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EP0236675B1 - Procédé pour produire du brai modifié et son application - Google Patents

Procédé pour produire du brai modifié et son application Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
pitch
alkylated
weight
reactive
pitches
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
EP87100273A
Other languages
German (de)
English (en)
Other versions
EP0236675A3 (en
EP0236675A2 (fr
Inventor
Winfried Dr. Boenigk
Maximilian Prof. Dr. Zander
Jürgen Dr. Stadelhofer
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.)
Rain Carbon Germany GmbH
Original Assignee
Ruetgerswerke AG
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 Ruetgerswerke AG filed Critical Ruetgerswerke AG
Publication of EP0236675A2 publication Critical patent/EP0236675A2/fr
Publication of EP0236675A3 publication Critical patent/EP0236675A3/de
Application granted granted Critical
Publication of EP0236675B1 publication Critical patent/EP0236675B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Inorganic Fibers (AREA)

Claims (10)

1. Procédé destiné à l'alkylation de brais, caractérisé en ce que les brais comportant 5 à 50% en poids, par rapport au brai, d'un composé alkyle réactif en Ci à C4 qui contient au moins une liaison multiple ou/et un substituant réactif et au moins un substituant aromatique qui ne possède pas lui-même d'autre substituant aliphatique réactif, sont alkylés en phase liquide, éventuellement sous pression, par addition de solvants ou/et de catalyseurs gazeux.
2. Procédé selon la revendication 1, caractérisé en ce que le brai est un résidu aromatique d'origine pétrolière ou charbonnière avec un point de ramollissement (Kraemer-Sarnow) dans le domaine de 40 à 150°C.
3. Procédé selon la revendication 1, caractérisé en ce que le groupe alkyle réactif est ajouté au brai en une quantité de 5 à 50% en poids, de préférence de 10 à 30% en poids par rapport au brai.
4. Procédé selon la revendication 1, caractérisé en ce que les substituants réactif sont des halogènes, des groupes hydroxyle, des groupes époxy ou des groupes thiol.
5. Procédé selon la revendication 1, caractérisé en ce que de l'HCI gazeux est utilisé en tant que catalyseur gazeux.
6. Brai alkylé pouvant être obtenu par le procédé selon les revendications 1 à 5, caractérisé en ce que le point de ramollissement du brai alkylé n'est que faiblement supérieur à celui du brai de départ et que la fraction de constituants insolubles dans la quinoléine n'est pas plus importante que dans le brai de départ.
7. Utilisation du brai alkylé selon la revendication 6 en tant qu'agent d'imprégnation pour des pièces moulées en carbone, éventuellement après élimination par distillation des composants à bas point d'ébullition ou fluxage avec des huiles aromatiques à point d'ébullition élevé.
8. Utilisation du brai alkylé selon la revendication 6 en tant que précurseur pour la préparation de coke hautement anisotrope, éventuellement après polycondensation thermique.
9. Utilisation du brai alkylé selon la revendication 6 en tant que précurseur pour des fibres de carbone, après traitement thermique sous vide, avec un point de ramollissement (K.-S.) situé entre 200 et 350°C, une teneur en matières non solubles dans la quinoléine de 15 à 50% en poids et une teneur en mé- sophases jusqu'à 100% en poids.
10. Utilisation du brai alkylé selon la revendication 6 en tant que liant pour la confection d'électrodes, éventuellement après élimination par distillation des composants à bas point d'ébullition ou fluxage avec des huiles aromatiques à point d'ébullition élevé.
EP87100273A 1986-03-12 1987-01-12 Procédé pour produire du brai modifié et son application Expired - Lifetime EP0236675B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863608130 DE3608130A1 (de) 1986-03-12 1986-03-12 Verfahren zur herstellung modifizierter peche und deren verwendung
DE3608130 1986-03-12

Publications (3)

Publication Number Publication Date
EP0236675A2 EP0236675A2 (fr) 1987-09-16
EP0236675A3 EP0236675A3 (en) 1987-12-16
EP0236675B1 true EP0236675B1 (fr) 1990-03-21

Family

ID=6296099

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87100273A Expired - Lifetime EP0236675B1 (fr) 1986-03-12 1987-01-12 Procédé pour produire du brai modifié et son application

Country Status (6)

