EP0358086B1 - Procédé pour augmenter la teneur en phase méso dans du brai - Google Patents

Procédé pour augmenter la teneur en phase méso dans du brai Download PDF

Info

Publication number
EP0358086B1
EP0358086B1 EP89115888A EP89115888A EP0358086B1 EP 0358086 B1 EP0358086 B1 EP 0358086B1 EP 89115888 A EP89115888 A EP 89115888A EP 89115888 A EP89115888 A EP 89115888A EP 0358086 B1 EP0358086 B1 EP 0358086B1
Authority
EP
European Patent Office
Prior art keywords
zone
pitch
zones
degassing
film
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
EP89115888A
Other languages
German (de)
English (en)
Other versions
EP0358086A1 (fr
Inventor
Rolf Marrett
Armin Eckert
Klaus Altfeld
Peter Oerlemans
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.)
Nouryon Faser Pensionsverwaltungs GmbH
Rain Carbon Germany GmbH
Original Assignee
Ruetgerswerke AG
Akzo Faser 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
Priority claimed from DE19883829986 external-priority patent/DE3829986A1/de
Application filed by Ruetgerswerke AG, Akzo Faser AG filed Critical Ruetgerswerke AG
Publication of EP0358086A1 publication Critical patent/EP0358086A1/fr
Application granted granted Critical
Publication of EP0358086B1 publication Critical patent/EP0358086B1/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
    • C10C1/00—Working-up tar
    • C10C1/19—Working-up tar by thermal treatment not involving distillation
    • 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
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • 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 increasing the content of mesophase in a pitch, wherein a high-molecular aromatic fraction based on coal tar and / or petroleum in the molten form and in the form of a thin, continuously moving film is thermally treated and volatile constituents during the thermal treatment removed by degassing.
  • Carbon fibers and threads are of great importance, for example as reinforcing fibers in plastics. You can inter alia be made of polyacrylonitrile or pitch precursor fibers.
  • Pitch fibers with a high mesophase content are formed by melt spinning a pitch that also has a high mesophase content.
  • Mesophase is understood to mean areas that contain aggregations of oriented molecular assemblies that still show flow behavior. Since the orientation is essentially in a certain direction, mesophasic regions behave optically anisotropically. For this reason, the mesophase in pitch is also referred to as an anisotropic phase or an anisotropic area.
  • the mesophase content of a pitch can be determined, for example, with polarized light, for example using a polarizing microscope.
  • the solubility properties of the pitch in certain solvents were also used to make statements about the mesophase content, since the mesophase is generally clear is less soluble than the non-oriented (isotropic) parts of the pitch.
  • pitches e.g. the coal tar or petroleum pitches obtained by known processes are isotropic without previous thermal treatment
  • their mesophase content must be increased by appropriate pretreatment if pitch fibers with a high mesophase content are to be obtained by melt spinning.
  • Methods have therefore been developed to increase the mesophase content of a pitch. It was found that by heat treatment under inert gas, e.g. in the range of 250 to 500 ° C, the mesophase content increases, which is due to chemical processes such as polymerization and physical processes, namely evaporation of low molecular weight, volatile isotropic components.
  • the advantage of the process is that the pitch can be thermally treated continuously as a thin film. This makes it possible to remove volatile constituents faster than when there are large pitch volumes during inpatient treatment.
  • This method also has several disadvantages.
  • First is the mesophase enrichment rate relatively low due to the low treatment temperature.
  • the low treatment temperature also has the disadvantage that the increase in the mesophase content is based almost exclusively on the removal of low molecular weight, volatile constituents, while hardly any formation of mesophase takes place due to polymerization.
  • the higher molecular weight isotropic regions are therefore retained, so that pitches with a very high mesophase content are not obtained with this method.
  • the pitch flows in the form of a laminar current without mechanical homogenization taking place.
  • the object of the present invention was to develop a method with which the content of mesophase in a pitch based on coal tar or petroleum can be increased in a short time without having to use such high temperatures that even larger ones can be obtained in a relatively short time disruptive amounts of difficult-to-melt products (coke) arise, the process should make it possible to increase the mesophase content if necessary up to 100% by weight and a separation between the isotropic phase and mesophase should be prevented, so that the mesophase obtained fortified pitch can be continuously fed to a melt spinning machine.
