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
  • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
  • C10C1/00—Working-up tar
• • 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

• the invention relates to a process for producing carbon fibers from coal tar pitch, in particular hard coal tar pitch, according to which the coal tar pitch is freed of infusible constituents prior to spinning by filtration, then the pitch filtrate is removed from a distillation to remove volatile constituents, then from the The pitch melt obtained and the spun pitch fibers are oxidized at a given oxidation temperature and carbonized at a given carbonization temperature.
• the invention comprises in the same way the production of carbon threads.
• Graphite fibers or threads can also be produced in a known manner from the carbon fibers or threads produced.
• a process for the production of carbon or graphite fibers or filaments from coal tar pitch is known, after which the coal tar pitch is spun from the melt and the pitch fibers obtained are subjected to oxidation, then carbonization and optionally graphitization.
• the coal tar pitch has a softening point of maximum 190 ° C (KS or Krämer-Sarnow) and is heated to a temperature up to 100 ° C above the softening point before spinning.
• the pitch melt obtained is essentially freed from the solid constituents at this temperature by filtration under elevated pressure.
• the solid or infusible components are identical to quinoline-insoluble components.
• the filtered pitch melt is either a distillate subjected to up to 350 ° C or, after cooling, ground into small pitch parts which are brought into contact with an aliphatic solvent with a boiling point of up to 70 ° C.
• the solvent with the pitch components dissolved therein is separated from the insoluble pitch components.
• the carbon fibers or threads spun from the pitch melt are dusted before carbonization with finely ground activated carbon, which is impregnated with liquid oxidation aids, and heated to 400 ° C. in an oxidizing atmosphere.
• the subsequent carbonization of the oxidized carbon filaments takes place at a temperature of approx. 1000 ° C (cf. DE-PS 24 19 659).
• the invention has for its object to provide a method for producing carbon fibers from coal tarpec, in particular hard coal tar pitch, of the type described above, according to which the thermal aftertreatment can be carried out extremely simply and quickly, so that the production of the carbon fibers or . -Overall becomes particularly efficient and economical.
• the pitch filtrate is treated in the thin-film evaporator at temperatures above 200 ° C. and under vacuum to 1 mbar to increase its softening point above 260 ° C. (KS).
• the invention is based on the knowledge that the softening point for coal-derived pitch or coal tar pitch can surprisingly be increased to over 260 ° C. if the distillation is carried out in a thin-film evaporator.
• Coal tar pitch with a high softening point is advantageous in that an increased crosslinking or mechanical strength is achieved in the course of the thermal aftertreatment. A significant reduction in volatile pitch components is also achieved. Due to the very short dwell times in the thin Layer evaporators do not re-form disturbing, ie infusible, quinoline-insoluble solids, so that a homogeneous and high-purity pitch melt is formed which is particularly suitable as a starting material for the production of carbon fibers and surprisingly spins even at a softening point> 200 ° C leaves.
• the invention also relates to a device for carrying out the claimed method, which is particularly suitable for the thermal aftertreatment of the pitch fibers and has at least one fiber deposit, an oxidation furnace and a carbonization furnace.
• This device is characterized by a lower revolving stage with the oxidation furnace, a vacuum retort, the carbonization furnace and a cooling retort, all treatment facilities in an open container construction,
• an upper revolving stage which can be rotated independently of the lower revolving stage and has a traversing device for treatment retorts for the temporary reception of the fiber deposit or fiber deposit with the pitch fibers to be treated,
• the traversing device transfers the treatment retorts to the respective retort lid from the upper revolving platform under the relevant retort lid and vice versa
• the lower revolving platform has at least one lifting device for each of the oxidation oven, the vacuum retort, the carbonization oven and the cooling retort and these treatment devices for Inclusion of the treatment retorts under the retort lid receptacle or the relevant retort lid can be moved and raised and vice versa.
