US3668110A - Pitch treatment means - Google Patents

Pitch treatment means Download PDF

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Publication number
US3668110A
US3668110A US84883A US3668110DA US3668110A US 3668110 A US3668110 A US 3668110A US 84883 A US84883 A US 84883A US 3668110D A US3668110D A US 3668110DA US 3668110 A US3668110 A US 3668110A
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Prior art keywords
pitch
solvent
particles
carried out
softening point
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Expired - Lifetime
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US84883A
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English (en)
Inventor
Frederick L Shea
Louis A Joe
Thomas W Martin
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LOUIS A JOE
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LOUIS A JOE
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Assigned to MANUFACTURERS HANOVER TRUST COMPANY A NY CORP. reassignment MANUFACTURERS HANOVER TRUST COMPANY A NY CORP. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREAT LAKES CARBON CORPORATION, A DE CORP
Assigned to MANUFACTURERS HANOVER TRUST COMPANY, AS CO-AGENT, CHASE MANHATTAN BANK, N.A., THE, AS CO-AGENT reassignment MANUFACTURERS HANOVER TRUST COMPANY, AS CO-AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREAT LAKES CARBON CORPORATION
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof

Definitions

  • ABSTRACT A spinnable pitch, useful in the manufacture of carbon filaments of continuous lengths, is prepared by the multiple solvent extraction of pitch, first by trituration of pitch particles with a low-boiling, aromatic solvent in which the bulk of pitch particles is essentially insoluble then by dissolution of the pitch in a solubilizing solvent, filtration, and evaporation of the solvent.
  • Carbon fibers have been produced from organic polymer fibers such as rayon or polyacrylonitrile by oxidation and carbonization of the fibers. The same process has been found to be applicable to manufacture carbon fibers from filaments of polyvinyl chloride, polyvinyl acetate, blown asphalt, and petroleum pitch.
  • Otani U.S. Pat. No. 3,392,216, July 9, I968, discloses and claims a method for the heat treatment of several of these pitch-like materials, particularly polyvinyl chloride.
  • the Otani method involves heating the starting material to 300-400 C. in an inert atmosphere to raise the softening point and improve the molecular weight range of the pitch-like material.
  • Coal tar pitch is particularly difiicult to use because of the presence of an insoluble second-phase material which must be removed prior to spinning. If allowed to remain when the fiber is drawn from the spinnerette, the particles of second-phase material will form stress points in the filament which tend to lower the strength of the filament. Nodules on the surface of the filament will render the filament unacceptable for use in certain applications.
  • These carbonized filaments have a tensile strength of 80,000 to 130,000 psi, a volume resistivity of l,280l ,600 micro-ohm inches, and an apparent density of about 1.65 g./cc. They are useful as substrates for boron deposition, and as fillers for carbon-carbon, carbon-resin, carbon-metal composites and other similarapplications where filamentary carbon is conven-tionally and advantageously employed.
  • This invention relates to an improved method of preparing a spinnable pitch-like material from pitches of petroleum, coal tar, and the pyrolysis of organic polymers origin.
  • this invention relates to a method of preparing such pitch-like material without subjecting the pitch precursor to heat treatment to raise the softening point, thus avoiding the potential for second phase carbon formations.
  • Fibers prepared from the pitch and oxidized and carbonized in the usual manner have improved characteristics.
  • a pitch from coal tar or petroleum, petrochemicals and the pyrolysis or organic polymers is l fabricated into small particles capable of being acted upon by an appropriate solvent to remove therefrom low boiling, low molecular weight material; 2) the resulting particles are contacted with such an essentially aromatic or equivalent solvent to remove such low boiling, low molecular weight materials at a temperature from about ambient room temperature to about the softening point of the pitch in contact with the solvent; (3) the particles are separated from the solvent; 4) the particles are then extracted with a solubilizing solvent; (5) the resulting suspension is filtered to remove the insoluble solid materials therefrom, and (6) the solvent of the second extraction is evaporated from the resulting filtrate to yield a spinnable pitch.
  • steps 1, 2, and 3 are removed until after the performance of step 6. That is, (l) the raw pitch is extracted in a solubilizing solvent; (2) filtered to remove the solid materials therefrom; (3) the sol vent is removed by evaporation; (4) the resulting solid or liquid filtered pitch is ground if necessary; (5) extracted by an appropriate solvent to remove the low-molecular weight components; and (6) separated from the extract.
  • the pitch when prepared by either of the above methods, need not be subjected to heating over long periods of time and is of a physically more uniform nature with respect to softening point and homogeneity than is a heat treated pitch.
  • the filaments manufactured therefrom when carbonized to 1,200 C. or above are stronger than those prepared from heat treated pitches.
  • the first step of the herein-described method is to mechanically or otherwise form the pitch into small particles, of the order of -l00 mesh. This can be done most conveniently by grinding or milling solid pitch or by nebulizing or atomizing a molten pitch and rapidly cooling the droplets to below their softening point so as to prevent coalescence. This nebulization can be accomplished in the presence of the aromatic or equivalent solvent useful for the subsequent process of this invention.
  • the above-formed pitch particles are then extracted by a selected solvent in such a quantity that from about 10 to about 30 percent of the pitch is extracted into the solvent, the soluble portion of the pitch being the low molecular weight components thereof.
  • the choice of solvent and solvent volume is determined by the desired softening point range of the final pitch product.
