EP0236675B1 - Process for producing modified pitch and its use - Google Patents

Process for producing modified pitch and its use Download PDF

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Publication number
EP0236675B1
EP0236675B1 EP87100273A EP87100273A EP0236675B1 EP 0236675 B1 EP0236675 B1 EP 0236675B1 EP 87100273 A EP87100273 A EP 87100273A EP 87100273 A EP87100273 A EP 87100273A EP 0236675 B1 EP0236675 B1 EP 0236675B1
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Prior art keywords
pitch
alkylated
weight
reactive
pitches
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German (de)
French (fr)
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EP0236675A3 (en
EP0236675A2 (en
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Winfried Dr. Boenigk
Maximilian Prof. Dr. Zander
Jürgen Dr. Stadelhofer
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Ruetgers Germany GmbH
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Ruetgerswerke AG
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    • 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
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/026—Working-up pitch, asphalt, bitumen by chemical means reaction with organic compounds

Definitions

  • the invention relates to a method for producing pitches with changed properties and the use of these pitches.
  • pitches and pitch-like residues from coal refining and mineral oil processing is extremely diverse.
  • the use in the construction sector as a binding agent, corrosion protection agent and insulating agent the use in the production of carbon or carbon molded bodies should be mentioned in particular.
  • the properties of the available pitches do not always correspond to the wishes of the processors, there has been no lack of attempts to modify the pitches in order to improve the desired properties.
  • the coking properties of pitches can be modified by removing unwanted components such as ash formers and fractions insoluble in quinoline.
  • the modification by thermal treatment and hydrogenation is also described in the literature. The hydrogenation is the most complex process.
  • JP-PS 7641,129 describes the quality improvement of petroleum and coal tar pitch by alkylating the potassium-containing pitch / solvent mixture with ethyl iodide and subsequent catalytic hydrogenation.
  • Quinoline-insoluble fractions (30% by weight of Ql) can be brought to a solution of 86% by weight by this treatment.
  • Needle coke can be produced from the QI-free pitch in a yield of 96% by weight.
  • the improved coking properties are attributable to the separation of the 01 and the hydrogenation, since alkylation with ethyl iodide in the presence of potassium alone does not improve the coking behavior, as stated above.
  • pitches by alkylation which are particularly suitable for the production of carbon, carbon moldings and their precursors and are not dealkylated before the polycondensation.
  • the object is achieved by alkylating a pitch with 5 to 50% by weight, based on the pitch of a reactive C 1 -C 4 -alkyl compound which contains at least one aromatic substituent and at least one multiple bond and / or one reactive substituent in liquid Phase, optionally under pressure, with the addition of solvents and / or gaseous catalysts.
  • hydroxyl groups, epoxy groups and thiol groups can be used as reactive substituents of the alkylating agent.
  • a catalyst has to be added or part of the hydroxy compounds have to be replaced by corresponding halogen compounds.
  • the catalyst must not remain in the alkylated pitch, since it accelerates the dealkylation during further processing by thermal treatment.
  • a solid catalyst such as AlCl 3 is unsuitable for this. Therefore only gaseous catalysts such as HCI are used.
  • Solvents are not required, but can be used especially at low alkylation temperatures or when using high-melting pitches.
  • the alkylating agent is preferably mixed in above the softening point (EP) of the pitch, in particular 60 K above the EP. At temperatures above the boiling point of the alkylating agent, the alkylation takes place under a pressure which corresponds to its vapor pressure at the alkylation temperature.
  • the alkylation can be carried out, for example, in a stirrer retort with a reflux condenser to prevent the evaporation of the alkylating agent.
  • the reaction time is dependent on the temperature and the alkylating agent used, 5-50% by weight, preferably 10-30% by weight, based on the pitch.
  • the alkylated pitch according to the invention usually shows a reduced viscosity and a lower content of toluene-insoluble (TI) and quinoline-insoluble (Ql) compared to the starting pitch.
  • TI toluene-insoluble
  • Ql quinoline-insoluble
  • the coking residue Conradson
  • a single-phase mesophase pitch is formed during thermal treatment as with hydrogenated pitches. This means that in the pitch according to the invention there is no dealkylation on thermal treatment, as is described in all known publications on alkylated pitches.
  • 100 parts by weight of a coal tar pitch with an EP (K.-S.) of 90 ° C are alkylated at 180 ° C with 10 parts by weight of a mixture of 90% by weight of benzyl alcohol and 10% by weight of benzyl chloride.
  • Benzyl chloride can be replaced by benzyl alcohol if dry HCl gas is passed through the liquid pitch during the reaction.
  • the reaction mixture is heated to 250 ° C. and kept at this temperature until the end of the water separation.
  • the analytical characteristics of the pitch change as follows through benzylation:
  • Filtered normal pitch as described in Example 1, is thermally treated under the same conditions as there.
  • the substance data are shown in Table 4. After 60 min. there is a phase separation into an isotropic pitch matrix (approx. 80% by weight) and an anisotropic bulk mesophase with a pour point that can no longer be determined after the separation. Two values are therefore given under the pitch sample 5, of which the first was measured on the pitch matrix and the second on the bulk mesophase.
  • Example 1 A comparison with the properties of the alkylated pitch in Example 1 clearly shows that the alkylation of a pitch according to the invention accelerates the polycondensation (TI and Q1 rise faster). Lower-boiling pitch components are also incorporated (the amount of distillate is lower) and the coking residue is higher, which indicates a high thermal stability of the alkylated pitch. In addition, no segregation takes place during the thermal treatment of the alkylated pitch.
  • the hydrogenation gives the pitch a better solubility than the alkylation and a lower viscosity.
  • the polymerization is delayed (Ql) and the amount of polymerizable ingredients is reduced (amount of distillate).
  • the mesophase pitch that forms in a much smaller amount also consists of a homogeneous phase as with alkylated pitch.
  • the advantageous properties of the alkylated pitches according to the invention such as the high coking residue or the low amount of distillate, the higher reactivity and the ability to form homogeneous mesophase pitches, improve its possible uses as a precursor for the production of shaped carbon bodies, as shown in the examples below becomes.
  • Alkylated pitch from Example 2 was mixed with petroleum coke of defined granulometry and fired to shaped bodies at temperatures up to 960 ° C.
  • the properties of the moldings were compared with test anodes from the same softening point.
  • the shaped articles made of benzylated pitch showed the same mechanical properties and the same burning properties with a 20% reduction in the burning time of the test bodies.
  • the petropech alkylated with chloromethylnaphthalene from Example 3 was investigated by means of "in situ hot stage microscopy" in a stream of N 2 . At a heating rate of 3 ° C / min, large mesophase areas are formed at temperatures between 350 and 400 ° C, which coke anisotropically when the temperature increases further. It is known that pitches with such behavior are suitable as precursors for needle coke.
  • the styrene alkylated pitch from Example 4 can be used as impregnation pitch.
  • the effect of the alkylation is visible when compared to a conventionally produced impregnation pitch.
  • 100 parts by weight of an alkylated pitch according to Example 1 are at 400 ° C under a pressure of 100 mbar for 60 min. thermally treated in an autoclave with stirring in an N 2 atmosphere. This creates a homogeneous mesophase pitch with an EP (K.-S.) of 270 ° C, a mesophase content of 72% by volume and a QI content of 27.3% by weight. Pitches of this type are outstandingly suitable as precursors for the production of carbon fibers, as is known from the literature.
  • precursors for carbon fibers with an EP K.-S.
  • an EP K.-S.
  • QI content 15 to 50% by weight
  • mesophase content of up to Produce 100 wt .-% in a simple manner.