• the invention further provides that the treatment facilities on the lower The rotating stage is offset by 90 ° to one another and arranged on a rotating circle which, in a vertical projection, exceeds the outer circumference of the upper rotating platform for the lateral passage of the treatment devices to be raised and for connecting the raised treatment devices to the respective retort cover below the in in the same way, retort lid receptacles offset by 90 ° to one another, each treatment device being assigned its own lifting device.
• At least two treatment retorts offset by 180 ° to one another can be placed simultaneously on the upper revolving stage, so that a treatment retort with pitch fibers to be treated can alternately be fed to the treatment system and a treatment retort with finished carbon fibers can be removed.
• the fiber tray is designed as a collapsible scissor gate for fiber loops hanging freely on horizontal bars and can be inserted in a retracted treatment position when pushed together.
• Scissors creel enables the storage of a strand consisting of a large number of individual pitch fibers or pitch threads, in such a way that no fiber or thread sticking occurs during the thermal aftertreatment and free shrinkage is made possible.
• Show it 1 shows a schematic process flow diagram for the production of carbon fibers
• Fig. 2 shows the device for thermal aftertreatment in a schematic plan view below the level
• coal tar pitch is freed from infusible or quinoline-insoluble constituents by filtration before spinning. Then the pitch filtrate becomes one
• the pitch fibers 2 spun from the pitch melt or hard pitch melt are oxidized using an oxidation aid such as activated carbon at a given oxidation temperature to make them infusible.
• the oxidized pitch fibers 2 are carbonized using an inert gas at a predetermined carbonization temperature to drive off volatile by-products.
• Pitch filtrate is continuously fed into a thin-film evaporator during the distillation and evenly distributed on the inner circumference by means of a rotating distributor ring. The rotor wiper blades moving along the evaporator zone capture the pitch filtrate and a thin film over the heating wall.
• the pitch granules are melted in an extruder 3.
• the pitch melt runs through a filter 4 and is fed to a centrifugal spinning head 6 by means of a metering pump 5.
• the spinning centrifuge which is provided with nozzle bores on its lower part, presses the pitch melt through the nozzle bores. Endless filaments are created, which are placed on a slowly rotating catch ring.
• the catch ring is with one
• the treatment retort 12 is heated to 350 ° C.
• air is passed through a filter 14 through a pump 14 via an electrical heat exchanger 15 and flows through the treatment retort 12 as hot oxidation air from bottom to top. Since volatile pitch components escape during the oxidation process, the exhaust air is first fed to a heat exchanger 16. Non-condensable pollutants are then burned in an externally flame-protected exhaust air combustion system.
• the subsequent carbonization process must be carried out under inert gas in order to avoid burning the pitch fibers 2.
• the treatment retort 12 is first evacuated. Since the treatment retort 12 is made of non-vacuum-proof thin sheet metal for the purpose of good heat transfer mass arm, the carbonization furnace 11 is moved down and heated to 1000 ° C., while the vacuum retort 13 is lifted from the basement under the treatment retort 12. A vacuum unit 17 is then put into operation. After a few minutes, the vacuum retort 13 or treatment retort 12 can be expanded to normal pressure with nitrogen. For safety reasons, nitrogen is purged again.
• the vacuum retort 13 is then lowered back into the basement and exchanged for the carbonization furnace 11, which has meanwhile been heated to 1000 ° C.
• Carbonization takes ten minutes for a while, during which volatile compounds are transported through preheated nitrogen via the treatment retort 12 for condensation or combustion of exhaust air.
• the scissors gate 9 taken, subjectedDivge ⁇ and transported to the cooling state where the From cooling the carbon fibers 1 to room temperature.
• the device for the thermal aftertreatment of the pitch fibers 2 has a lower rotating stage 18 with the oxidation furnace 10, the vacuum retort 13, the carbonation furnace 11 and a cooling retort 19. All treatment devices 10, 11, 13, 19 are designed in an open container construction for receiving treatment retorts 12.
• an upper rotating platform 20, which can be rotated independently of the lower rotating platform 18, is provided with a traversing device for treatment retorts 12 for temporarily receiving the fiber trays 9 with the pitch fibers 2 to be treated.
