EP0120698A2 - Matériel précurseur pour la fabrication d'objet façonné en carbone - Google Patents

Matériel précurseur pour la fabrication d'objet façonné en carbone Download PDF

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Publication number
EP0120698A2
EP0120698A2 EP84302048A EP84302048A EP0120698A2 EP 0120698 A2 EP0120698 A2 EP 0120698A2 EP 84302048 A EP84302048 A EP 84302048A EP 84302048 A EP84302048 A EP 84302048A EP 0120698 A2 EP0120698 A2 EP 0120698A2
Authority
EP
European Patent Office
Prior art keywords
components
precursor
pitch
precursor material
oxidizable
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.)
Ceased
Application number
EP84302048A
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German (de)
English (en)
Other versions
EP0120698A3 (fr
Inventor
Ghazi Dickakian
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Exxon Research and Engineering Co
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 EI Du Pont de Nemours and Co, Exxon Research and Engineering Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0120698A2 publication Critical patent/EP0120698A2/fr
Publication of EP0120698A3 publication Critical patent/EP0120698A3/fr
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues

Definitions

  • This invention relates to the manufacture of carbon artifacts such as carbon fibers, and more particularly to a new precursor for carbon artifact manufacture that is custom blended from individual and distinct components of one or more feedstocks.
  • a polycondensed aromatic feedstock can be transformed into a pitch precursor by a variety of thermal or catalytic processes.
  • Ashland pitch nos. 240,170 or 212 can be produced by a thermal- treatment of catalytic cracking residue.
  • Catalytic cracking residue pitch is produced according to U.S.
  • Patent 4,271,006 by a vacuum heat-soaking process;or by heat-soaking a steam cracking tar residue as described in our European Publication 67581-A; or by heat-soaking a distillate of a steam cracking tar residue, as described in our European Publications 1U0198-A ana 86607-A; or by heat-soaking distillate from coal processing such as in a coal liquefication process as described in our European Publications 99753-A and 86609-A.
  • pitch precursor An understanding of the characteristics and the chemical structure of the various molecules (or parts) of a pitch precursor is necessary to process and spin the pitch (or fraction) into 8-12 microns "green” fibers. After spinning, the precursor is oxidized (at 220-300°C) to transform the "green” fiber infusable, and then, carbonized at 1400-2000°C into high tensile strength carbon fibers.
  • This invention is based upon a new concept in carbon artifact manufacture, wherein a precursor can be manufactured by blending extracted components of at least one pitch to give an optimized mixture having the proper chemistries and rheology to provide high strength carbon artifacts.
  • High tensile strength pitch-derived carbon fibers are produced by spinning a carbonaceous material with a specific composition of matter.
  • This composition generally speaking, comprises two major parts: (1) a low molecular weight, low aromaticity, isotropic, volatile plasticizer part; and (2) a high softening, high aromaticity, thermally-stable, anisotropic part. These two parts must be present in appropriate proportions to produce a molten carbonaceous material with the desired softening, fluidity, rheology, volatility and stability suitable for producing high strength carbon fibers.
  • the invention has further defined and separated individual components within these two major fractions, and has further blended these components in given proportions to provide a customized blend.
  • this invention recognizes that individual components can be cross-blended from different feedstocks, e.g. oxidizable components from a coal distillate feedstock pitch can be blended with plasticizers from a cat cracker bottom feedstock pitch.
  • This invention has realized that not all pitches or fractions of pitches are suitable for carbon fiber production, and that too much or too little of certain components can severely effect the final carbon artifact product.
  • a typical cat cracker bottom pitch can be separated into eight components or fractions by solvent extraction techniques:
  • composition analysis is carried out as follows: the material to be tested is introduced into a glass reactor equipped with a mechanical agitator and electrically heated from the outside. The solvent is then added and the mixture agitated vigorously and heated to the desired temperature for the desired time. The insolubles are filtered using fritered glass filters, dried under reduced pressure at around 100°C and the insolubles yield calculated. Summary of the conditions of the solvent analysis is as follows:
  • the "P 2 " component which is usually present in the total cat cracker bottom pitch in a percentage by weight of between 10 and 20%, can now be blended into a customized precursor mixture in a lower percentage such as 5% or a higher percentage such as 30%.
  • the other components can be likewise manipulated.
  • a precursor can be fabricated, which has characteristics never before achieved by conventional fractional treatments or by processing.
  • synthetic materials may also be added to the customized blend.
  • Synthetic materials suitable as components for preparing a carbon precursor of our invention can be one or more of the following:
  • this invention for the first time teaches the custom blending of different components or fractions of pitches to achieve a precursor having a specific and controllable composition.
  • This type of precursor will be capable of providing a final carbon artifact product of higher strength and quality.
  • this invention correlates the relationship between various component fractions of the precursor and the strength of the final product.
  • This invention pertains to the fabrication of a customized precursor for use in carbon artifact manufacture.
  • the customized precursor has a specific composition, because it is custom blended from individual and separate components and/or fractions of one or more pitches.
  • the various components fall within two major catagories: (1) the plasticizers or non-oxidizables; and (2) the hard, oxidizable fractions. These two parts of every precursor must be blended in proper proportions. In order to achieve a precursor having the desired rheology and chemical structure for spinning into carbon fibers, the precursor must contain a minimum amount of plasticizer components. In order to achieve high strength fibers, the precursor should contain a certain minimum amount of the hard, oxidizable components.
  • the blended precursor should have a given ratio by weight between oxidizable and non-oxidizable components, respectively, in an approximate range of 2.3 to 5.0; 1, and preferrably 4.0:l.
  • the precursor should have a range of ratios between non-oxidizables and oxidizables of approximately 0.43 to 0.20 and preferrably 0.25.
