EP0286499B1 - Pitch for binding electrodes and process for preparing said pitch - Google Patents
Pitch for binding electrodes and process for preparing said pitch Download PDFInfo
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- 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
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- pitch
- weight
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- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000011282 treatment Methods 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000004458 analytical method Methods 0.000 claims abstract description 4
- 239000011295 pitch Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 8
- 230000035515 penetration Effects 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- 239000011305 binder pitch Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000006253 pitch coke Substances 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 13
- 230000007704 transition Effects 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011269 tar Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 6
- 230000035800 maturation Effects 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241001644893 Entandrophragma utile Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (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)
- Coupling Device And Connection With Printed Circuit (AREA)
- Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
La présente invention concerne les brais, en particulier les brais de goudrons de houille, sans toutefois être limitée à ces derniers.The present invention relates to pitches, in particular the pitches of coal tar, without however being limited to the latter.
Les brais de goudrons de houille sont constitués par le concentrat de la distillation des goudrons de houille. Les brais sont des mélanges complexes :
- 1 ) de molécules polyaromatiques, éventuellement porteuses de courtes chaînes aliphatiques ;
- 2) de molécules polaires à caractère acide ou basique (phénols, naphtols, carbazole, bases pyridini- ques, etc.) ;
- 3) éventuellement, de particules insolubles en suspension (particules de type noir de carbone, cénos- phères ou particules de coke polluées plus ou moins par des impuretés minérales).
- 1) polyaromatic molecules, possibly carrying short aliphatic chains;
- 2) polar molecules with an acidic or basic character (phenols, naphthols, carbazole, pyridine bases, etc.);
- 3) possibly, insoluble particles in suspension (particles of the carbon black type, cenospheres or coke particles polluted more or less by mineral impurities).
On caractérise les brais et les goudrons par leur taux de substances insolubles dans les différents solvants ; ainsi, il est d'usage de considérer les trois fractions suivantes :
- 1) les résines a, constituées par la fraction insoluble dans la quinoléine ;
- 2) les résines p, constituées par la fraction insoluble dans le toluène et soluble dans la quinoléine ; et,
- 3) les résines y, constituées par la fraction soluble dans le toluène.
- 1) resins a, constituted by the fraction insoluble in quinoline;
- 2) p resins, consisting of the fraction insoluble in toluene and soluble in quinoline; and,
- 3) the resins y, constituted by the fraction soluble in toluene.
On peut alors distinguer les goudrons servant à la préparation de brais selon leur teneur en résines α; on appellera goudrons «bas a», les goudrons renfermant moins de 2% en poids de résines a.We can then distinguish the tars used for the preparation of pitches according to their content of α resins; tars will be called "low a", the tars containing less than 2% by weight of resins a.
La distillation des goudrons de houille permet d'obtenir, en des quantités sensiblement égales, d'une part, des huiles (benzène, toluène, xylène, les produits correspondants phénoliques et méthylés, naphtalène, huiles moyennes, anthracène, chrysène, etc.), et, d'autre part, le concentrat ou brai.The distillation of 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.
Parmi les applications des brais, on peut mentionner notamment leur utilisation en tant que liants dans la fabrication des électrodes de carbone ou de graphite, lesquelles sont utilisées pour la production d'aluminium et de métaux ferreux ou non ferreux.Among the applications of 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.
Les brais sont caractérisés par différentes données analytiques, dont la connaissance permet d'apprécier leur valeur d'usage pour l'application choisie ; on donnera ci-après une définition des différentes caractéristiques des brais qui seront évoquées dans le présent mémoire descriptif:
- - le point de ramollissement C.I.A. (Cube In Air), exprimé en °C, grandeur déterminée selon la norme ASTM D 3104-77;
- - la teneur en résines a et la teneur en résines a+p (ou fraction insoluble dans le toluène) (exprimées en % en poids) obtenues par les modes opératoires indiqués dans les normes respectivement ISO 6791 et ISO 6376 ;
- - la teneur en carbone fixe (exprimée en % en poids), qui traduit le rendement en coke ou le pouvoir en carbone du brai, cette teneur étant calculée selon la norme ISO 6998 ;
- - l'affinité brai-coke mesurée selon le test de pénétration décrit par P. Couderc, P. Hyvernat et G.L. Le- marchand dans la revue «FUEL, 1986, Vol. 65, 2, 281-287» ; ce test permet de caractériser les propriétés de pénétration et d'écoulement des brais dans un lit de coke (écoulement rapide ou retardé ; pénétration complète ou incomplète). Les courbes d'écoulement obtenues permettent d'obtenir deux températures caractéristiques :
- - T2 : température finale de pénétration
- - Tr : température obtenue par extrapolation du début de la courbe d'écoulement ;
- - la mesure, par analyse calorimétrique différentielle (effectuée dans les conditions suivantes : un échantillon de 20 mg de brai est porté à 140°C, puis refroidi en 3 minutes jusqu'à -100°C, puis réchauffé à la vitesse de 30°C par minute),de la température et du domaine de transition vitreuse : Tg et ATg.
