pitch.
  • oils benzene, toluene, xylene, the corresponding phenolic and methylated products, naphthalene, medium oils, anthracene, chrysene, etc.
  • pitches mention may be made in particular of their use as binders in the manufacture of carbon or graphite electrodes, which are used for the production of aluminum and ferrous or non-ferrous metals.
  • pitches When one starts from a tar containing more than 4% of a resins, one obtains, by simple distillation, pitches meeting these specifications. By differential thermal analysis, it can be seen that these pitches always have a glass transition domain ATg of the order of 55 ° C.
  • the present invention is based on the observation that the quality of a binding binder for an electrode can be further improved when it also has a glass transition domain ATg clearly more restricted than those known hitherto. As has just been indicated, no manufacturing process has yet made it possible to achieve this result so far.
  • the Depositing Company has now discovered that it is possible to achieve pitch maturation by means of high frequency wave treatment.
  • This treatment makes it possible to increase the fixed carbon content of the pitch, while retaining a good affinity for coke and while significantly reducing its glass transition domain.
  • the pitch according to the invention has an A Tg domain less than or equal to 40 ° C.
  • a subject of the present invention is also a process for manufacturing a pitch as defined above, a process according to which a pitch having a content of quinoline insoluble substances of less than 4% by weight approximately is subjected to a wave treatment. having a frequency between 0.9 and 300 GHz.
  • High frequency wave treatment consists of converting electrical energy into heat in dielectric (insulating) materials containing polar molecules.
  • the polar molecules subjected to the electromagnetic field, move away or approach violently, causing by collision a release of heat.
  • a conventional frequency of about 2.45 GHz is used.
  • the treatment is carried out in principle at atmospheric pressure; however, it is safe to operate under a pressure of up to 20 bar.
  • the temperature at which the treatment is carried out is controlled by the amount of electrical energy supplied to the system (magnetron). It is preferably between 350 and 450 ° C, in particular between 380 and 420 ° C.
  • the duration of the treatment is preferably between 1 and 1200 minutes. The shorter the temperature, the higher the temperature.
  • process of the present invention can be carried out continuously or batchwise.
  • An important advantage of the method according to the invention lies in a significant reduction in the duration of treatment, allowing an increase in productivity.
  • this heating mode makes it possible to avoid the coking and cracking phenomena mentioned above. We can therefore work without inconvenience with higher temperatures and shorter durations.
  • the present invention also relates to an electrode containing a binding pitch as defined above or obtained by a manufacturing process as defined above.
  • the pitch is preheated to a temperature of the order of 200 ° C. in a melter, before being conveyed to an electrically heated tubular oven, operating continuously.
  • the melter used consists of a closed reactor, with a capacity of 130 liters, fitted with mechanical stirring, and heated externally with regulation, by electrical resistors placed in a steel envelope and capable of delivering a total power of 30 kW.
  • the steel envelope constitutes a “calorie reservoir” and allows excess calories to be removed by injection of compressed air, if it is deemed necessary.
  • the pitch can thus be heated quickly to the desired temperature, while avoiding overheating points.
  • the pitch thus preheated in the melter whose viscosity is of the order of 50 centipoise, is then conveyed to the furnace continuously by means of a gear pump.
  • a gear pump This consists of a stainless steel body, fitted with a double preheating jacket; it allows flow rates of the order of 2 to 20 liters per hour.
  • the double jacket and all the tubes carrying the pitch are heated thanks to an oil bath, at a temperature of the order of 200 ° C.
  • the tubular oven is made of stainless steel and has a capacity of 4 liters. It is heated by means of electric resistors, delivering a total power of 4 kW and also placed in a double steel jacket having the same function as that equipping the melter. Maintaining the maturation temperature in the oven is ensured by regulation. Above the oven, a pyrex column head is placed which allows the volatile products to condense in order to limit their loss, such products playing an important role in the polycondensation reaction.
  • the pitch leaving the oven at the maturation temperature is cooled by the same oil bath playing the role of exchanger. Bottom and drain valves are placed in the system, in different places, and allow the rapid evacuation of the pitch at the end of the reaction or at any time. The pitch is then collected and weighed continuously.
  • Example 1 a coal tar pitch having a CIA softening point of 84.7 ° C is subjected to heat treatment, under the conditions described above, at the temperature of 405 ° C. and for 175 minutes . , a content of substances insoluble in quinoline (resins a) equal to 3.3% by weight, a content of resins a + equal to 24.1% by weight and a fixed carbon content equal to 48.0% by weight .
  • the binding pitch obtained at the end of this treatment has the characteristics indicated in the table below.
  • Example 2 the binder pitch obtained in Example 1 is subjected to flash distillation under a pressure of 0.145 bar so as to remove 4.5% of the oil it contains.
  • the binding pitch obtained at the end of this distillation has the characteristics indicated in the table below.
  • the equipment described above replacing the electric oven with a microwave applicator.
  • the latter consists of eight sections of guide stacked and offset from each other by 90 ° . Each of these sections is connected to a magnetron which can output 800 W, but voluntarily limited to 400 W to protect the magnetron against poor adaptation.
  • These magnetrons operate at a frequency of 2.45 GHz.
  • the stack of waveguides is traversed by a quartz reactor, with a useful capacity of 1000 cm 3 , in which the liquid pitch circulates.
  • a quartz sheath plunges into the reactor and allows, when the magnetrons are not in service, to measure the temperature within the liquid.
  • a thermocouple allows temperature regulation.
  • Example 3 the same pitch of coal tars as that described in Example 1 is subjected to treatment by high frequency waves, under the conditions described above, at the temperature of 415 ° C. and for 45 minutes.
  • the binding pitch obtained at the end of this treatment has the characteristics indicated in the table below.
  • the binder pitch obtained in Example 3 is subjected to flash distillation under a pressure of 0.145 bar, so as to remove 4.5% by weight (Example 4) and 1.3% respectively. weight (example 5) of the oil it contains.
  • the binding pitches obtained at the end of these distillations have the characteristics indicated in the table below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inert Electrodes (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coupling Device And Connection With Printed Circuit (AREA)