  • the object was achieved by a process according to the preamble of claim 1, which is characterized in that a high-molecular aromatic fraction which can contain mesophase is used, this fraction being mechanically formed continuously into a thin film with a layer thickness of about 0.007 to 2 cm and this film is mechanically forcibly conveyed in succession using shear forces through at least one homogenization zone and at least one degassing zone, with mechanical homogenization of the film in the homogenization zone (s) and easy removal in the degassing zone (s) volatile constituents is carried out, the temperature of the film in the homogenization zone (s) and in the degassing zone (s) being in the range from 320 ° to 470 ° C.
  • a high molecular weight aromatic fraction based on coal tar and / or petroleum is used for the process, ie mixtures can also be used. Such fractions are also commonly referred to as coal tar or petroleum-based pitches.
  • the term "pitch" is therefore used for these starting substances.
  • Isotropic pitches can be produced from coal or petroleum using known methods. For example, volatile constituents can be isolated from hard coal by treatment at approximately 1100 ° C., condensed and then distilled at approximately 400 ° C. The residue is coal tar pitch. Petroleum pitch can also be obtained from petroleum as the residue of a distillation. These pitches, which are normally completely isotropic, can be used in this form for the process according to the invention.
  • they are preferably pretreated in a suitable manner so that they have a mesophase content of 30 to 90% by volume. It is particularly favorable if the pitch used already has a mesophase content of 70-90%. A smaller amount of volatile constituents then has to be removed during the thermal treatment of the thin film, for example in an extruder, than with lower mesophase contents in the starting material. The result is that a very high mesophase content, for example up to 100%, is achieved in a relatively short time in a gentle manner.
  • Suitable pretreatment methods are known and consist, for example, of filtration for the purpose of removing constituents which are very difficult to melt (coke) and / or other solid constituents and distillation, and, if appropriate, of thermal treatment to form mesophase, for example in the range from 300 to 350 ° C. if necessary an extraction with solvent.
  • a thermal treatment, subsequent filtration and then a further thermal treatment can also be carried out.
  • Pitches treated in this way can, before they are used for the process according to the invention, be subjected to a further pretreatment, for example a separation and decanting process. In the latter case, there is a mechanical separation of two liquid phases that are not soluble in one another.
  • the mesophase phase is used for the process according to the invention.
  • These separation methods are advantageous because, if used, the preceding thermal treatment can be relatively short, which means that less solid components and highly viscous products are formed.
  • the previous thermal treatment can be short because it is sufficient only to achieve a relatively low mesophase content.
  • the enrichment then takes place through the separation process. If necessary, the mesophase-rich phase can be filtered again after the separation process and freed from solvent.
  • the pitch used for the method according to the invention preferably already has a content of 30 to 90% by volume, in particular 70-90% by volume, of mesophase.
  • the mesophase content is determined as follows:
  • Particles made of solid, crushed pitch with an average diameter of 2 to 2.8 mm are embedded in Epofix (hardenable resin).
  • Epofix hardenable resin
  • the mass is hardened and disks with a diameter and a thickness of about 2.5 cm each are produced from the material obtained, rubbed with silicon carbide paper and then polished first with silicon carbide paper of 2400 and then of 4000 mesh. A final polishing is done with diamond paste.
  • Photographic images of the polished samples are taken using a polarizing microscope. Circularly polarized light is used to obtain adequate contrast.
  • the isotropic portions or (in the case of phase inversion) the mesophasic portions are outlined with a pen on the A4 format images.
  • the area fraction of the framed portions is measured by means of an optical measuring device (Context Vision Image Analyzer).
  • the process is particularly favorable because of the lower content of isotropic and volatile components. Even with a mesophase content of the starting pitch of up to 90%, the process is still advantageous because it may be desirable to further increase the content due to the required quality of the pitch or carbon fibers to be produced.
  • the high molecular weight aromatic fraction (pitch) used for the process according to the invention which after pretreatment and cooling in solid form, e.g. in the form of particles, or in molten form, is continuously processed in the method according to the invention. In the event that it is in solid form, it is first melted.