Abstract

1. A process for the alkylation of pitches, characterized in that the pitches are alkylated with from 5 to 50% by weight relative to the pitch of a reactive C1 to C4 alkyl compound, which contains at least one multiple bond or/and a reactive substituent and at least one aromatic substituent which itself has no further reactive aliphatic substituent, in the liquid phase, where appropriate under pressure, with the addition of solvents or/and gaseous catalysts.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Pechen mit veränderten Eigenschaften und die Verwendung dieser Peche.The invention relates to a method for producing pitches with changed properties and the use of these pitches.

Die Verwendung von Pechen und pechartigen Rückständen aus der Kohleveredelung und der Mineralölaufarbeitung ist außerordentlich vielfältig. Neben dem Einsatz im Baubereich als Binde-, Korrosionsschutz- und Isoliermittel ist insbesondere die Verwendung bei der Herstellung von Kohlenstoff bzw. Kohlenstoff-Formkörpern zu nennen. Da die Eigenschaften der verfügbaren Peche nicht immer den Wünschen der Weiterverarbeiter entsprechen, hat es nicht an Versuchen gefehlt, die Peche zu modifizieren, um so die gewünschten Eigenschaften zu verbessern. Es ist bekannt, daß die Verkokungseigenschaften von Pechen durch Abtrennen ungewünschter Bestandteile wie etwa Aschebildnern und in Chinolin unlöslicher Fraktionen modifiziert werden können. Weiterhin ist in der Literatur die Modifizierung durch thermische Behandlung und Hydrierung beschrieben. Die Hydrierung ist dabei das aufwendigste Verfahren. Der Einfluß der Alkylierung von benzolunlöslichen (BI)/chinolinlöslichen (QS) (ß-Harzen) und chinolinunlöslichen Fraktionen von Steinkohlenteerpech (QI) ist ebenfalls untersucht worden (Fuel 1974, 53(4), 253-7). Die Alkylierung mit z. B. Alkylhalogeniden verbessert die Löslichkeit in Benzol, aber im Gegensatz zur Hydrierung wird keine Verbesserung der Graphitierbarkeit und der Koksstruktur erreicht. Ähnliche Untersuchungen an chinolinunlöslichen Fraktionen von Petroleumpechen wurden durchgeführt (Fuel 1975, 54(4), 265-8). Bei der Alkylierung mit Kalium und Ethyljodid können 60 % in eine benzollösliche Form umgewandelt werden. Die Verkokungseigenschaften werden nicht verbessert. Durch eine katalytische Hydrierung wird das alkylierte Pech wieder dealkyliert.The use of pitches and pitch-like residues from coal refining and mineral oil processing is extremely diverse. In addition to the use in the construction sector as a binding agent, corrosion protection agent and insulating agent, the use in the production of carbon or carbon molded bodies should be mentioned in particular. Since the properties of the available pitches do not always correspond to the wishes of the processors, there has been no lack of attempts to modify the pitches in order to improve the desired properties. It is known that the coking properties of pitches can be modified by removing unwanted components such as ash formers and fractions insoluble in quinoline. The modification by thermal treatment and hydrogenation is also described in the literature. The hydrogenation is the most complex process. The influence of the alkylation of benzene-insoluble (BI) / quinoline-soluble (QS) (β-resins) and quinoline-insoluble fractions of coal tar pitch (QI) has also been investigated (Fuel 1974, 53 (4), 253-7). The alkylation with z. B. Alkyl halides improves the solubility in benzene, but in contrast to the hydrogenation, no improvement in the graphitizability and the coke structure is achieved. Similar studies have been carried out on quinoline-insoluble fractions of petroleum particles (Fuel 1975, 54 (4), 265-8). When alkylated with potassium and ethyl iodide, 60% can be converted to a benzene-soluble form. The coking properties are not improved. The alkylated pitch is dealkylated again by catalytic hydrogenation.