- - the CIA (Cube In Air) softening point, expressed in ° C, quantity determined according to standard ASTM D 3104-77;
- the content of resins a and the content of resins a + p (or fraction insoluble in toluene) (expressed in% by weight) obtained by the procedures indicated in the standards ISO 6791 and ISO 6376 respectively;
- - the fixed carbon content (expressed in% by weight), which reflects the coke yield or the carbon power of the pitch, this content being calculated according to ISO standard 6998;
- - the pitch-coke affinity measured according to the penetration test described by P. Couderc, P. Hyvernat and GL Le-marchand in the review “FUEL, 1986, Vol. 65, 2, 281-287 ”; this test makes it possible to characterize the penetration and flow properties of the pitches in a coke bed (rapid or delayed flow; complete or incomplete penetration). The flow curves obtained allow two characteristic temperatures to be obtained:
- - T 2 : final penetration temperature
- - T r : temperature obtained by extrapolation from the start of the flow curve;
- - the measurement, by differential scanning calorimetry (carried out under the following conditions: a sample of 20 mg of pitch is brought to 140 ° C, then cooled in 3 minutes to -100 ° C, then reheated at the speed of 30 ° C per minute), the temperature and the glass transition range: Tg and A Tg.
Un brai-liant jugé satisfaisant pour la fabrication d'une électrode de carbone ou de graphite, respecte généralement les spécifications suivantes :
- - un point de ramollissement C.I.A. de l'ordre de 100 à 130°C ;
- - une teneur en résines a de l'ordre de 8 à 15% en poids;
- - une teneur en résines a + p de l'ordre de 28 à 35% en poids ;
- - une teneur en carbone fixe de l'ordre de 54 à 62% en poids ; et
- - une bonne affinité brai-coke (écoulement rapide ou peu retardé, pénétration complète).
- - a CIA softening point of the order of 100 to 130 ° C;
- - A resin content has of the order of 8 to 15% by weight;
- - A resin content a + p of the order of 28 to 35% by weight;
- - a fixed carbon content of the order of 54 to 62% by weight; and
- - a good pitch-coke affinity (rapid or slightly delayed flow, complete penetration).
Lorsque l'on part d'un goudron contenant plus de 4% de résines a, on obtient, par simple distillation, des brais répondant à ces spécifications. Par analyse thermique différentielle, on constate que ces brais ont toujours un domaine de transition vitreuse ATg de l'ordre de 55°C.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.
En revanche, lorsque l'on distille un goudron «bas α», on obtient, pour le même point de ramollissement, un brai dont la teneur en résines a est au plus égale à 5% en poids, la teneur en résines a + p est de l'ordre de 25% en poids, et la teneur en carbone fixe est inférieure à 54% en poids. Ce brai, bien qu'ayant une bonne affinité envers le coke, est considéré comme trop pauvre en carbone. Pour pallier à cette déficience, il est possible de réaliser un traitement thermique à des températures supérieures à 350°C. Dans ces conditions, les brais obtenus présentent des teneurs en carbone fixe et en résines a + p acceptables. En revanche,leur affinité envers le coke est difficilement contrôlable. De plus, on note une nette augmentation du domaine de transition vitreuse ATg.On the other hand, when a “low α” tar is distilled, one obtains, for the same softening point, a pitch whose resin content a is at most equal to 5% by weight, the resin content a + p is of the order of 25% by weight, and the fixed carbon content is less than 54% by weight. This pitch, although having a good affinity for coke, is considered to be too low in carbon. To overcome this deficiency, it is possible to carry out a heat treatment at temperatures above 350 ° C. Under these conditions, the pitches obtained have fixed carbon and a + resin contents p acceptable. However, their affinity for coke is difficult to control. In addition, there is a marked increase in the glass transition domain A Tg.