  • the melted pitch is mechanically formed into a thin film with a layer thickness of approximately 0.007 to 2 cm.
  • the film is then passed through at least one homogenization zone and at least one degassing zone.
  • the film is moved further by mechanical forced conveyance, preferably essentially in the horizontal direction.
  • the advantage of horizontal arrangement of the equipment or horizontal movement of the pitch film is that the degassing step can be carried out more easily in this case.
  • the apparatus in which these treatment steps take place is therefore preferably arranged horizontally or approximately horizontally.
  • the pitch film is also mechanically positively conveyed through these zones, preferably in a substantially horizontal direction.
  • the use of more than one homogenization zone and degassing zone has the advantage that the pressure can be reduced and the temperature can be increased step by step from one zone to the next, while limits can be set here in the first homogenization and degassing zone due to the high content of volatile constituents.
  • the film is homogenized by means of mechanical action. This is done in order to mix (emulsify) the mesophasic and isotropic components, which are poorly soluble in one another. Whether the mesophase is emulsified in the isotropic phase or vice versa depends on the quantitative relationship between the two phases.
  • the homogenization avoids phase separation and a more uniform, faster and more controllable removal is more volatile Components in the subsequent degassing zone (s) reached.
  • the removal of volatile, ie low-molecular isotropic fractions causes an increase in the weight fraction of (non-volatile) mesophase.
  • the mesophase content can increase due to further polymerization and orientation of the molecules at the temperatures used in the homogenization and degassing zones. Since it should normally be avoided that the pitch is oxidized during homogenization and degassing, in this case the access of media reacting with the pitch under oxidation must be excluded.
  • the homogenization zones are preferably closed off from the environment. so that no special precautions need to be taken in these zones to prevent oxidation. However, if they are in connection with the environment, the homogenization zones may have to be operated under inert gas.
  • Volatile components must be removed and removed in the degassing zones. It is preferred to work in the degassing zones under oxygen-free inert gas. For reasons of cost, nitrogen is preferred as the inert gas, but noble gases such as argon or other gases or gas mixtures which do not react with the pitch can also be used. It is advantageous if the inert gas is not stationary over the pitch film, but is moved in the degassing zones over the surface of the pitch film. This can happen by supplying inert gas at the beginning of the respective degassing zone and withdrawing the inert gas together with the vaporized volatile constituents at the end of the degassing zone. Due to the movement of the inert gas, it acts as an entraining or carrier gas and enables the volatile constituents derived from the pitch to be removed more quickly.
  • the temperature of the pitch film is in the range from 320 to 470 ° C. At temperatures below 320 ° C and above 470 ° C, the method could in principle also be used. However, since the increase in the mesophase content proceeds more slowly with falling temperature and the risk of coking increases at very high temperatures, the process is expediently carried out within the temperature range mentioned. It is advantageous here if the apparatus used is heated to the same or a higher temperature in a degassing zone than in the respective preceding homogenization zone. In this way it can be achieved that the evaporation of volatile constituents takes place primarily in the degassing zones in which these constituents are discharged to the environment.
  • the pitch film in the homogenization zone (s) has a temperature in the range from 370 ° to 470 ° C. and / or in the degassing zones likewise has a temperature in the range from 370 to 470 ° C.
  • the melted pitch is mechanically formed into a thin film and continuously mechanically forcibly conveyed and thermally treated in this form.
  • the film can be formed, for example, by suitable stripping devices in the apparatus.
  • the pitch film obtained in this way has a layer thickness in the range from approximately 0.007 to 2 cm. Even thinner layers can result in difficulties in handling or further conveying, above all because the layer thickness can decrease in the course of the thermal treatment due to the evaporation of volatile constituents.
  • the thickness of the molten pitch film is in the range of 0.007 to 0.5 cm. It is particularly advantageous if the layer thickness of the film in the homogenization zone (s) is greater than in the subsequent degassing zone (s).