Die Alkylierung von Asphalt mit Dodecylchlorid durch Friedel-Crafts-Reaktion ergibt ein lösliches aber schlecht graphitierbares Material (Nenryo Kyokai-Shi 1975, 54(12), 994 - 1001). In der JP-PS 7641,129 ist die Qualitätsverbesserung von Petroleum- und Kohleteerpech durch Alkylieren des Kalium enthaltenden Pech/Lösungsmittel-Gemisches mit Ethyljodid und anschließendem katalytischem Hydrieren beschrieben. Chinolinunlösliche Fraktionen (30 Gew.-% Ql) lassen sich durch diese Behandlung zu 86 Gew.-% in Lösung bringen. Aus dem QI-freien Pech kann Nadelkoks in einer Ausbeute von 96 Gew.- % erzeugt werden. Die verbesserten Verkokungseigenschaften sind der Abtrennung des 01 und der Hydrierung zuzurechnen, da die Alkylierung mit Ethyljodid in Gegenwart von Kalium allein keine Verbesserung des Verkokungsverhaltens bewirkt, wie oben ausgeführt.The alkylation of asphalt with dodecyl chloride by Friedel-Crafts reaction results in a soluble but poorly graphitizable material (Nenryo Kyokai-Shi 1975, 54 (12), 994-1001). JP-PS 7641,129 describes the quality improvement of petroleum and coal tar pitch by alkylating the potassium-containing pitch / solvent mixture with ethyl iodide and subsequent catalytic hydrogenation. Quinoline-insoluble fractions (30% by weight of Ql) can be brought to a solution of 86% by weight by this treatment. Needle coke can be produced from the QI-free pitch in a yield of 96% by weight. The improved coking properties are attributable to the separation of the 01 and the hydrogenation, since alkylation with ethyl iodide in the presence of potassium alone does not improve the coking behavior, as stated above.

Die Alkylierung durch eine Friedel-Crafts-Reaktion verbessert zwar die Löslichkeit selbst von in Chinolin unlöslichen Pechfraktionen, nicht aber das Verkokungsverhalten (Sekiyu Gakkai-Shi 1978, 21 (1), 16 - 21). Die Verkokungseigenschaften werden deutlich schlechter. Auch wenn das Ausgangspech zu anisotropem Koks verkokbar ist, wird aus dem alkylierten Pech ein nichtgraphitierbarer Koks erhalten.The alkylation by a Friedel-Crafts reaction improves the solubility of even pitch fractions insoluble in quinoline, but not the coking behavior (Sekiyu Gakkai-Shi 1978, 21 (1), 16-21). The coking properties become significantly worse. Even if the initial pitch can be coked to anisotropic coke, a non-graphitizable coke is obtained from the alkylated pitch.

Es besteht daher die Aufgabe, durch Alkylieren Peche herzustellen, die sich besonders gut zur Herstellung von Kohlenstoff, Kohlenstoff-Formkörpern und deren Precursoren eignen und nicht bereits vor der Polykondensation dealkyliert werden.There is therefore the task of producing pitches by alkylation which are particularly suitable for the production of carbon, carbon moldings and their precursors and are not dealkylated before the polycondensation.

Die Aufgabe wird gelöst durch Alkylieren eines Peches mit 5 bis 50 Gew.-%, bezogen auf das Pech einer reaktiven Ci- bis C4-Alkylverbindung, die mindestens einen aromatischen Substituenten und wenigstens eine Mehrfachbindung oder/und einen reaktiven Substituenten enthält, in flüssiger Phase, gegebenenfalls unter Druck, unter Zusatz von Lösungsmitteln oder/und gasförmigen Katalysatoren.The object is achieved by alkylating a pitch with 5 to 50% by weight, based on the pitch of a reactive C 1 -C 4 -alkyl compound which contains at least one aromatic substituent and at least one multiple bond and / or one reactive substituent in liquid Phase, optionally under pressure, with the addition of solvents and / or gaseous catalysts.