Par ailleurs, l'expérience montre que de tels traitements, lorsqu'ils sont effectués dans des conditions industrielles, s'accompagnent de phénomènes de cokéfaction et craquages liés à l'existence de gradients thermiques au voisinage de la paroi du four.Furthermore, experience shows that such treatments, when carried out under industrial conditions, are accompanied by coking and cracking phenomena linked to the existence of thermal gradients in the vicinity of the wall of the furnace.
La présente invention est basée sur la constatation que la qualité d'un brai liant pour électrode peut être encore améliorée lorsqu'il présente en outre un domaine de transition vitreuse ATg nettement plus restreint que ceux connus jusqu'alors. Comme on vient de l'indiquer, aucun procédé de fabrication ne permettait toutefois d'atteindre ce résultat jusqu'à présent.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.
La Société déposante a maintenant découvert qu'il est possible de réaliser une maturation du brai au moyen d'un traitement par ondes haute frequence. Ce traitement permet d'augmenter la teneur en carbone fixe du brai, tout en lui conservant une bonne affinité envers le coke et tout en diminuant significativement son domaine de transition vitreuse.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.
La présente invention a donc d'abord pour objet un brai liant pour électrode, possédant :
- - un point de ramollissement C.I.A. compris entre 80°C et 150°C,
- - une teneur en substances insolubles dans la quinoléine supérieure ou égale à 4% en poids,
- - une teneur en résines a+p comprise entre 28 et 40% en poids, et
- - une teneur en carbone fixe, déterminée selon la norme ISO 6998, au moins égale à 51 % en poids, caractérisé en ce que son domaine de transition vitreuse ATg, déterminé par analyse calorimétrique différentielle, est inférieur ou égal à 50°C.
- - a CIA softening point between 80 ° C and 150 ° C,
- - a content of substances insoluble in quinoline greater than or equal to 4% by weight,
- a content of resins a + p of between 28 and 40% by weight, and
- - a fixed carbon content, determined according to ISO 6998, at least equal to 51% by weight, characterized in that its glass transition range A Tg, determined by differential scanning calorimetry, is less than or equal to 50 ° C.
De manière plus particulièrement préférée, le brai selon l'invention possède un domaine ATg inférieur ou égal à 40°C.More particularly preferably, the pitch according to the invention has an A Tg domain less than or equal to 40 ° C.
Outre les caractéristiques précitées, le brai selon l'invention pourra avantageusement posséder l'une ou l'autre des propriétés d'écoulement suivantes, déterminées selon le test de pénétration précité (en utilisant une granulométrie moyenne du lit de coke de 120 µm environ et une vitesse de chauffe de 20°C par heure) :
- - un retard à l'écoulement T2- Ti au plus égal à 15°C ;
- - une température finale de pénétration T2 au plus égale à 180°C.
- - A delay in flow T 2 - Ti at most equal to 15 ° C;
- - a final penetration temperature T 2 at most equal to 180 ° C.
La présente invention a également pour objet un procédé de fabrication d'un brai tel que défini ci-dessus, procédé suivant lequel on soumet un brai présentant une teneur en substances insolubles dans la quinoléine inférieure à 4% en poids environ à un traitement par ondes ayant une fréquence comprise entre 0,9 et 300 GHz.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.
Le traitement par ondes haute fréquence consiste à convertir de l'énergie électrique en chaleur dans des matériaux diélectriques (isolants) contenant des molécules polaires. Les molécules polaires, soumises au champ électromagnétique, s'éloignent ou se rapprochent violemment, provoquant par collision un dégagement de chaleur.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.
De manière avantageuse, on utilise une fréquence classique de 2,45 GHz environ.Advantageously, a conventional frequency of about 2.45 GHz is used.
Conformément à la présente invention, on effectue le traitement en principe à la pression atmosphérique ; cependant, on peut sans inconvénient opérer sous une pression pouvant aller jusqu'à 20 bars.In accordance with the present invention, the treatment is carried out in principle at atmospheric pressure; however, it is safe to operate under a pressure of up to 20 bar.
La température à laquelle on effectue le traitement est contrôlée par la quantité d'énergie électrique fournie au système (magnétron). Elle est, de préférence, comprise entre 350 et 450°C, en particulier entre 380 et 420°C.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.
La durée du traitement est, de préférence, comprise entre 1 et 1200 minutes. Elle est d'autant plus courte que la température est plus élevée.The duration of the treatment is preferably between 1 and 1200 minutes. The shorter the temperature, the higher the temperature.