  • the thickness of the film is determined by the equipment used and can, for example, about suitable adjustable scraper elements can be set specifically.
  • a particularly favorable embodiment of the method according to the invention is characterized in that the homogenization zone (s) is or are sealed gas-tight with respect to the environment and that no constituents are removed from the pitch in the homogenization zone (s). If necessary, an increased pressure must be applied.
  • This embodiment in which in the homogenization zone (s) those components which are volatile at the present temperature and at normal pressure are also not removed from the pitch, is particularly favorable since these components are then still available for the formation of mesophase stand.
  • anthracene and naphthalene both of which are found in coal tar pitch, are well suited for the formation of mesophase due to condensation reactions at elevated temperatures. If these components are not removed, they can form mesophase in the homogenization zone.
  • the mesophase formed in this way is then no longer volatile in the subsequent degassing zone.
  • the preferred embodiment mentioned thus leads to an increase in the overall yield of pitch enriched with mesophase.
  • the homogenization zone is sealed off from the environment. It may be necessary or useful to work with a certain excess pressure in the homogenization zone.
  • This embodiment of the process in which no constituents are removed in the homogenization zone (s), can be carried out so that they all existing homogenization zones or only a part of them, for example only the first.
  • the extruder has openings in the degassing zone (s) through which volatile constituents escape, and the homogenization zone (s) are sealed off from the environment in a gas-tight manner.
  • the process according to the invention is expediently carried out in such a way that a pressure in the range from 10 ⁇ 2 to 1200 mbar is present in the degassing zone (s) during the thermal treatment of the pitch film.
  • the pressure in the first degassing zone is not too low, ie a pressure in the range from 100 to 1200 mbar. Because in this zone the particularly volatile components are removed. Too much evacuation in this area could result in products with higher boiling points also being removed, so that evaporation that is too rapid and uncontrolled could occur. The evaporation of volatile constituents can even be reduced somewhat in the first degassing zone, if necessary, by applying a slight excess pressure.
  • the process is therefore preferably carried out in such a way that a pressure in the range from 100 to 1200 mbar is present in the first degassing zone and a pressure in the range from 10 ⁇ 2 to 100 mbar in the other degassing zones which may be present.
  • a pressure in the range from 100 to 1200 mbar is present in the first degassing zone and a pressure in the range from 10 ⁇ 2 to 100 mbar in the other degassing zones which may be present.
  • the second degassing zone and possibly in further degassing zones it is in fact possible to lower the pressure considerably since In the first degassing zone, a significant part of the volatile products have already been removed.
  • By gradually lowering the pressure with continuous degassing steps it is possible to control the degassing (evaporation) in a controlled manner due to the different volatilities.
  • the method according to the invention succeeds because of the short residence time at high temperatures and because of controllable, faster removal of volatile components without reaching these disadvantages such high levels of mesophase.
  • the pitches obtained in this way, with 85 to 100% mesophase content, are very suitable for melt spinning, and the pitch threads obtained in this way, after preoxidation and carbonization or graphitization, give carbon or graphite threads with high strength and modulus values.
  • the volatile constituents, possibly together with inert gas, removed in the degassing zones can be collected and reused. For example, they or portions thereof can be re-added to an isotropic pitch which is then thermally treated as described above to form mesophase.
  • the homogenization takes place mechanically in the corresponding zones under the influence of shear forces e.g. through kneading or stirring elements. Possibly. shear forces can also be applied during the degassing and / or transport steps (e.g. during delivery to the homogenization zone or in the melting zone).
  • shear forces e.g. through kneading or stirring elements. Possibly. shear forces can also be applied during the degassing and / or transport steps (e.g. during delivery to the homogenization zone or in the melting zone).
  • the process according to the invention can preferably be carried out in an extruder in which there is at least one homogenization zone and at least one degassing zone, the film being heated before reaching the homogenization zone.
  • the pitch is introduced into the extruder, melted by heating in the first zone and formed into a film by an extruder screw, which is positively conveyed by the moving screw, preferably in the horizontal direction.