  • a pitch solubilizing solvent, quinoline used in a solvent to pitch ratio of 1:l (V/V) is adequate and a non-solubilizing solvent, benzene, in a 1:l (V/V) ratio is satisfactory to the practice of this invention. It is preferred to use a solid to solvent ratio of about 1:5 (V/V) when benzene is used as a solvent.
  • the extraction can be carried out at from about the freezing point of the solvent to about the softening point of the pitch.
  • the solvent can be recovered and reused, safety and economics dictate the use of a relatively large volume of solvent at or about room temperature.
  • about l-lO volumes of benzene per volume of pitch is capable of performing the extraction depending upon the temperature at which the extraction is carried out.
  • any residual solvent contained in the pitch is removed therefrom prior to further treatment of the pitch such as dissolution of the pitch in the second solvent by the method of this invention.
  • This solvent removal can be effected by the usual vacuum stripping or evaporative techniques carried out at or below atmospheric pressure. It is advantageous to use vacuum removal of the solvent in order to raise the relative vapor pressure thereof.
  • the resulting solid pitch particles are then dissolved in a sufficient quantity of a pitch solubilizing solvent to dissolve at least 45 percent of the pitch based upon the total quantity of starting pitch. This dissolution can be accomplished at from the freezing point to the reflux temperature of the solvent.
  • the solvent useful for this dissolution can be the same or a different solvent from that used in the first extractive step. If the solvent is the same, it is obvious that a greater quantity of solvent will be necessary and/or a higher temperature will be required to carry out the dissolution at this point. If the solvents are different, the volume and temperature of dissolution are so chosen to provide a pitch of the proper softening range and physical characteristics. For example, if benzene is used as a solvent, a solvent-pitch ratio of 4:1 (V/W) is appropriate for the first extraction at room temperature, and a solventpitch ratio of 50:1 (V/W) at reflux temperature is useful for the second extraction to provide a final product having a softening range of 240-260 C. from a 150 C. softening point starting pitch. The same effect can be accomplished by using a benzene solvent in 5:1 solvent-pitch ratio and a quinoline solvent in :1 solvent pitch ratio for the two extractive steps.
  • the next step in the purification process is the separation of the second-phase insoluble material, commonly called quinoline insolubles, from the pitch-solvent mixture. This separation is carried out by filtration, centrifugation, or similar separation technique.
  • the filtrate is then stripped of the solvent.
  • the stripping operation is preferably carried out at less than atmospheric pressure in order to avoid heating the pitch to a temperature at which rearrangement and cracking can occur.
  • a quinoline-pitch (10:1) mixture is heated for about 8.5 hours, ultimately attaining a temperature of 235 C. at 0.15 mm. (in.) in order to completely remove the quinoline therefrom.
  • Solvents useful for the dissolution steps of this invention include acetone, benzene, toluene, o, m, p-xylene, Tetralin, methyl ethyl ketone, quinoline, isoquinoline, indole, pyridine, quinoxaline, pyridine, pyrimidine, pyrazine, 01-, and ,B-methylnaphthylene, dimethyl formamide, dimethyl acetamide, dimethylsulfoxide, dimethylsulfone, and the like, and mixtures thereof in appropriate concentrations to carry out the manipulative steps as required by this invention.
  • the suspension is filtered, and the filter cake washed with 300 ml. of hexane and dried in vacuo for 4 hours. A residue of 294 g. is obtained which is mixed with 2,940 g. of quinoline for 10 minutes at 60-70C.
  • the suspension is filtered using 25 g. of diatomaceous earth as a filter aid.
  • EXAMPLE 2 A coal tar pitch of similar origin to that of Example 1 10 g.) is extracted by stirring with 100 ml. of quinoline at about room temperature for one hour. The mixture is filtered and the residue washed well with 10 ml. of quinoline. The filtrates are combined and the solvent removed therefrom by evaporation in vacuum.
  • the resulting residue is ground to 100 mesh and extracted by stirring into 4 volumes (W/V) of a mixture of benzenehexane (3:1).
  • EXAMPLE 3 A polyvinyl chloride pitch of softening point l50-l60 C. is milled to l00 mesh and the resulting powder is extracted with 4 volumes (W/V) of a 10:1 (V/V) mixture of acetonebenzene at the freezing point of the solvent mixture. After stirring the mixture for one hour, the pitch is separated by decantation and the residue dried in vacuo. A second solvent mixture comprising pyridine-benzene, 20:1 (V/V) is added to the solid pitch powder. The mixture is refluxed for 12 hours and then filtered. The filtrate is evaporated to dryness resulting i a spinnable pitch of softening point over 250 C.
  • EXAMPLE 5 is separated and conducted into a second catalytic cracking zone.
  • the side stream of cycle oil therefrom is heated to a temperature of 525 C. in a thermal cracking unit maintained at about 400 psi.
  • the vapors are stripped and recovered for gas and gasoline and the high boiling aromatic cut having the following characteristics is used as starting material.
  • the above-defined starting material, 100 g. is triturated with 2.5 liters of a mixture of benzene-quinoline, 100:1 (V/V), at about 5 C. for 20 minutes.
  • the pitch is separated by decantation of the benzene-quinoline solvent.
  • the pitch is ground to l 00 mesh and then added to another benzene-quinoline mixture, 2.5 liters of a 1:50 (V/V) solution at ambient room temperature.
  • the solvent effects essentially complete solution.
  • the solid particles are collected therefrom by adsorption on charcoal and centrifugation of the solids.
  • the solution is then evaporated to dryness to provide a spinnable pitch.
  • a method for the preparation of a spinnable pitch which comprises a. grinding a pitch into small particles;
  • a method for the preparation of a spinnable pitch which comprises a. extracting the pitch with a solubilizing solvent in sulfcient quantity to dissolve at least 45 percent of the pitch;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Inorganic Fibers (AREA)
US84883A 1970-10-28 1970-10-28 Pitch treatment means Expired - Lifetime US3668110A (en)