Country Link
US (1) US4943365A (fr)
EP (1) EP0236675B1 (fr)
JP (1) JPS62220582A (fr)
CS (1) CS262682B2 (fr)
DE (2) DE3608130A1 (fr)
PL (1) PL152346B1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140346085A1 (en) * 2013-05-24 2014-11-27 Gs Caltex Corporation Method of preparing pitch for carbon fiber
CN104178194A (zh) * 2013-05-27 2014-12-03 Gs加德士 碳纤维用沥青的制备方法
US9162955B2 (en) 2013-11-19 2015-10-20 Uop Llc Process for pyrolysis of a coal feed
TWI657127B (zh) * 2017-01-20 2019-04-21 台灣中油股份有限公司 增密劑
CN108485694B (zh) * 2018-04-11 2021-01-19 北京化工大学 一种共碳化法制备优质中间相沥青的方法
RU2687899C2 (ru) * 2018-11-01 2019-05-16 Чингиз Николаевич Барнаков Способ получения пека из отходов ректификации кубового остатка стирола
CN114959949B (zh) * 2022-04-27 2023-06-13 北京化工大学 一种稠环芳烃基碳纤维及其制备方法
CN115466626B (zh) * 2022-09-21 2024-01-12 武汉科技大学 一种高品质各向同性沥青的制备方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA891474A (en) * 1972-01-25 W. Walsh John Improved petroleum pitch binder
BE549777A (fr) *
DE410419C (de) * 1923-03-01 1925-03-06 Hoechst Ag Verfahren zur Herstellung nicht verharzender Produkte aus Urteer
US2247375A (en) * 1937-12-16 1941-07-01 Atlantic Refining Co Treatment of bituminous materials
US2545963A (en) * 1948-12-02 1951-03-20 Standard Oil Dev Co Process for producing asphalt compositions
GB899598A (en) * 1959-12-10 1962-06-27 Chemical Engineering Wiltons L Improvements in and relating to binding materials for carbon articles
US3769249A (en) * 1973-03-01 1973-10-30 Brien Corp O Thermosetting plastics and method therefor
JPS5140889B2 (fr) * 1973-10-25 1976-11-06
JPS5235367B2 (fr) * 1974-01-29 1977-09-08
FR2308893A1 (fr) * 1975-04-23 1976-11-19 Creusot Loire Echangeur tubulaire a embouts, travaillant a chaud et sous pre ssion
US4021356A (en) * 1975-09-10 1977-05-03 Texaco Inc. Alkoxylated asphalts as co-surfactants in surfactant oil recovery processes usable in formations containing water having high concentrations of polyvalent ions such as calcium and magnesium
US4317809A (en) * 1979-10-22 1982-03-02 Union Carbide Corporation Carbon fiber production using high pressure treatment of a precursor material
JPS5790093A (en) * 1980-11-27 1982-06-04 Cosmo Co Ltd Treatment of petroleum heavy oil
SU1022985A1 (ru) * 1980-12-05 1983-06-15 Кузнецкий Филиал Восточного Научно-Исследовательского Углехимического Института Способ стабилизации каменноугольного пека
JPS57147586A (en) * 1981-03-10 1982-09-11 Nippon Carbon Co Ltd Modification of pitch for carbon fiber
SU992560A1 (ru) * 1981-04-17 1983-01-30 Berdnikov Mikhail P Способ получени модифицированного таллового пека
US4464248A (en) * 1981-08-11 1984-08-07 Exxon Research & Engineering Co. Process for production of carbon artifact feedstocks
US4457828A (en) * 1982-03-30 1984-07-03 Union Carbide Corporation Mesophase pitch having ellipspidal molecules and method for making the pitch
US4465585A (en) * 1982-03-30 1984-08-14 Union Carbide Corporation Cholesteric mesophase pitch
US4431513A (en) * 1982-03-30 1984-02-14 Union Carbide Corporation Methods for producing mesophase pitch and binder pitch
CA1187653A (fr) * 1983-02-25 1985-05-28 Samuel Cukier Brais resistant a l'oxydation
US4469585A (en) * 1983-05-09 1984-09-04 Samuel Cukier Oxidation resistant pitches
US4631181A (en) * 1984-03-31 1986-12-23 Nippon Steel Corporation Process for producing mesophase pitch

Also Published As

Publication number Publication date
CS47387A2 (en) 1988-08-16
EP0236675A3 (en) 1987-12-16
DE3761984D1 (de) 1990-04-26
CS262682B2 (en) 1989-03-14
EP0236675A2 (fr) 1987-09-16
PL152346B1 (en) 1990-12-31
PL264563A1 (en) 1988-05-12
US4943365A (en) 1990-07-24
JPS62220582A (ja) 1987-09-28
DE3608130A1 (de) 1987-09-17

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