  • the homogenization can take place by means of, if appropriate, moving device components attached to the housing walls, for example in the form of a kneading treatment.
  • twin-screw mixer as an extruder, in which the two screws (screws) have the same or different directions of rotation and thus enable thorough homogenization of the thin film.
  • Suitable screw kneaders are available on the market. However, other equipment can be used if they enable the process steps mentioned to be carried out.
  • the advantage of using an extruder is that there is a wide margin for pressure control during the process.
  • the pressure in the homogenization zone (s) can be set to different values than in the degassing zone (s). If there are several homogenization zones, there may also be a different pressure in each of them. The same applies to several degassing zones.
  • pressure and temperature can be set so that the pitch enriched with mesophase can be fed continuously to a melt spinning machine. Continuous melt spinning is an economically advantageous method for producing pitch threads.
  • reaction accelerators chemically increase the rate of mesophase formation. Examples are elemental sulfur or Lewis acids such as boron trifluoride, which can be removed again during the degassing steps. Reaction accelerators can be added to either the pitch or the inert gas.
  • a preferred embodiment of the method according to the invention consists in continuously feeding the pitch obtained with mesophase to a melt spinning machine. This can also be accomplished in the form of forced conveyance by means of appropriate transport devices. In this way, the increase in Mesophase content and spinning into threads in a particularly economical manner.
  • the melt spinning machine which can be of a known type, pitch threads are spun, preferably multifilament threads with a single titer in the range from 0.6 to 2 dtex.
  • These threads can first be pre-oxidized by known methods and then carbonized and optionally graphitized. In this way, carbon or graphite threads can be obtained which, due to their mechanical data, are well suited for a wide variety of uses, for example as reinforcing fibers in plastic matrices.
  • a filtered coal tar pitch that had been thermally treated and already contained mesophase was decanted to obtain a mesophase-enriched fraction.
  • This fraction had a mesophase content of 74% by volume. It served as the starting material for the process according to the invention.
  • the pitch obtained as described above was fed at a rate of 1.68 kg / h into a commercially available extruder (ZSK 30 twin-screw kneader from Werner and Pfleiderer).
  • the extruder contained a melting zone, transport elements, one Homogenization zone, a degassing zone and again a transport unit.
  • the transport elements (screws) conveyed the pitch at a rotation of 200 rpm.
  • the melted pitch was formed into a film during transport.
  • the temperature in the heating section was approx. 296 ° C, in the transport zone between the heating zone and the homogenization zone approx. 375 ° C, in the homogenization zone and in the degassing zone in each case approx. 449 ° C.
  • Nitrogen was added in the degassing zone, the pressure here was set to approximately 150 mbar.
  • the layer thickness of the pitch film in the degassing zone was approximately 2 mm. After the degassing zone, the film was cooled to 400 ° C. and then removed from the extruder.
  • the pitch obtained had a mesophase content of 89% by volume.
  • Example 1 The pitch used in Example 1 was treated by the process according to the invention in the same apparatus as in the case of Example 1. The following sizes were changed:
  • the pitch obtained had a mesophase content of 81% by volume.
  • a pitch based on coal tar which had been thermally treated, hydrogenated, filtered and then thermally treated again and which had a mesophase content of 88% by volume, served as the starting material.
  • This pitch was fed into an extruder as in Example 1 at a feed rate of 0.32 kg / h.
  • the extruder contained a melting zone and then three consecutive transport elements, a homogenization zone and a degassing zone. After the third degassing zone, another transport unit followed.
  • the pitch was melted at 320 ° C. in the melting zone, and it was formed into a film by the subsequent transport elements in front of the first homogenization zone.
  • the transport elements promoted the bad luck at a speed of 200 rpm.
  • the layer thickness of the pitch film was approximately 2 mm in all homogenization and degassing zones.
  • the temperature up to and including the second degassing zone was approximately 320 ° C., in the third homogenization zone approximately 360 ° C.
  • the third degassing zone approximately 446 ° C.
  • nitrogen was used as the inert gas
  • the pressure in the first degassing zone was approximately 1000 mbar
  • the film was cooled to 330 ° C.
  • the pitch removed from the extruder had a mesophase content of 99.9% by volume.

