EP1525342B1 - Verfahren und anlage zur thermischen behandlung von natrium-enthaltenden kohlenstoffprodukten - Google Patents
Verfahren und anlage zur thermischen behandlung von natrium-enthaltenden kohlenstoffprodukten Download PDFInfo
- Publication number
- EP1525342B1 EP1525342B1 EP03748208A EP03748208A EP1525342B1 EP 1525342 B1 EP1525342 B1 EP 1525342B1 EP 03748208 A EP03748208 A EP 03748208A EP 03748208 A EP03748208 A EP 03748208A EP 1525342 B1 EP1525342 B1 EP 1525342B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sodium
- oven
- exhaust pipe
- neutralizing agent
- pipe
- 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
Links
- 239000011734 sodium Substances 0.000 title claims abstract description 46
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 44
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000010438 heat treatment Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 23
- 238000009434 installation Methods 0.000 title claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000002347 injection Methods 0.000 description 20
- 239000007924 injection Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 16
- 238000006386 neutralization reaction Methods 0.000 description 15
- 239000000835 fiber Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000007833 carbon precursor Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 150000003388 sodium compounds Chemical class 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920006282 Phenolic fiber Polymers 0.000 description 1
- ZILJFRYKLPPLTO-UHFFFAOYSA-N [C].[B].[Si] Chemical compound [C].[B].[Si] ZILJFRYKLPPLTO-UHFFFAOYSA-N 0.000 description 1
- 230000001594 aberrant effect Effects 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- 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
Definitions
- the invention relates to the high temperature heat treatment of carbon products containing sodium, and more particularly to the treatment of gaseous effluents produced during the heat treatment.
- a particular field of application of the invention is the production of textures or preforms made of carbon fibers intended to constitute fibrous reinforcements for parts made of composite material such as carbon / resin composite, for example C / epoxy or C / phenolic composite, or thermostructural composite, for example carbon / carbon composite (C / C) or ceramic matrix composite and carbon reinforcement.
- composite material such as carbon / resin composite, for example C / epoxy or C / phenolic composite, or thermostructural composite, for example carbon / carbon composite (C / C) or ceramic matrix composite and carbon reinforcement.
- Such fibrous textures are usually obtained from carbon precursor fibers that are better able to undergo the textile operations required for shaping these textures.
- carbon precursor fibers are preoxidized polyacrylonitrile (PAN) fibers, pitch fibers, phenolic fibers, and rayon fibers.
- PAN polyacrylonitrile
- the second step is generally carried out under reduced pressure and under a purge of neutral gas such as nitrogen.
- the second step is usually carried out before densification of the fibrous texture by the resin, carbon or ceramic matrix of the composite material.
- the densification can be carried out by a liquid route, that is to say impregnation with a liquid compound, such as a resin, precursor of the material of the matrix, and transforming this precursor by heat treatment.
- the densification can also be carried out by gaseous means, that is to say by chemical vapor infiltration, the two processes, the liquid route and the gaseous route being well known and possibly associable.
- the object of the invention is to provide a method which avoids the aforementioned drawback by preventing the formation on the walls of gaseous effluent extraction pipes of potentially dangerous deposits at the stage of cleaning these pipes.
- This object is achieved by a process of the type in which the carbon products are heated in an oven, under a purge of neutral gas and under reduced pressure, with continuous extraction out of the effluent furnace.
- gas containing in particular sublimed sodium by an effluent discharge pipe, in which process, in accordance with the invention, at least one sodium neutralization product is injected into the effluent discharge pipe, immediately downstream of the effluent gas outlet out of the oven.
- sodium neutralization product is meant a product to obtain a stable sodium compound and fairly easily removed.
- a relatively easy handling product for example water vapor or preferably carbon dioxide, optionally mixed with water vapor, is preferably chosen.
- the neutralization product may be injected at or downstream of a bend formed by the effluent gas discharge pipe out of the oven.
- the injected neutralization product may further be diluted in a neutral gas such as nitrogen.
- the neutralization product can be continuously injected into the gaseous effluent stream extracted from the furnace during the heat treatment, so as to form a stable and easily removable sodium compound and avoid the deposition of sodium on the pipe wall of the furnace. evacuation.