Als Pech können alle mineralöl- oder kohlestämmigen hochsiedenden aromatischen Rückstände mit einem Erweichungspunkt (Kraemer-Sarnow) zwischen 40 und 150 °C verwendet werden wie beispielsweise Krackrückstände, Aromatenextrakte, Steinkohlenpeche, Kohleöle und ähnliches. Bevorzugt werden dabei feststofffreie Peche.As a bad luck, all mineral oil or coal-derived high-boiling aromatic residues with a softening point (Kraemer-Sarnow) between 40 and 150 ° C can be used, such as cracking residues, aromatic extracts, hard coal pitches, coal oils and the like. Solids-free pitches are preferred.

Als reaktive Substituenten des Alkylierungsmittels kommen neben Halogenen Hydroxylgruppen, Epoxigruppen und Thiolgruppen in Frage. Bei der Verwendung von hydroxylsubstituierten Alkylierungsmitteln muß im Gegensatz zu halogensubstituierten ein Katalysator zugesetzt oder ein Teil der Hydroxyverbindungen durch entsprechende Halogenverbindungen ersetzt werden. Der Katalysator darf jedoch nicht im alkylierten Pech verbleiben, da er die Dealkylierung bei der Weiterverarbeitung durch thermische Behandlung beschleunigt. Ein fester Katalysator wie beispielsweise AlCl3 ist hierfür ungeeignet. Daher werden nur gasförmige Katalysatoren wie HCI verwendet.In addition to halogens, hydroxyl groups, epoxy groups and thiol groups can be used as reactive substituents of the alkylating agent. When using hydroxyl-substituted alkylating agents, in contrast to halogen-substituted ones, a catalyst has to be added or part of the hydroxy compounds have to be replaced by corresponding halogen compounds. However, the catalyst must not remain in the alkylated pitch, since it accelerates the dealkylation during further processing by thermal treatment. A solid catalyst such as AlCl 3 is unsuitable for this. Therefore only gaseous catalysts such as HCI are used.

Lösungsmittel sind nicht erforderlich, können aber verwendet werden insbesondere bei niedrigen Alkylierungstemperaturen oder wenn hochschmelzende Peche eingesetzt werden.Solvents are not required, but can be used especially at low alkylation temperatures or when using high-melting pitches.

Das Alkylierungsmittel wird vorzugsweise oberhalb des Erweichungspunktes (EP) des Peches, insbesondere 60 K oberhalb des EP's, diesem zugemischt. Bei Temperaturen oberhalb des Siedepunktes des Alkylierungsmittels findet die Alkylierung unter einem Druck statt, die seinem Dampfdruck bei der Alkylierungstemperatur entspricht. Die Alkylierung kann beispielsweise in einer Rührwerksretorte mit Rückflußkühler durchgeführt werden, um das Abdampfen des Alkylierungsmittels zu verhindern.The alkylating agent is preferably mixed in above the softening point (EP) of the pitch, in particular 60 K above the EP. At temperatures above the boiling point of the alkylating agent, the alkylation takes place under a pressure which corresponds to its vapor pressure at the alkylation temperature. The alkylation can be carried out, for example, in a stirrer retort with a reflux condenser to prevent the evaporation of the alkylating agent.

Die Reaktionszeit ist von der Temperatur und dem eingesetzten Alkylierungsmittel, 5 - 50 Gew.-% vorzugsweise 10 - 30 Gew.-% bezogen auf das Pech, abhängig. Das erfindungsgemäß alkylierte Pech zeigt wie die bekannten alkylierten Peche meist eine verminderte Viskosität und einen geringeren Gehalt an Toluolunlöslichem (TI) und Chinolinunlöslichem (Ql) verglichen mit dem Ausgangspech. Im Gegensatz zu den bekannten alkylierten Pechen erhöht sich jedoch der Verkokungsrückstand (Conradson), und es wird bei thermischer Behandlung wie bei hydrierten Pechen ein einphasiges Mesophasenpech gebildet. Das bedeutet, daß bei dem erfindungsgemäßen Pech keine Dealkylierung bei thermischer Behandlung stattfindet, wie sie in allen bekannten Veröffentlichungen über alkylierte Peche beschrieben wird.The reaction time is dependent on the temperature and the alkylating agent used, 5-50% by weight, preferably 10-30% by weight, based on the pitch. Like the known alkylated pitches, the alkylated pitch according to the invention usually shows a reduced viscosity and a lower content of toluene-insoluble (TI) and quinoline-insoluble (Ql) compared to the starting pitch. In contrast to the known alkylated pitches, however, the coking residue (Conradson) increases, and a single-phase mesophase pitch is formed during thermal treatment as with hydrogenated pitches. This means that in the pitch according to the invention there is no dealkylation on thermal treatment, as is described in all known publications on alkylated pitches.

Die Erfindung und die Eigenschaften der nach dem Verfahren hergestellten Peche wird in den nachfolgenden Beispielen näher erläutert. Sie sind Ausführungsbeispiele zur Erläuterung der praktischen Durchführung und sollen nicht den Umfang der Erfindung einschränken.The invention and the properties of the pitches produced by the process are explained in more detail in the examples below. They are exemplary embodiments to explain the practical implementation and are not intended to limit the scope of the invention.