Landscapes

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

Claims (24)

1. Procédé pour l'augmentation de la teneur en mésophase d'un brai, dans lequel on traite thermiquement une fraction aromatique à haut poids moléculaire, à base de goudron de houille et/ou de pétrole, à l'état fondu et sous forme d'un film mince, en mouvement continu, et, pendant le traitement thermique, on élimine par dégazage les composants volatils, caractérisé en ce que l'on utilise une fraction aromatique à haut poids moléculaire qui peut contenir une mésophase, cette fraction étant en continu mise mécaniquement sous forme d'un film mince ayant une épaisseur de couche d'environ 0,007 à 2 cm, et ce film étant amené mécaniquement sous contrainte, avec utilisation de forces de cisaillement, successivement à travers au moins une zone d'homogénéisation et au moins une zone de dégazage, une homogénéisation mécanique du film étant effectuée dans la ou les zone(s) d'homogénéisation et une élimination des composants aisément volatils étant effectuée dans la ou les zone(s) de dégazage, la température du film dans la ou les zone(s) d'homogénéisation et dans la ou les zone(s) de dégazage étant dans la plage de 320 à 470°C.
2. Procédé selon la revendication 1, caractérisé en ce que, après avoir quitté la zone de dégazage, le film est amené sous contrainte à travers une ou plusieurs zones d'homogénéisation et de dégazage qui se trouvent en alternance les unes par rapport aux autres.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le traitement thermique est effectué dans une extrudeuse dans laquelle sont présentes au moins une zone d'homogénéisation et au moins une zone de dégazage, le film étant chauffé avant d'atteindre la zone d'homogénéisation.
4. Procédé selon la revendication 3, caractérisé en ce que l'on utilise, en tant qu'extrudeuse, un malaxeur à vis jumelées.
5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce que la ou les zone(s) d'homogénéisation est(sont) isolée(s) de l'environnement de façon étanche aux gaz et en ce que dans la ou les zone(s) d'homogénéisation, aucun composant n'est éliminé hors du brai.
6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que, dans la ou les zone(s) d'homogénéisation et dans la ou les zone(s) de dégazage, le film est amené sous contrainte pratiquement en orientation horizontale.
7. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que l'épaisseur de couche du film dans la ou les zone(s) d'homogénéisation est plus grande que dans la ou les zone(s) de dégazage y faisant suite.
8. Procédé selon une ou plusieurs des revendications 1 à 7, caractérisé en ce que l'épaisseur de couche du film, dans la(les) zone(s) d'homogénéisation et dans la(les) zone(s) de dégazage, est dans la plage allant de 0,007 à 0,5 cm.
9. Procédé selon une ou plusieurs des revendications 1 à 8, caractérisé en ce que la température du film dans la ou les zone(s) d'homogénéisation et/ou dans la(les) zone(s) de dégazage est dans la plage allant de 370 à 470°C.
10. Procédé selon une ou plusieurs des revendications 1 à 9, caractérisé en ce que la température du film est abaissée après que celui-ci a quitté la dernière zone de dégazage.
11. Procédé selon une ou plusieurs des revendications 1 à 10, caractérisé en ce que dans la(les) zone(s) de dégazage, règne une pression dans la plage allant de 10⁻² à 1200 mbars.
12. Procédé selon la revendication 11, caractérisé en ce que, dans la première zone de dégazage, règne une pression dans la plage allant de 100 à 1200 mbars, et dans les autres zones de dégazage éventuellement présentes, règne une pression dans la plage allant de 10⁻² à 100 mbars.
13. Procédé selon une ou plusieurs des revendications 1 à 12, caractérisé en ce que le dégazage est effectué sous gaz inerte dans la(les) zone(s) de dégazage.
14. Procédé selon la revendication 13, caractérisé en ce que l'on utilise, en tant que gaz inerte, de l'azote ou de l'argon.
15. Procédé selon la revendication 13 ou 14, caractérisé en ce que, dans la(les) zone(s) de dégazage, le gaz inerte est mis en mouvement au-dessus de la surface du film de brai.
16. Procédé selon une ou plusieurs des revendications 1 à 15, caractérisé en ce que le film, après la dernière zone de dégazage, est amené en continu à une machine de filage par fusion, et en ce qu'un filage en fils de brai est effectué au moyen de celle-ci.
17. Procédé selon la revendication 16, caractérisé en ce que sont filés par extrusion des fils multifilaments ayant un titre unitaire dans la plage allant de 0,6 à 2 dtex.
18. Procédé selon la revendication 16 ou 17, caractérisé en ce que les fils sont ensuite préoxydés, soumis à une carbonisation et éventuellement à une graphitisation.
19. Procédé selon une ou plusieurs des revendications 1 à 18, caractérisé en ce que le temps de séjour du film de brai dans la(les) zones(s) d'homogénéisation et de dégazage, ainsi que les températures et les pressions, sont choisis de manière qu'après la dernière zone de dégazage, le brai présente une teneur en mésophase de 85 à 100% en volume.
20. Procédé selon une ou plusieurs des revendications 1 à 19, caractérisé en ce que la fraction aromatique à haut poids moléculaire qui est utilisée est un brai qui a été obtenu par filtration, distillation, éventuellement traitement thermique et éventuellement extraction d'un brai de goudron de houille ou d'un brai de pétrole.
21. Procédé selon la revendication 20, caractérisé en ce que, après filtration, distillation et éventuellement traitement thermique et extraction, le brai utilisé a été post-traité au moyen d'une séparation mécanique de deux phases liquides non solubles l'une dans l'autre, et la phase la plus riche des deux en mésophase a été réutilisée, et, après le post-traitement, a été éventuellement encore filtrée et séparée du solvant.
22. Procédé selon une ou plusieurs des revendications 1 à 21, caractérisé en ce que la fraction aromatique à haut poids moléculaire utilisée est un brai qui présente une teneur en mésophase de 30 à 90% en volume.
23. Procédé selon la revendication 22, caractérisé en ce que la teneur en mésophase du brai utilisé se situe dans la plage allant de 70 à 90% en volume.
24. Procédé selon une ou plusieurs des revendications 1 à 23, caractérisé en ce que le procédé est mis en oeuvre avec utilisation d'un accélérateur de réaction ajouté.
EP89115888A 1988-09-03 1989-08-29 Procédé pour augmenter la teneur en phase méso dans du brai Expired - Lifetime EP0358086B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3829986 1988-09-03
DE19883829986 DE3829986A1 (de) 1988-09-03 1988-09-03 Verfahren zur erhoehung des mesophasenanteils in pech
DE3918705 1989-06-08
DE3918705 1989-06-08