Claims (12)

1. Pechbindemittel für Elektroden, mit:
- einem C.I.A. Erweichungspunkt zwischen 80°C und 150°C,
- einem Gehalt an in Chinolin unlöslichen Substanzen von größer oder gleich 4 Gew.-%,
- einem Gehalt an Harzen a + von 28 - 40 Gew.-%, und
- einem Gehalt an festem Kohlenstoff, bestimmt nach der Norm ISO 6998, von mindestens 51 Gew.-%, dadurch gekennzeichnet, daß deren Glasübergangsbereich ATg, bestimmt durch kalorimetrische Differentialanalyse, bei 50°C oder darunter liegt.
2. Pechbindemittel nach Anspruch 1, dadurch gekennzeichnet, daß der Glasübergangsbereich ATg bei 40°C oder darunter liegt.
3. Pechbindemittel nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß es einen Fließverzug T2-T1 in einem Test zur Bestimmung der Pech-Koksaffinität von höchstens 15°C aufweist.
4. Pechbindemittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es eine Penetrations-Endtemperatur T2 in einem Test zur Bestimmung der Pech-Koksaffinität von höchstens 180°C aufweist.
5. Verfahren zur Hestellung eines Pechbindemittels für Elektroden gemäß der Definition nach einem der Ansprüche 1-4, dadurch gekennzeichnet, daß man ein Pechbindemitttel, das einen Gehalt an in Chinolin unlöslichen Substanzen von kleiner 4 Gew.-% aufweist, einer Behandlung mit Wellen einer Frequenz von 0,9 - 300 GHz unterzieht.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß man eine Frequenz von 2,45 GHz verwendet.
7. Verfahren nach einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, daß man die Behandlung bei atmosphärischem Druck durchführt.
8. Verfahren nach einem der Ansprüche 5 und 6, dadurch gekennzeichnet, daß man die Behandlung bei einem Druck von bis zu 20 Bar durchführt.
9. Verfahren nach einem der Ansprüche 5-8, dadurch gekennzeichnet, daß man bei einer Temperatur von 350-450°C arbeitet.
10. Verfahren nach einem der Ansprüche 5-9, dadurch gekennzeichnet, daß man die Behandlung über eine Dauer von 1-1200 Minuten durchführt.
11. Verfahren nach einem der Ansprüche 5-10, dadurch gekennzeichnet, daß man im Anschluß an die Behandlung eine ergänzende Destillation durchführt, um den gewünschten C.I.A. Erweichungspunkt zu erreichen.
12. Elektrode, dadurch gekennzeichnet, daß sie ein Pechbindemittel nach einem der Ansprüche 1-4 oder erhältlich nach einem der Ansprüche 5-11 enthält.
EP19880400709 1987-03-24 1988-03-23 Elektrodenbindemittelpech und Verfahren zur Herstellung derselben Expired - Lifetime EP0286499B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88400709T ATE55776T1 (de) 1987-03-24 1988-03-23 Elektrodenbindemittelpech und verfahren zur herstellung derselben.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8704054A FR2612935B1 (fr) 1987-03-24 1987-03-24 Brai liant pour electrode et son procede de fabrication
FR8704054 1987-03-24

Publications (2)