Beispiel 1example 1

100 Gew.-Teile filtriertes Steinkohlenteernormalpech mit einem Erweichungspunkt (EP) nach Kraemer-Sarnow (K.-S.) von 72 °C, einem Verkokungsrückstand (Conradson) von 44,6 Gew.-%, 23,2 Gew.-% TI, 0,3 Gew.-% Ql und folgender Elementaranalyse:

  • C92,6 %
  • H4,7 %
  • N1,3%
  • SO,6%

werden in einem Rührkessel mit Rückflußkühler geschmolzen und auf 160 °C erhitzt. Danach werden unter Rühren 30 Gew.-Teile Benzylchlorid zudosiert, das Gemisch auf 250 °C erwärmt und diese Temperatur 5 h lang gehalten. Die Eigenschaften des so erhaltenen alkylierten Peches (1) sind in der Tabelle 1 enthalten.100 parts by weight of filtered coal tar pitch with a softening point (EP) according to Kraemer-Sarnow (K.-S.) of 72 ° C, a coking residue (Conradson) of 44.6% by weight, 23.2% by weight TI, 0.3% by weight of Ql and the following elementary analysis:
  • C92.6%
  • H4.7%
  • N1.3%
  • SO, 6%

are melted in a stirred vessel with reflux condenser and heated to 160 ° C. 30 parts by weight of benzyl chloride are then metered in with stirring, the mixture is heated to 250 ° C. and this temperature is maintained for 5 hours. The properties of the alkylated pitch (1) thus obtained are shown in Table 1.

Zur Charakterisierung des Verhaltens dieses Peches bei thermischer Behandlung wird eine Probe unter Schutzgas und langsamen Rühren bei einem Druck von 130 mbar bis auf 400 °C erwärmt und diese Temperatur gehalten. Bei Erreichen dieser Temperatur und dann alle 30 min wird eine Probe gezogen, um EP bzw. Fließpunkt (Fp) nach der Schmelzpunktbestimmung von Dr. Tottoli, TI, QI und Verkokungsrückstand zu bestimmen. Außerdem wird der Destillatanfall auf den Einsatz bezogen gemessen. Die Ergebnisse sind in der Tabelle 1 aufgeführt, wobei die bei Erreichen von 400 °C gezogene Probe mit (2) gekennzeichnet und alle folgenden fortlaufend numeriert sind.

Figure imgb0001
To characterize the behavior of this pitch during thermal treatment, a sample is heated under protective gas and slowly stirring at a pressure of 130 mbar up to 400 ° C. and this temperature is maintained. When this temperature is reached and then every 30 minutes, a sample is taken to determine the EP or pour point (Fp) after the melting point determination by Dr. Determine Tottoli, TI, QI and coking residue. In addition, the amount of distillate is measured based on the use. The results are shown in Table 1, the sample taken when 400 ° C. has been reached identified by (2) and all subsequent ones are numbered consecutively.
Figure imgb0001

Beispiel 2Example 2

100 Gew.-Teile eines Steinkohlenteerpechs mit einem EP (K.-S.) von 90 °C werden bei 180 °C mit 10 Gew.-Teilen einer Mischung aus 90 Gew.-% Benzylalkohol und 10 Gew.-% Benzylchlorid alkyliert. Benzylchlorid kann durch Benzylalkohol ersetzt werden, wenn bei der Umsetzung trockenes HCI-Gas durch das flüssige Pech geleitet wird. Das Reaktionsgemisch wird auf 250 °C erwärmt und bei dieser Temperatur bis Ende der Wasserabscheidung gehalten. Die analytischen Kenndaten des Pechs ändern sich durch Benzylierung wie folgt:

Figure imgb0002
100 parts by weight of a coal tar pitch with an EP (K.-S.) of 90 ° C are alkylated at 180 ° C with 10 parts by weight of a mixture of 90% by weight of benzyl alcohol and 10% by weight of benzyl chloride. Benzyl chloride can be replaced by benzyl alcohol if dry HCl gas is passed through the liquid pitch during the reaction. The reaction mixture is heated to 250 ° C. and kept at this temperature until the end of the water separation. The analytical characteristics of the pitch change as follows through benzylation:
Figure imgb0002

Beispiel 3Example 3

Zu 100 Gew.-Teilen eines Petropechs werden bei 200 °C 30 Gew.-Teile Chlormethylnaphthalin langsam zugetropft. Die Temperatur wird innerhalb von 3 h auf 250 °C erhöht und weitere 3 h bei 250 °C gehalten. In Tabelle 3 sind die analytischen Kenndaten des Einsatzmaterials und des erfindungsgemäß alkylierten Pechs gegenübergestellt.