Publications (2)

Publication Number Publication Date
EP0358086A1 EP0358086A1 (fr) 1990-03-14
EP0358086B1 true EP0358086B1 (fr) 1992-02-05

Family

ID=25871823

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89115888A Expired - Lifetime EP0358086B1 (fr) 1988-09-03 1989-08-29 Procédé pour augmenter la teneur en phase méso dans du brai

Country Status (4)

Country Link
US (1) US4976845A (fr)
EP (1) EP0358086B1 (fr)
JP (1) JPH02107695A (fr)
DE (1) DE58900814D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002040754A1 (fr) * 2000-11-15 2002-05-23 Conoco Inc. Procede de traitement de pre-filage destine a un brai en mesophase solvate
US6523614B2 (en) * 2001-04-19 2003-02-25 Halliburton Energy Services, Inc. Subsurface safety valve lock out and communication tool and method for use of the same
CA2636887C (fr) * 2003-10-27 2012-03-13 Baker Hughes Incorporated Soupape de surete de fond recuperable et methode
JP2023515548A (ja) * 2020-02-24 2023-04-13 カーボン ホールディングス インテレクチュアル プロパティズ， エルエルシー 石炭から高融点炭化水素を製造するためのシステム及び方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1002362A (en) * 1963-01-11 1965-08-25 South Eastern Gas Board Thermal treatment of pitch

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732332A (en) * 1956-01-24 Geller
US1404435A (en) * 1912-12-26 1922-01-24 Gevers-Orban Emile Process of presenting the hydrocarbon in the form of a thin film of large surface area to the action of an oxidizing agent
US1742933A (en) * 1924-03-17 1930-01-07 Sun Oil Co Process of mineral-oil distillation
US1794542A (en) * 1927-01-20 1931-03-03 Piron Emil Distilling hydrocarbons
US2076498A (en) * 1928-09-10 1937-04-06 Sf Bowser & Co Inc Film-forming means in vacuum system for removing impurities from oils
US2095470A (en) * 1932-10-14 1937-10-12 Sf Bowser & Co Inc Method and apparatus for purifying liquids
DE1458577B1 (de) * 1961-06-08 1971-03-04 Thor Power Tool Co Geraet zur erzeugung von druckmittelimpulsen fuerden antrieb eines hydraulischen werkzeugs
US3348600A (en) * 1966-08-05 1967-10-24 Artisan Ind Thin-film-type fluid processing apparatus
US4016247A (en) * 1969-03-31 1977-04-05 Kureha Kagaku Kogyo Kabushiki Kaisha Production of carbon shaped articles having high anisotropy
US3974264A (en) * 1973-12-11 1976-08-10 Union Carbide Corporation Process for producing carbon fibers from mesophase pitch
US4042486A (en) * 1974-06-24 1977-08-16 Kureha Kagaku Kogyo Kabushiki Kaisha Process for the conversion of pitch into crystalloidal pitch
DE2810332C2 (de) * 1978-03-10 1982-08-05 Rütgerswerke AG, 6000 Frankfurt Verfahren zur Abtrennung von chinolinunlöslichen Bestandteilen aus Steinkohlenteerpech
JPS6057478B2 (ja) * 1978-06-28 1985-12-14 呉羽化学工業株式会社 炭素繊維用ピツチの製造法
US4271006A (en) * 1980-04-23 1981-06-02 Exxon Research And Engineering Company Process for production of carbon artifact precursor
DE3024423C2 (de) * 1980-06-28 1982-09-23 Rütgerswerke AG, 6000 Frankfurt Verwendung pikrierbarer Pechfraktionen zur Herstellung von anisotropem Kohlenstoff
JPS5876523A (ja) * 1981-10-29 1983-05-09 Nippon Oil Co Ltd ピツチ系炭素繊維の製造方法
US4497789A (en) * 1981-12-14 1985-02-05 Ashland Oil, Inc. Process for the manufacture of carbon fibers
JPS58115120A (ja) * 1981-12-28 1983-07-08 Nippon Oil Co Ltd ピツチ系炭素繊維の製造方法
JPS58220805A (ja) * 1982-06-15 1983-12-22 Nippon Oil Co Ltd 炭素繊維用前駆体ピツチの製造方法
DE3509861C2 (de) * 1984-03-26 1986-03-06 Idemitsu Kosan Co. Ltd., Tokio/Tokyo Pechmaterial für einen kohlenstoffhaltigen Formkörper und Verfahren zu seiner Herstellung
JPS60202189A (ja) * 1984-03-26 1985-10-12 Idemitsu Kosan Co Ltd 炭素材用ピッチの製造方法
US4551225A (en) * 1984-05-23 1985-11-05 E. I. Du Pont De Nemours And Company High anisotropic pitch
JPH0627172B2 (ja) * 1985-10-02 1994-04-13 三菱石油株式会社 光学的異方性ピッチの製造方法
DE3702720A1 (de) * 1987-01-30 1988-08-11 Bergwerksverband Gmbh Pechmaterial aus kohleteerpech, verfahren zu dessen herstellung sowie verwendung des pechmaterials