De plus, après le traitement selon l'invention, on pourra procéder, comme on le fait d'habitude,. à une distillation complémentaire, par exemple sous pression réduite, pour atteindre le point de ramollissement C.I.A. désiré.In addition, after the treatment according to the invention, it will be possible to proceed, as usual. additional distillation, for example under reduced pressure, to reach the desired C.I.A. softening point.
Par ailleurs, le procédé de la présente invention peut être mis en oeuvre en continu ou en discontinu.Furthermore, the process of the present invention can be carried out continuously or batchwise.
Un avantage important du procédé selon l'invention, par rapport aux procédés traditionnels par chauffage électrique, réside dans une diminution importante de la durée de traitement, permettant une augmentation de la productivité. De plus, ce mode de chauffage permet d'éviter les phénomènes de cokéfaction et de craquage évoqués plus haut. On peut donc sans inconvénient travailler avec des températures plus élevées et des durées plus courtes.An important advantage of the method according to the invention, compared to traditional methods by electric heating, lies in a significant reduction in the duration of treatment, allowing an increase in productivity. In addition, 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.
La présente invention a également pour objet une électrode contenant un brai liant tel que défini ci-dessus ou obtenu par un procédé de fabrication tel que défini ci-dessus.The present invention also relates to an electrode containing a binding pitch as defined above or obtained by a manufacturing process as defined above.
Dans les exemples qui suivent, on a comparé le traitement thermique de maturation de brai en continu, d'une part, par un chauffage classique dans un four électrique par effet Joule, et, d'autre part, par un traitement au moyen d'ondes haute fréquence selon l'invention, dans un four à micro-ondes.In the examples which follow, a comparison has been made of the heat treatment for continuous pitch maturation, on the one hand, by conventional heating in an electric oven by Joule effect, and, on the other hand, by treatment by means of high frequency waves according to the invention, in a microwave oven.
On préchauffe le brai jusqu'à une température de l'ordre de 200°C dans un fondoir, avant de l'acheminer vers un four tubulaire chauffé électriquement, fonctionnant en continu .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.
Le fondoir utilisé consiste en un réacteur fermé, d'une capacité de 130 litres, muni d'une agitation mécanique, et chauffé extérieurement avec régulation, par des résistances électriques placées dans une enveloppe en acier et pouvant délivrer une puissance totale de 30 kW. L'enveloppe en acier constitue un «réservoir à calories> et permet d'évacuer les calories en excès par injection d'air comprimé, si on le juge nécessaire. Le brai peut ainsi être chauffé rapidement jusqu'à la température désirée, tout en évitant les points de surchauffe.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.
Le brai ainsi préchauffé dans le fondoir, dont la viscosité est de l'ordre de 50 centipoises, est ensuite véhiculé vers le four en continu grâce à une pompe à engrenages. Celle-ci est constituée d'un corps en acier inoxydable, muni d'une double enveloppe de préchauffage ; elle permet d'avoir des débits de l'ordre de 2 à 20 litres par heure. La double enveloppe et tous les tubes véhiculant le brai sont réchauffés grâce à un bain d'huile, à une température de l'ordre de 200°C.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. 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.
Le four tubulaire est en acier inoxydable et il présente une capacité de 4 litres. Il est chauffé au moyen de résistances électriques, délivrant une puissance totale de 4 kW et placé également dans une double enveloppe en acier ayant la même fonction que celle équipant le fondoir. Le maintien de la température de maturation dans le four est assuré par régulation. Au-dessus du four, est placée une tête de colonne en pyrex qui permet de condenser les produits volatils afin d'en limiter la perte, de tels produits jouant un rôle important dans la réaction de polycondensation.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.
Le brai sortant du four à la température de maturation est refroidi par le même bain d'huile jouant le rôle d'échangeur. Des vannes de fond de cuve et de vidange sont placées dans le système, à différents endroits, et permettent l'évacuation rapide du brai en fin de réaction ou à tout moment. Le brai est ensuite recueilli et pesé en continu.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.
Avec le dispositif précité, on a pu opérer à une température allant jusqu'à environ 405°C. Toutefois, il est très difficile de dépasser cette température, en raison du départ très important, à la pression atmosphérique, de produits volatils lors de la maturation, de tels départs étant favorisés par des réactions de craquage dues à des effets thermiques au voisinage de la paroi. En effet, on observe une différence de température entre la paroi et le coeur du four qui est de l'ordre de 20°C, à la température de traitement précitée, pour un débit de l'ordre de 2,7 litres par heure.With the above-mentioned device, it was possible to operate at a temperature of up to approximately 405 ° C. However, it is very difficult to exceed this temperature, due to the very large departure, at atmospheric pressure, of volatile products during the maturation, such departures being favored by cracking reactions due to thermal effects in the vicinity of the wall. Indeed, there is a temperature difference between the wall and the core of the oven which is of the order of 20 ° C, at the aforementioned treatment temperature, for a flow rate of the order of 2.7 liters per hour.