  • ratios may also be expressed in terms of plasticizers versus non-plasticizers or toluene solubles versus toluene insolubles.
  • a high strength fiber will usually be derived from a precursor having a maximum percentage of plasticizing material of up to about 30% by weight.
  • the plasticizer may comprise more than one component or at least one synthetic substance.
  • a precursor By blending various individual pitch components, a precursor can be obtained having a chosen chemistry. More than one feedstock can be used to provide specific precursor components.
  • a typical precursor material for the manufacture of a carbon artifact can comprise the following approximate range percentage by weight of a group of components including:
  • Each component of the above precursor can be blended in a given ratio with respect to the total precursor. Also a given component can be added to a given pitch, pitch fraction, or pitch fraction derivative.
  • Each component of the precursor can be stored in individual bins or silos.
  • a computer can be used to control the rate or quantity of components being discharged from the silos.
  • Automatic balances may be used to measure the blending solids.
  • Each component of the custom blended precursor can be obtained from a pitch by solvent extraction prior to being stored.
  • the computer may also be used in the manufacturing process to synthetically prepare at least one component before blending takes place.
  • the computer can be used to regulate the mixing of the components and any subsequent chemical or physical treatments.
  • this invention pertains to the fabrication of a precursor used in the manufacture of a carbon artifact, such as carbon fibers.
  • the invention features extracting individual components from mesophase pitches prepared from one or more feedstocks such as: (1) cat cracker bottoms; (2) steam cracker tars; (3) coal distillates; and (4) synthetics.
  • FIG. 1 a block diagram is shown of typical individual components P I ; P 2 ; O 1 ; 0 2 and 0 3 of a pitch derived from a feedstock such as a cat cracker bottom. These components can be obtained by standard solvent extraction techniques to provide eight different fractions as follows:
  • the five individual components P 1 ; P 2 ; O 1 ; 0 2 and 0 3 can be custom blended in weight percentage ranges as shown. These ranges will generally provide workable precursors for the manufacture of carbon arti - facts.
  • the crushed pitch was mixed with toluene and filter aid (at a specific pitch:toluene ratio), heated to reflux for one hour with continuous agitation and then filtered hot (90-100 0 C) to remove insolubles.
  • the filtrated was then diluted at a specific pitch:solvent ratio with a blend of toluene and heptane (specific toluene:heptane ratio) and cooled to 20°C over 4.0 hours to reject (precipitate) the desired fraction of the pitch.
  • the pitch fraction was then filtered (centrifuge), washed first with toluene (specific pitch:toluene ratio) and finally with n-heptane (specific pitch:heptane ratio). The fraction was then dried at 120-150°C under reduced pressure for 12-16 hours.
  • the fractions were spun using a 200 micron hole spinnerette, the green fibers were then oxidized at 250 to 270°C/2-5 hours and then carbonized at 1500 to 1700°C for 30 minutes.
  • Tables 1 and 2 below present the weight percentages of the fractions and extraction ratios for each of the precursor components depicted in Figure 2.
  • the characteristics of the fractions composing a pitch are very different physically, thermally (volatilization, decomposition and coking), and chemically (aromaticity and carbon/hydrogen atomic ratio).
  • This invention has found that a correct proportion or ratio of the various fractions are absolutely necessary, especially the content of the softer plasticizer fraction and the harder toluene or pyridine insoluble fractions.
  • the weight ratio of oxidizables versus non-oxidizables should be in an approximate range of 2.3 to 5.0.
  • a correct quantity of the plasticizer is required to achieve a satisfactory softening and fluidity of the molten pitch for spinning of the molten mass into 8-12 micro fibers. Satisfactory softening and fluidity is required for the proper orientation of the mesophase in the spun carbon fiber.
  • plasticizer fractions which are defined as “P I " and “P 2 " can be prepared separately or combined together. These plasticizer fractions are prepared by extraction from a pitch or from a fraction of a pitch. Plasticizer, “P l “ is prepared by extracting the pitch (or fraction) with n-heptane at reflux conditions, filtering the insolubles and recovering plasticizer, "Pi” from the filtrate by distillation under reduced pressure or preferably by roto-evaporation or thin film evaporation under reduced pressure.
  • Plasticizer "P 2" is prepared by treating the n-heptane insolubles fraction of a pitch (or fraction) with toluene at reflux conditions, filtering the toluene insolubles and then recovering plasticizer “P 2 " from the filtrate by distillation or roto-e ⁇ aporation under reduced pressure.
  • the combined plasticizers, P 1 and P 2 can be prepared by extracting a pitch or a fraction with toluene at reflux conditions for one hour, filtering the toluene insolubles and then recovering the combined plasticizers from the filtrate by distillation, roto-evaporation or thin-film evaporation.
  • the high softening fractions which are suitable for blending can also be mixed with the one or two synthetic plasticizers to prepare the desired composition.
  • Pitch, toluene insolubles, pyridine insolubles or n-heptane insolubles can be prepared by other specific processes and conditions.
  • the composition of any of the above fractions prepared by extraction vary according to the extraction condition and feed:solvent ratio used.
  • the custom blending of this invention can be computer controlled as schematically depicted in Figure 3.
  • Specific or individual components of one or more feedstocks can each be stored in respective bins or silos 10.
  • a computer 11 is connected to each bin 10 to control the discharge rate or the amount of component materials dispensed from each silo 10, to provide a unique custom blended precursor.
  • the computer 11 can also be used to control or regulate other plant processes such as heat soaking, extraction, etc.
  • the unique precursor will comprise a given ratio of each component with respect to the total precursor, such that desired properties will obtain in the resulting carbon artifact.
  • the computer 11 may also be used to control or regulate the synthesis of synthetic components, the flow of materials in the manufacturing plant, and the rate of mixing and blending of the various components.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Fibers (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Carbon And Carbon Compounds (AREA)
EP84302048A 1983-03-28 1984-03-27 Matériel précurseur pour la fabrication d'objet façonné en carbone Ceased EP0120698A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47929483A 1983-03-28 1983-03-28
US479294 1983-03-28