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1002362A (en) * 1963-01-11 1965-08-25 South Eastern Gas Board Thermal treatment of pitch

Also Published As

Publication number Publication date
DE58900814D1 (de) 1992-03-19
EP0358086A1 (fr) 1990-03-14
JPH02107695A (ja) 1990-04-19
US4976845A (en) 1990-12-11

Similar Documents

Publication Publication Date Title
DE2842723C2 (de) Verfahren zur Herstellung eines im wesentlichen vollständig anisotropen und zu 100 % aus Mesophase bestehenden Peches
DE3881058T2 (de) Verfahren zur mesophase-peche-herstellung.
DE69308134T2 (de) Verfahren zur herstellung von lösungsmittel enthaltendem pech und damit hergestellten kohlenstoffgegenständen
DE69132940T2 (de) Solvatierte mesophasenpeche
DE2457970C3 (de) Verfahren zur Herstellung von Kohlenstoff-Fasern
DE2457991B2 (de) Verfahren zur Herstellung von Kohlenstoff-Fasern
DE3012627C2 (fr)
DE68903460T2 (de) Verfahren zur herstellung von spitzenleistungspechkohlenstoffasern zusammen mit der herstellung von pech fuer kohlenstoffasern fuer jeden zweck.
DE3330575C2 (fr)
US3995014A (en) Process for producing carbon fibers from mesophase pitch
DE2752511C3 (de) Verfahren zur Herstellung eines Rohmaterials für die Erzeugung von Nadelkoks
DE3143818C2 (fr)
DE3116606C2 (fr)
DE3546613C2 (fr)
DE2747495C2 (de) Verfahren zum kontinuierlichen Herstellen eines Kokses
DE68919283T2 (de) Verfahren zur Herstellung von kohlenstoffhaltigen Fasern mit verbesserten physikalischen Druckeigenschaften.
EP0358086B1 (fr) Procédé pour augmenter la teneur en phase méso dans du brai
EP0499267A2 (fr) Procédé et installation pour le fractionnement industriel de polymères
DE68908651T2 (de) Herstellung von elastischen Graphit-Materialen.
DE3231682A1 (de) Verfahren zur herstellung von kohlenstoffasern mit hoher festigkeit und hohem modul
DE3606397C2 (fr)
DE69228663T2 (de) Auf Pech basierte Kohlenstoffasern und Verfahren zu deren Herstellung
DE2350769A1 (de) Verfahren zur herstellung graphitisierbarer kohlenstoff-fasern
DE3829986A1 (de) Verfahren zur erhoehung des mesophasenanteils in pech
DE2559537A1 (de) Verfahren zur umwandlung von pech in kristalloides pech

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19900414

17Q First examination report despatched

Effective date: 19901205

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RUETGERSWERKE AKTIENGESELLSCHAFT

Owner name: AKZO FASER AKTIENGESELLSCHAFT

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19920205

Ref country code: FR

Effective date: 19920205

Ref country code: NL

Effective date: 19920205

Ref country code: GB

Effective date: 19920205

REF Corresponds to:

Ref document number: 58900814

Country of ref document: DE

Date of ref document: 19920319

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930501