Selon l'exemple 1, on soumet à traitement thermique, dans les conditions décrites ci-dessus, à la température de 405°C et pendant 175 minutes, un brai de goudrons de houille possédant un point de ramollissement C.I.A. de 84,7°C, une teneur en substances insolubles dans la quinoléine (résines a) égale à 3,3% en poids, une teneur en résines a + égale à 24,1% en poids et une teneur en carbone fixe égale à 48,0% en poids. Le brai liant obtenu à l'issue de ce traitement possède les caractéristiques indiquées au tableau ci-après.According to 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.
Selon l'exemple 2, on soumet le brai liant obtenu à l'exemple 1 à une distillation éclair sous une pression de 0,145 bar de manière à éliminer 4,5% de l'huile qu'il contient. Le brai liant obtenu à l'issue de cette distillation possède les caractéristiques indiquées au tableau ci-après.According to 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.
On utilise l'appareillage décrit précédemment, en remplaçant le four électrique par un applicateur de micro-ondes. Ce dernier est constitué par huit tronçons de guide empilés et décalés les uns par rapport aux autres de 90°. Chacun de ces tronçons est relié à un magnétron pouvant débiter 800 W, mais volontairement limité à 400 W pour protéger le magnétron contre une mauvaise adaptation. Ces magnétrons fonctionnent à la fréquence de 2,45 GHz. L'empilage de guides d'onde est traversé par un réacteur en quartz, d'une capacité utile de 1000cm3, dans lequel circule le brai liquide. Une gaine en quartz plonge dans le réacteur et permet, lorsque les magnétrons ne sont pas en service, de mesurer la température au sein du liquide. A la sortie du réacteur, un thermocouple permet la régulation en température.We use 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. At the outlet of the reactor, a thermocouple allows temperature regulation.
Contrairement au traitement thermique dans un four électrique, le traitement effectué dans l'appareillage décrit ci-dessus permet :
- - de traiter des brais, avec un débit de 2,7 I/h, à toute température allant jusqu'à 450°C ;
- - de supprimer la période de préchauffage ;
- - de ramener la puissance utile à 2,7 kW au lieu de 3,2 kW.
- - to treat pitches, with a flow rate of 2.7 I / h, at any temperature up to 450 ° C;
- - to eliminate the preheating period;
- - reduce the useful power to 2.7 kW instead of 3.2 kW.
Selon l'exemple 3, on soumet au traitement par ondes hautes fréquences, dans les conditions décrites ci-dessus, à la température de 415°C et pendant 45 minutes, le même brai de goudrons de houille que celui décrit à l'exemple 1. Le brai liant obtenu à l'issue de ce traitement possède les caractéristiques indiquées au tableau ci-après.According to 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.
Selon les exemples 4 et 5, on soumet le brai liant obtenu à l'exemple 3 à une distillation éclair sous une pression de 0,145 bar, de manière à éliminer respectivement 4,5% en poids (exemple 4) et 1,3% en poids (exemple 5) de l'huile qu'il contient. Les brais liants obtenus à l'issue de ces distillations possèdent les caractéristiques indiquées au tableau ci-après.
Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88400709T ATE55776T1 (en) | 1987-03-24 | 1988-03-23 | ELECTRODE BINDER PITCH AND METHOD OF MAKING THE SAME. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8704054A FR2612935B1 (en) | 1987-03-24 | 1987-03-24 | BINDING PIT FOR ELECTRODE AND MANUFACTURING METHOD THEREOF |
FR8704054 | 1987-03-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0286499A1 EP0286499A1 (en) | 1988-10-12 |
EP0286499B1 true EP0286499B1 (en) | 1990-08-22 |
Family
ID=9349351
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19880400709 Expired - Lifetime EP0286499B1 (en) | 1987-03-24 | 1988-03-23 | Pitch for binding electrodes and process for preparing said pitch |
Country Status (14)
Country | Link |
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US (1) | US5120424A (en) |
EP (1) | EP0286499B1 (en) |
JP (1) | JPH02502650A (en) |
AT (1) | ATE55776T1 (en) |
AU (1) | AU607760B2 (en) |
BR (1) | BR8807335A (en) |
CA (1) | CA1304199C (en) |
DE (1) | DE3860473D1 (en) |
ES (1) | ES2016675B3 (en) |
FR (1) | FR2612935B1 (en) |
GR (1) | GR3000922T3 (en) |
NZ (1) | NZ223941A (en) |
WO (1) | WO1988007571A1 (en) |
ZA (1) | ZA881882B (en) |
Families Citing this family (3)
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DE69228663T2 (en) * | 1991-12-25 | 1999-09-30 | Mitsubishi Chemical Corp., Tokio/Tokyo | Pitch-based carbon fibers and processes for making them |
RU2288938C1 (en) * | 2005-10-10 | 2006-12-10 | Общество с ограниченной ответственностью "Инженерно-технологический центр" | Method of preparing binding pitch for electrode materials |
CN1970689B (en) * | 2006-12-13 | 2010-05-12 | 上海奥韦通工程技术有限公司 | Process for preparing modified asphalt |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1323457A (en) * | 1962-06-01 | 1963-04-05 | Coal Tar Res Ass | Improvements in the manufacture of coal tar-based products |
FR2250571B1 (en) * | 1973-11-12 | 1980-01-04 | British Petroleum Co | |
JPS59758B2 (en) * | 1976-08-03 | 1984-01-09 | 理化学研究所 | Scale adhesion prevention method |
US4096056A (en) * | 1976-10-21 | 1978-06-20 | Witco Chemical Corporation | Method of producing an impregnating petroleum pitch |
FR2392143A1 (en) * | 1977-05-25 | 1978-12-22 | British Petroleum Co | PROCESS FOR MANUFACTURING CARBON OR GRAPHITE FIBERS FROM NATURAL ORGANIC MATERIAL FIBERS BY USE OF 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 (en) * | 1981-09-07 | 1994-12-07 | 東燃株式会社 | Optically anisotropic carbonaceous pitch and its manufacturing method |
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 (en) * | 1982-02-22 | 1983-08-25 | Toa Nenryo Kogyo Kk | Preparation of optically anisotropic pitch having uniformity and low softening point |
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 |
-
1987
- 1987-03-24 FR FR8704054A patent/FR2612935B1/en not_active Expired
-
1988
- 1988-03-16 ZA ZA881882A patent/ZA881882B/en unknown
- 1988-03-18 NZ NZ223941A patent/NZ223941A/en unknown
- 1988-03-21 AU AU15421/88A patent/AU607760B2/en not_active Ceased
- 1988-03-21 BR BR888807335A patent/BR8807335A/en not_active Application Discontinuation
- 1988-03-21 JP JP63502914A patent/JPH02502650A/en active Pending
- 1988-03-21 WO PCT/FR1988/000145 patent/WO1988007571A1/en unknown
- 1988-03-23 AT AT88400709T patent/ATE55776T1/en active
- 1988-03-23 EP EP19880400709 patent/EP0286499B1/en not_active Expired - Lifetime
- 1988-03-23 DE DE8888400709T patent/DE3860473D1/en not_active Expired - Lifetime
- 1988-03-23 CA CA000562237A patent/CA1304199C/en not_active Expired - Fee Related
- 1988-03-23 ES ES88400709T patent/ES2016675B3/en not_active Expired - Lifetime
-
1990
- 1990-10-11 GR GR90400752T patent/GR3000922T3/en unknown
-
1991
- 1991-01-16 US US07/643,143 patent/US5120424A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE3860473D1 (en) | 1990-09-27 |
FR2612935A1 (en) | 1988-09-30 |
US5120424A (en) | 1992-06-09 |
NZ223941A (en) | 1989-10-27 |
GR3000922T3 (en) | 1991-12-10 |
JPH02502650A (en) | 1990-08-23 |
AU607760B2 (en) | 1991-03-14 |
ES2016675B3 (en) | 1990-11-16 |
EP0286499A1 (en) | 1988-10-12 |
WO1988007571A1 (en) | 1988-10-06 |
AU1542188A (en) | 1988-11-02 |
ATE55776T1 (en) | 1990-09-15 |
FR2612935B1 (en) | 1989-06-09 |
CA1304199C (en) | 1992-06-30 |
ZA881882B (en) | 1990-01-31 |
BR8807335A (en) | 1990-03-13 |
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