Figure imgb0003
30 parts by weight of chloromethylnaphthalene are slowly added dropwise to 100 parts by weight of a petropech at 200 ° C. The temperature is raised to 250 ° C. in the course of 3 hours and kept at 250 ° C. for a further 3 hours. Table 3 compares the analytical characteristics of the feed and the pitch pitch alkylated according to the invention.
Figure imgb0003

Beispiel 4Example 4

100 Gew.-Teile carbostämmigen Pechs mit einem EP (K.-S.) von 41 °C, einem Verkokungsrückstand nach Conradson von 31,2 Gew.-%, 13,2 Gew.-% TI und 3,5 Gew.-% 01 werden auf 140 °C erwärmt. Unter Rühren werden 20 Gew.-Teile Styrol zudosiert. Nach Zugabe wird die Temperatur langsam bis auf 250 °C erhöht. 3 h nach Erreichen der Endtemperatur werden leichtflüchtige Nebenprodukte abdestilliert und der Erweichungspunkt des Pechs durch thermische Behandlung auf 70 °C erhöht. Das mit Styrol umgesetzte Pech besitzt folgende Eigenschaften: EP (K.-S.) 71 °C; TI 25,2 Gew.-%;QI 3,0 Gew.-%; Verkokungsrückstand (Conradson) 46,6 Gew.-%.100 parts by weight of carbo-derived pitch with an EP (K.-S.) of 41 ° C, a coking residue according to Conradson of 31.2% by weight, 13.2% by weight of TI and 3.5% by weight. % 01 are heated to 140 ° C. 20 parts by weight of styrene are metered in with stirring. After the addition, the temperature is slowly increased to 250 ° C. 3 h after reaching the final temperature, volatile by-products are distilled off and the softening point of the pitch is raised to 70 ° C. by thermal treatment. The pitch reacted with styrene has the following properties: EP (K.-S.) 71 ° C; TI 25.2% by weight; QI 3.0% by weight; Coking residue (Conradson) 46.6% by weight.

Beisoiel5 (Vergleich)Beisoiel5 (comparison)

Filtriertes Normalpech, wie im Beispiel 1 beschrieben, wird unter den gleichen Bedingungen wie dort thermisch behandelt. Die Stoffdaten sind in der Tabelle 4 wiedergegeben. Nach 60 min. kommt es zu einer Phasentrennung in eine isotrope Pechmatrix (ca. 80 Gew.-%) und eine anisotrope Bulkmesophase mit einem nach der Abtrennung nicht mehr bestimmbaren Fließpunkt. Unter der Pechprobe 5 sind daher jeweils zwei Werte angegeben, von denen der erste an der Pechmatrix gemessen wurde und der zweite an der Bulkmesophase.

Figure imgb0004
Filtered normal pitch, as described in Example 1, is thermally treated under the same conditions as there. The substance data are shown in Table 4. After 60 min. there is a phase separation into an isotropic pitch matrix (approx. 80% by weight) and an anisotropic bulk mesophase with a pour point that can no longer be determined after the separation. Two values are therefore given under the pitch sample 5, of which the first was measured on the pitch matrix and the second on the bulk mesophase.
Figure imgb0004

Der Vergleich mit den Eigenschaften des alkylierten Peches in Beispiel 1 zeigt deutlich, daß durch die erfindungsgemäße Alkylierung eines Peches die Polykondensation beschleunigt wird (TI und Ql steigen schneller an). Dabei werden auch niedriger siedende Pechkomponenten eingebunden (die Destillatmenge ist geringer) und der Verkokungsrückstand liegt höher, was auf eine hohe thermische Stabilität des alkylierten Peches hindeutet. Außerdem findet bei der thermischen Behandlung des alkylierten Peches keine Entmischung statt.A comparison with the properties of the alkylated pitch in Example 1 clearly shows that the alkylation of a pitch according to the invention accelerates the polycondensation (TI and Q1 rise faster). Lower-boiling pitch components are also incorporated (the amount of distillate is lower) and the coking residue is higher, which indicates a high thermal stability of the alkylated pitch. In addition, no segregation takes place during the thermal treatment of the alkylated pitch.

Beispiel 6 (Vergleich)Example 6 (comparison)

In einem Rührwerksautoklaven werden 100 Gew.-Teile Normalpech entsprechend Beispiel 1 mit 300 Gew.-Teilen 1.2.3.4.-Tetrahydrochinolin unter Rühren bei 25 bar auf 430 °C erhitzt und diese Temperatur 15 min. gehalten. Nach Abdestillieren des Lösungsmittels wird ein hydriertes Pech (1) mit den in der Tabelle 5 aufgeführten Eigenschaften erhalten. Eine Probe dieses Peches wird wie im Beispiel 1 thermisch behandelt. Die Analysenergebnisse sind entsprechend der Tabelle 1 des Beispiels 1 der Tabelle 5 zu entnehmen.

Figure imgb0005
In a stirrer autoclave, 100 parts by weight of normal pitch according to Example 1 with 300 parts by weight of 1.2.3.4.-tetrahydroquinoline are heated to 430 ° C. with stirring at 25 bar and this tempera 15 min. held. After the solvent has been distilled off, a hydrogenated pitch (1) with the properties listed in Table 5 is obtained. A sample of this pitch is treated thermally as in Example 1. The analysis results are shown in Table 1 of Example 1 in Table 5.
Figure imgb0005

Durch die Hydrierung erhält das Pech eine bessere Löslichkeit als durch die Alkylierung und eine niedrigere Viskosität. Die Polymerisation wird allerdings verzögert (Ql) und die Menge an polymerisierbaren Inhaltsstoffen verringert (Destillatmenge). Das sich in wesentlich geringerer Menge bildende Mesophasenpech besteht ebenfalls aus einer homogenen Phase wie beim alkylierten Pech.The hydrogenation gives the pitch a better solubility than the alkylation and a lower viscosity. However, the polymerization is delayed (Ql) and the amount of polymerizable ingredients is reduced (amount of distillate). The mesophase pitch that forms in a much smaller amount also consists of a homogeneous phase as with alkylated pitch.