• Above the upper rotating platform 20 there is a loading level 21 with at least one loading opening 22 and at least one retort lid receptacle 23 for retort lid 24 with connection for air and inert gas supply, vacuum and air.
• the traversing device transfers the treatment retorts 12 for connection to the respective retort cover 24 from the upper turntable 20 below the hitting retort lid 24 and vice versa.
• the lower turntable 18 has at least one lifting device 25 for the oxidation furnace 10, the vacuum retort 13, the carbonization furnace 11 and the cooling retort 19. These treatment devices can be moved to accommodate the treatment retorts 12 under the retort lid receptacles 23 or the relevant retort lid 24 and raised or vice versa.
• the treatment devices 10, 11, 13, 19 are displaceable on the lower turntable 18 by 90 ° to one another and arranged on a rotating circle which, in vertical projection, the outer periphery of the upper turntable 20 for passing the upper turntable 20 to be raised to the side for lateral pass ⁇ the treatment devices 10, 11, 13, 19 to be raised and for connecting the raised treatment devices to the respective retort cover 24 extends below the retort cover receptacles 23, which are offset by 90 ° to one another.
• Each treatment device 10, 11, 13, 19 is assigned an egg-like lifting device 25, so that one of the four processes oxidation, evacuation, carbonization and cooling can take place at the same time under each retort lid 24.
• At least two treatment retorts 12 offset from one another by 180 ° C. can be placed simultaneously on the upper rotating stage 20.
• the fiber tray is designed as a collapsible scissors gate 9 for fiber loops hanging freely on horizontal bars and, when pushed together, can be inserted into a treatment retort 12 in each case.
• the device works as follows if one of the four processes of oxidation, evacuation, carbonization and cooling takes place simultaneously under each retort lid 24:
• the upper rotating stage 20 rotates by 180 ° C. While a scissor gate 9 with finished carbon fibers 1 is removed from the other treatment retort 12, the lower rotating stage 18 rotates by 90 °, so that the cooling retort 19 against the Oxidation furnace 10 is replaced.
• the oxidation furnace 10 - a low temperature furnace - is moved from below over the treatment retort 12. During the now following oxidation process it gets hot
• Oxidation air is passed through the treatment retort 12 and the oxidation furnace 10 is heated in accordance with the optimized temperature profile.
• the hot process gases are led to the exhaust air purification.
• the oxidation furnace 10 is moved down to the lower rotating stage 18.
• the vacuum retort 13 is via the lifting device 25 from below via the treatment retort
• the treatment retort 12 is still flushed with nitrogen while relieving pressure.
• the vacuum retort 13 is moved down to the lower rotating platform 18.
• the carbonization furnace 11 is moved from below over the treatment retort 12 by means of the lifting device 25. During the subsequent carbonization process, preheated embroidery is passed through the treatment retort 12 and transports the volatile compounds to the exhaust system. Fig. 13) The carbonization furnace 11 is moved down to the lower rotating stage 18.
• the pitch fibers 2 are cooled by supplying cold nitrogen to temperatures below 600 ° C.
• the further cooling can take place in the cooling station 19 with cold air.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Fibers (AREA)
• Working-Up Tar And Pitch (AREA)
• Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
• Peptides Or Proteins (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

Country Status (10)

Cited By (4)

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Citations (7)

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• 1987
  • 1987-02-07 DE DE19873703825 patent/DE3703825A1/de active Granted
• 1988
  • 1988-01-05 AT AT88900817T patent/ATE71132T1/de not_active IP Right Cessation
  • 1988-01-05 WO PCT/EP1988/000003 patent/WO1988005805A1/de active IP Right Grant
  • 1988-01-05 AU AU11038/88A patent/AU1103888A/en not_active Abandoned
  • 1988-01-05 EP EP88900817A patent/EP0302084B1/de not_active Expired - Lifetime
  • 1988-01-05 DE DE8888900817T patent/DE3867365D1/de not_active Expired - Fee Related
  • 1988-01-15 IN IN37/CAL/88A patent/IN168504B/en unknown
  • 1988-02-04 DD DD88312675A patent/DD279907A5/de unknown
  • 1988-02-05 ES ES8800325A patent/ES2006553A6/es not_active Expired
  • 1988-02-05 GR GR880100060A patent/GR1000124B/el unknown
  • 1988-02-06 CN CN198888100656A patent/CN88100656A/zh active Pending

Patent Citations (7)

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