Publication Number Publication Date
EP0286499A1 EP0286499A1 (de) 1988-10-12
EP0286499B1 true EP0286499B1 (de) 1990-08-22

Family

ID=9349351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880400709 Expired - Lifetime EP0286499B1 (de) 1987-03-24 1988-03-23 Elektrodenbindemittelpech und Verfahren zur Herstellung derselben

Country Status (14)

Country Link
US (1) US5120424A (de)
EP (1) EP0286499B1 (de)
JP (1) JPH02502650A (de)
AT (1) ATE55776T1 (de)
AU (1) AU607760B2 (de)
BR (1) BR8807335A (de)
CA (1) CA1304199C (de)
DE (1) DE3860473D1 (de)
ES (1) ES2016675B3 (de)
FR (1) FR2612935B1 (de)
GR (1) GR3000922T3 (de)
NZ (1) NZ223941A (de)
WO (1) WO1988007571A1 (de)
ZA (1) ZA881882B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69228663T2 (de) * 1991-12-25 1999-09-30 Mitsubishi Chem Corp Auf Pech basierte Kohlenstoffasern und Verfahren zu deren Herstellung
RU2288938C1 (ru) * 2005-10-10 2006-12-10 Общество с ограниченной ответственностью "Инженерно-технологический центр" Способ получения пека-связующего для электродных материалов
CN1970689B (zh) * 2006-12-13 2010-05-12 上海奥韦通工程技术有限公司 一种改质沥青的生产工艺

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1323457A (fr) * 1962-06-01 1963-04-05 Coal Tar Res Ass Perfectionnements apportés à la fabrication des produits à base de goudrons de houille
FR2250571B1 (de) * 1973-11-12 1980-01-04 British Petroleum Co
JPS59758B2 (ja) * 1976-08-03 1984-01-09 理化学研究所 スケ−ル付着防止法
US4096056A (en) * 1976-10-21 1978-06-20 Witco Chemical Corporation Method of producing an impregnating petroleum pitch
FR2392143A1 (fr) * 1977-05-25 1978-12-22 British Petroleum Co Procede de fabrication de fibres de carbone ou de graphite a partir de fibres de matieres organiques naturelles par utilisation d'hyperfrequences
DE2966700D1 (en) * 1978-06-15 1984-03-29 Gte Laboratories Inc High strength silicon nitride
JPS57125289A (en) * 1981-01-28 1982-08-04 Toa Nenryo Kogyo Kk Preparation of optically anisotropic carbonaceous pitch
JPH0699693B2 (ja) * 1981-09-07 1994-12-07 東燃株式会社 光学的異方性炭素質ピツチおよびその製造方法
US4427530A (en) * 1982-02-08 1984-01-24 Exxon Research And Engineering Co. Aromatic pitch derived from a middle fraction of a cat cracker bottom
JPS58142976A (ja) * 1982-02-22 1983-08-25 Toa Nenryo Kogyo Kk 均質低軟化点光学的異方性ピッチの製法
US4518482A (en) * 1982-07-19 1985-05-21 E. I. Du Pont De Nemours And Company Pitch for direct spinning into carbon fibers derived from a coal distillate feedstock
US4548703A (en) * 1982-07-19 1985-10-22 E. I. Du Pont De Nemours And Company Pitch for direct spinning into carbon fibers
US4581123A (en) * 1983-03-28 1986-04-08 E. I. Du Pont De Nemours And Company Custom blended precursor for carbon artifact manufacture
US4518483A (en) * 1983-06-27 1985-05-21 E. I. Du Pont De Nemours And Company Aromatic pitch from asphaltene fractions
CA1193574A (en) * 1983-07-14 1985-09-17 Jeffrey K.S. Wan Hydrodesulphurization of hydrocracked pitch
US4664774A (en) * 1984-07-06 1987-05-12 Allied Corporation Low solids content, coal tar based impregnating pitch

Also Published As

Publication number Publication date
FR2612935A1 (fr) 1988-09-30
NZ223941A (en) 1989-10-27
AU1542188A (en) 1988-11-02
US5120424A (en) 1992-06-09
CA1304199C (fr) 1992-06-30
ZA881882B (en) 1990-01-31
EP0286499A1 (de) 1988-10-12
ATE55776T1 (de) 1990-09-15
ES2016675B3 (es) 1990-11-16
DE3860473D1 (de) 1990-09-27
JPH02502650A (ja) 1990-08-23
BR8807335A (pt) 1990-03-13
WO1988007571A1 (fr) 1988-10-06
AU607760B2 (en) 1991-03-14
GR3000922T3 (en) 1991-12-10
FR2612935B1 (fr) 1989-06-09

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