Publications (2)

Publication Number Publication Date
EP0120698A2 true EP0120698A2 (fr) 1984-10-03
EP0120698A3 EP0120698A3 (fr) 1985-04-03

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EP84302048A Ceased EP0120698A3 (fr) 1983-03-28 1984-03-27 Matériel précurseur pour la fabrication d'objet façonné en carbone

Country Status (4)

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EP (1) EP0120698A3 (fr)
JP (1) JPS59189168A (fr)
AU (1) AU2620984A (fr)
CA (1) CA1224604A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0250899A1 (fr) * 1986-06-02 1988-01-07 Mitsubishi Oil Company, Limited Procédé pour la production de brai ayant un point d'amollissement bas
US4910605A (en) * 1986-02-18 1990-03-20 Matsushita Electric Industrial Co., Ltd. Video signal recording method and apparatus for field-segment recording
WO2019240949A1 (fr) * 2018-06-15 2019-12-19 Exxonmobil Research And Engineering Company Modification de la dépendance à la température de la viscosité du brai pour la fabrication d'articles en carbone

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3093573A (en) * 1959-12-15 1963-06-11 Exxon Research Engineering Co Asphalts of improved resistance to flow
EP0026647A1 (fr) * 1979-09-28 1981-04-08 Union Carbide Corporation Brai à mésophase, procédés pour sa production et fibres fabriquées à partir de celui-ci
US4271006A (en) * 1980-04-23 1981-06-02 Exxon Research And Engineering Company Process for production of carbon artifact precursor
EP0057108A2 (fr) * 1981-01-28 1982-08-04 Toa Nenryo Kogyo Kabushiki Kaisha Procédé de préparation de brai carboné optiquement anisotrope

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3093573A (en) * 1959-12-15 1963-06-11 Exxon Research Engineering Co Asphalts of improved resistance to flow
EP0026647A1 (fr) * 1979-09-28 1981-04-08 Union Carbide Corporation Brai à mésophase, procédés pour sa production et fibres fabriquées à partir de celui-ci
US4271006A (en) * 1980-04-23 1981-06-02 Exxon Research And Engineering Company Process for production of carbon artifact precursor
EP0057108A2 (fr) * 1981-01-28 1982-08-04 Toa Nenryo Kogyo Kabushiki Kaisha Procédé de préparation de brai carboné optiquement anisotrope

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910605A (en) * 1986-02-18 1990-03-20 Matsushita Electric Industrial Co., Ltd. Video signal recording method and apparatus for field-segment recording
EP0250899A1 (fr) * 1986-06-02 1988-01-07 Mitsubishi Oil Company, Limited Procédé pour la production de brai ayant un point d'amollissement bas
US4793912A (en) * 1986-06-02 1988-12-27 Mitsubishi Oil Co., Ltd. Process for producing a pitch having a low softening point
WO2019240949A1 (fr) * 2018-06-15 2019-12-19 Exxonmobil Research And Engineering Company Modification de la dépendance à la température de la viscosité du brai pour la fabrication d'articles en carbone

Also Published As

Publication number Publication date
JPS59189168A (ja) 1984-10-26
CA1224604A (fr) 1987-07-28
EP0120698A3 (fr) 1985-04-03
AU2620984A (en) 1984-10-04

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Inventor name: DICKAKIAN, GHAZI