Beispiel 7 (Vergleich)Example 7 (comparison)

100 Gew.-Teile Benzolextrakt eines Normalpechs entsprechend Beispiel 1 werden mit 3 Gew.-Teilen AI-C13 versetzt.100 parts by weight of benzene extract of a normal pitch according to Example 1 are mixed with 3 parts by weight of AI-C1 3 .

Danach werden 31,3 Gew.-Teile in Benzol gelöstes n-Butylchlorid bei 50 °C unter Rühren zugetropft und die Temperatur auf 80 °C erhöht. Nach 2 h Reaktionszeit wird das Reaktionsprodukt neutral gewaschen und das Lösungsmittel bei 200 °C und 5 mbar abdestilliert. Das als Rückstand anfallende butylierte Pech ist durch die in Tabelle 6 angegebenen Werte charakterisiert. Der Butylgehalt errechnet sich aus dem C/H-Verhältnis zu 7 Gew.-%. Der Verkokungsrückstand ist drastisch zurückgegangen. Dies ist nicht allein auf die bei der thermischen Behandlung beobachtete Dealkylierung zurückzuführen. Das Pech selbst ist thermisch instabil geworden. Die thermische Crackung konkurriert mit Polymerisationsreaktionen. Mesophasen können sich nicht ausbilden. Die Ursachen hierfür können sowohl an der leichten Abspaltbarkeit der Butylgruppen liegen als auch daran, daß es nahezu unmöglich ist, den Katalysator vollständig aus der Pechlösung zu entfernen.

Figure imgb0006
Thereafter, 31.3 parts by weight of n-butyl chloride dissolved in benzene are added dropwise at 50 ° C. with stirring and the temperature is increased to 80 ° C. After a reaction time of 2 h, the reaction product is washed neutral and the solvent is distilled off at 200 ° C. and 5 mbar. The butylated pitch obtained as a residue is characterized by the values given in Table 6. The butyl content is calculated from the C / H ratio at 7% by weight. The coking residue has decreased drastically. This is not solely due to the dealkylation observed in the thermal treatment. The pitch itself has become thermally unstable. Thermal cracking competes with polymerization reactions. Mesophases cannot develop. The reasons for this can be due to the fact that the butyl groups can easily be split off, as well as the fact that it is almost impossible to completely remove the catalyst from the pitch solution.
Figure imgb0006

Die vorteilhaften Eigenschaften der erfindungsgemäß alkylierten Peche, wie beispielsweise der hohe Verkokungsrückstand bzw. der geringe Destillatanfall, die höhere Reaktivität und die Fähigkeit, homogene Mesophasenpeche zu bilden, verbessern seine Einsatzmöglichkeiten als Precursor für die Herstellung von Kohlenstoff-Formkörpern, wie in den nachfolgenden Beispielen gezeigt wird.The advantageous properties of the alkylated pitches according to the invention, such as the high coking residue or the low amount of distillate, the higher reactivity and the ability to form homogeneous mesophase pitches, improve its possible uses as a precursor for the production of shaped carbon bodies, as shown in the examples below becomes.

Beispiel 8Example 8

Alkyliertes Pech aus Beispiel 2 wurde mit Petrolkoks definierter Granulometrie gemischt und bei Temperaturen bis 960 °C zu Formkörpern gebrannt. Die Eigenschaften der Formkörper wurden mit Testanoden aus Pechen gleichen Erweichungspunktes verglichen. Die Formkörper aus benzyliertem Pech zeigten gleiche mechanische Eigenschaften und gleiche Abbrandeigenschaften bei einer um 20 % reduzierten Brenndauer der Testkörper.Alkylated pitch from Example 2 was mixed with petroleum coke of defined granulometry and fired to shaped bodies at temperatures up to 960 ° C. The properties of the moldings were compared with test anodes from the same softening point. The shaped articles made of benzylated pitch showed the same mechanical properties and the same burning properties with a 20% reduction in the burning time of the test bodies.

Beispiel 9Example 9

Das mit Chlormethylnaphthalin alkylierte Petropech aus Beispiel 3 wurde mittels "in situ-Heiztischmikroskopie" im N2-Strom untersucht. Bei einer Aufheizgeschwindigkeit von 3 °C/min entstehen bei Temperaturen zwischen 350 und 400 °C großflächige Mesophasenbereiche, die bei weiterer Temperaturerhöhung anisotrop verkoken. Es ist bekannt, daß Peche mit derartigen Verhalten als Precursor für Nadelkokse geeignet sind.The petropech alkylated with chloromethylnaphthalene from Example 3 was investigated by means of "in situ hot stage microscopy" in a stream of N 2 . At a heating rate of 3 ° C / min, large mesophase areas are formed at temperatures between 350 and 400 ° C, which coke anisotropically when the temperature increases further. It is known that pitches with such behavior are suitable as precursors for needle coke.