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US8488370A 1970-10-28 1970-10-28

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US (1) US3668110A (enrdf_load_stackoverflow)
JP (1) JPS526372B1 (enrdf_load_stackoverflow)
CA (1) CA941104A (enrdf_load_stackoverflow)
FR (1) FR2113351A5 (enrdf_load_stackoverflow)
GB (1) GB1352625A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917806A (en) * 1973-09-27 1975-11-04 Kureha Chemical Ind Co Ltd Method for the preparation of carbon moldings and activated carbon molding therefrom
US3919387A (en) * 1972-12-26 1975-11-11 Union Carbide Corp Process for producing high mesophase content pitch fibers
US3953345A (en) * 1973-05-29 1976-04-27 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the production of activated carbon spheres containing nitrogen
USRE29101E (en) * 1972-09-30 1977-01-04 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the preparation of carbon moldings and activated carbon moulding therefrom
US4032607A (en) * 1974-09-27 1977-06-28 Union Carbide Corporation Process for producing self-bonded webs of non-woven carbon fibers
US4277324A (en) * 1979-04-13 1981-07-07 Exxon Research & Engineering Co. Treatment of pitches in carbon artifact manufacture
US4279660A (en) * 1979-09-06 1981-07-21 Izumi Kamo Process for the recovery and reutilization of the used materials in existing asphalt pavements
EP0097048A3 (en) * 1982-06-14 1984-02-22 Exxon Research And Engineering Company Production of optically anisotropic pitches

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4208267A (en) * 1977-07-08 1980-06-17 Exxon Research & Engineering Co. Forming optically anisotropic pitches

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871181A (en) * 1955-06-15 1959-01-27 Consolidation Coal Co Method of removing finely divided solid particles from hydrocarbonaceous liquids
US2953501A (en) * 1957-07-18 1960-09-20 R O M Societa Azionaria Raffin Apparatus for extraction by the double solvent method
US3079326A (en) * 1960-03-30 1963-02-26 Consolidation Coal Co Double solvent refining of tar
US3200062A (en) * 1962-04-30 1965-08-10 Phillips Petroleum Co Pitch recovery and its utilization in a cracking process
US3278415A (en) * 1963-05-15 1966-10-11 Chevron Res Solvent deasphalting process
US3373101A (en) * 1964-01-24 1968-03-12 Union Oil Co Friedel-crafts catalyst plus bitumen to produce pitch of increased beta resin content

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871181A (en) * 1955-06-15 1959-01-27 Consolidation Coal Co Method of removing finely divided solid particles from hydrocarbonaceous liquids
US2953501A (en) * 1957-07-18 1960-09-20 R O M Societa Azionaria Raffin Apparatus for extraction by the double solvent method
US3079326A (en) * 1960-03-30 1963-02-26 Consolidation Coal Co Double solvent refining of tar
US3200062A (en) * 1962-04-30 1965-08-10 Phillips Petroleum Co Pitch recovery and its utilization in a cracking process
US3278415A (en) * 1963-05-15 1966-10-11 Chevron Res Solvent deasphalting process
US3373101A (en) * 1964-01-24 1968-03-12 Union Oil Co Friedel-crafts catalyst plus bitumen to produce pitch of increased beta resin content

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE29101E (en) * 1972-09-30 1977-01-04 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the preparation of carbon moldings and activated carbon moulding therefrom
US3919387A (en) * 1972-12-26 1975-11-11 Union Carbide Corp Process for producing high mesophase content pitch fibers
US3953345A (en) * 1973-05-29 1976-04-27 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the production of activated carbon spheres containing nitrogen
US3917806A (en) * 1973-09-27 1975-11-04 Kureha Chemical Ind Co Ltd Method for the preparation of carbon moldings and activated carbon molding therefrom
US4032607A (en) * 1974-09-27 1977-06-28 Union Carbide Corporation Process for producing self-bonded webs of non-woven carbon fibers
US4277324A (en) * 1979-04-13 1981-07-07 Exxon Research & Engineering Co. Treatment of pitches in carbon artifact manufacture
US4279660A (en) * 1979-09-06 1981-07-21 Izumi Kamo Process for the recovery and reutilization of the used materials in existing asphalt pavements
EP0097048A3 (en) * 1982-06-14 1984-02-22 Exxon Research And Engineering Company Production of optically anisotropic pitches

Also Published As

Publication number Publication date
DE2153567B2 (de) 1975-10-23
CA941104A (en) 1974-02-05
FR2113351A5 (enrdf_load_stackoverflow) 1972-06-23
DE2153567A1 (de) 1972-05-04
GB1352625A (en) 1974-05-08
JPS526372B1 (enrdf_load_stackoverflow) 1977-02-22

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Free format text: SECURITY INTEREST;ASSIGNOR:GREAT LAKES CARBON CORPORATION, A DE CORP;REEL/FRAME:004376/0430

Effective date: 19850228

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Owner name: MANUFACTURERS HANOVER TRUST COMPANY, AS CO-AGENT

Free format text: SECURITY INTEREST;ASSIGNOR:GREAT LAKES CARBON CORPORATION;REEL/FRAME:005016/0550

Effective date: 19890112