Beispiel 10Example 10

Das mit Styrol alkylierte Pech aus Beispiel 4 kann als Imprägnierpech verwendet werden. Der Effekt der Alkylierung wird bei Vergleich mit einem konventionell hergestellten Imprägnierpech sichtbar.The styrene alkylated pitch from Example 4 can be used as impregnation pitch. The effect of the alkylation is visible when compared to a conventionally produced impregnation pitch.

Figure imgb0007
Figure imgb0007

Die höhere Reaktivität des alkylierten Pechs bei thermischer Behandlung erklärt höhere Verkokungsrückstände. Die geänderte chemische Struktur bewirkt gleichzeitig eine für die Anwendung wichtige Viskositätssenkung.The higher reactivity of the alkylated pitch during thermal treatment explains higher coking residues. The changed chemical structure also brings about an important reduction in viscosity for the application.

Beispiel 11Example 11

100 Gew.-Teile eines alkylierten Peches nach Beispiel 1 werden bei 400 °C unter einem Druck von 100 mbar 60 min. in einem Autoklaven unter Rühren in N2-Atmosphäre thermisch behandelt. Dabei entsteht ein homogenes Mesophasenpech mit einem EP (K.-S.) von 270 °C, einem Mesophasengehalt von 72 Vol.-% und einem QI-Gehalt von 27,3 Gew.-%. Peche dieser Art sind hervorragend als Precursor für die Herstellung von Kohlenstoff-Fasern geeignet, wie aus der Literatur bekannt ist.100 parts by weight of an alkylated pitch according to Example 1 are at 400 ° C under a pressure of 100 mbar for 60 min. thermally treated in an autoclave with stirring in an N 2 atmosphere. This creates a homogeneous mesophase pitch with an EP (K.-S.) of 270 ° C, a mesophase content of 72% by volume and a QI content of 27.3% by weight. Pitches of this type are outstandingly suitable as precursors for the production of carbon fibers, as is known from the literature.

Durch Variation der Parameter der thermischen Behandlung und des Alkylierungsmittels lassen sich Precursor für Kohlenstoff-Fasern mit einem EP (K.-S.) zwischen 200 und 350 °C, einem QI-Gehalt von 15 bis 50 Gew.-% und einem Mesophasengehalt bis 100 Gew.-% in einfacher Weise herstellen.By varying the parameters of the thermal treatment and the alkylating agent, precursors for carbon fibers with an EP (K.-S.) between 200 and 350 ° C., a QI content of 15 to 50% by weight and a mesophase content of up to Produce 100 wt .-% in a simple manner.

Claims (10)

1. A process for the alkylation of pitches, characterized in that the pitches are alkylated with from 5 to 50% by weight relative to the pitch of a reactive Ct to C4 alkyl compound, which contains at least one multiple bond or/and a reactive substituent and at least one aromatic substituent which itself has no further reactive aliphatic substituent, in the liquid phase, where appropriate under pressure, with the addition of solvents or/and gaseous catalysts.
2. A process according to claim 1, characterized in that the pitch is an aromatic mineral-oil- or carbon- derived residue with a softening point (Kraemer-Sarnow) in the range of 40 and 150°C.
3. A process according to claim 1, characterized in that the reactive alkyl group is added to the pitch in a quantity of from 5 to 50% by weight, preferably from 10 to 30% by weight relative to the pitch.
4. A process according to claim 1, characterized in that the reactive substituents are halogens, hydroxyl groups, epoxy groups or thiol groups.
5. A process according to claim 1, characterized in that HCI gas is used as a gaseous catalyst.
6. An alkylated pitch obtainable by the process according to claims 1 to 5, characterized in that the softening point of the alkylated pitch is only slightly higher than that of the starting pitch, and the proportion of constituents insoluble in quinoline is not greater than in the starting pitch.
7. The use of the alkylated pitch according to claim 6, where appropriate after distilling off low-boiling components or fluxes with high-boiling aromatic oils as impregnation agents for carbon moulding bodies.
8. The use of the alkylated pitch according to claim 6, where appropriate after thermal polycondensation as a precursor for the preparation of high-anisotropic coke.
9. The use of the alkylated pitch according to claim 6 after thermal treatment under vacuum with a softening point (K.-S.) of between 200 and 350°C, a quinoline-insoluble content of from 15 to 50% by weight and a mesophase content of up to 100% by weight as a precursor for carbon fibres.
10. The use of the alkylated pitch according to claim 6, where appropriate after distilling off low boiling components or fluxes with high-boiling aromatic oils as binders in the manufacture of electrodes.
EP87100273A 1986-03-12 1987-01-12 Process for producing modified pitch and its use Expired - Lifetime EP0236675B1 (en)

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US9162955B2 (en) * 2013-11-19 2015-10-20 Uop Llc Process for pyrolysis of a coal feed
TWI657127B (en) * 2017-01-20 2019-04-21 台灣中油股份有限公司 Densifying agent
CN108485694B (en) * 2018-04-11 2021-01-19 北京化工大学 Method for preparing high-quality mesophase pitch by co-carbonization method
RU2687899C2 (en) * 2018-11-01 2019-05-16 Чингиз Николаевич Барнаков Method of producing pitch from waste fractionation of still residue of styrene
CN114959949B (en) * 2022-04-27 2023-06-13 北京化工大学 Condensed ring aromatic hydrocarbon carbon fiber and preparation method thereof
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