- the neutralization product is injected into the evacuation pipe after the end of the heat treatment in order to neutralize the sodium deposited on the wall of the evacuation pipe, before cleaning it.
- the invention also aims to provide an installation for implementing the method.
- a heat treatment plant for carbon products containing sodium of the type comprising an oven, means for supplying the oven with neutral gas for scavenging, and a line for extracting gaseous effluent out of the oven, installation which further comprises, according to the invention means for injecting a sodium neutralization product in the extraction pipe immediately after the exit of the furnace.
- High temperature heat treatment means a treatment at a temperature usually greater than that encountered by the textures during carbonization, that is to say a temperature greater than 1000 ° C., typically between 1400 ° C. and 2000 ° C. ° C at 2200 ° C or 2500 ° C.
- the heat treatment is carried out under reduced pressure, below atmospheric pressure, preferably below 50 kPa, typically between 0.1 kPa and 50 kPa, preferably below 5 kPa, and under a purge of neutral gas such as nitrogen or argon.
- the process according to the invention is applicable to the removal of sodium present at low levels in fibers, for example less than 80 ppm, or at a much higher content, greater than 3500 ppm.
- the figure 1 shows very schematically an oven 10 comprising a susceptor 12 of cylindrical shape and vertical axis which laterally delimits a volume or enclosure 11 for loading products (not shown) of carbon.
- the susceptor 12 for example graphite, is surmounted by a cover 14, is heated by inductive coupling with an inductor 16 which surrounds the susceptor with the interposition of a thermal insulator 18.
- the inductor is powered by a circuit 20 which delivers a current depending on the need for heating the oven.
- the inductor can be divided into several sections on the height of the oven. Each section is powered separately with electric power to define different heating zones in the oven in which the temperature can be regulated independently.
- the bottom of the furnace is formed of a thermal insulator 22 covered with a furnace hearth 24, for example made of graphite, on which the susceptor 12 rests.
- the assembly is housed in an envelope 26, for example metal, sealed by a removable cover 28.
- a pipe 30 provided with a valve 31 is connected to a source (not shown) of inert gas, for example nitrogen N 2 .
- the pipe 30 supplies the oven 10 with inert scanning gas to the upper part thereof, possibly through several inlets 32 opening at different locations around the casing 26 of the oven.
- An extraction device 40 is connected to an outlet duct 42 of the furnace passing through the bottom thereof, to extract the gaseous effluent produced during the heat treatment of the carbon products, in order to remove residual sodium in particular.
- the device 40 is connected to the outlet duct 42 by an evacuation pipe 44 provided with a carbon dioxide injection inlet 46 CO 2 .
- the pipe 44 forms a bend 44 has at its extremity connected by a flange 45 to the outlet duct 42 of the furnace.
- the injection inlet 46 is connected to a pipe 48 connected to a source (not shown) of CO 2 gas and provided with a valve 49.
- the pipe 48 is extended by a nozzle 50 which penetrates into the pipe 44 in order to inject the CO 2 gas in this pipe towards the downstream end of the elbow 44a and to avoid an accidental injection of the CO 2 gas inside the furnace by the exit pipe 42.
- Several points of injection of CO 2 gas spaced apart from each other along the pipe 44 may be provided.
- the CO 2 injection is carried out as close as possible to the outlet of the furnace, at a level where the sodium contained in the effluent is always in sublimated form.
- the injection at a bend of the pipe 44 promotes a mixture by turbulence between the gaseous effluent and CO 2 .
- Two columns 52, 54 provided with trays 53, 55 imposing a tortuous path to the gases are connected in series between the pipe 44 and a pipe 56 provided with a valve 57.
- a pump 58 is mounted on the pipe 56, between the valve 57 and a valve 59 in order to be able to switch on or isolate the pump 58.
- the pump 58 makes it possible to establish the desired reduced pressure level in the furnace. Although only one pump is shown, the presence of two pumps can be considered for the sake of redundancy.
- the gaseous effluent extracted by the pump 58 is fed to a burner 60 which supplies a stack 62.
- the oven 10 is equipped with temperature sensors connected to the control circuit 20 in order to set the heating temperature to the desired value.
- Two sensors 64 for example, is used, 64 b consist of pyrometers optical sighting, which are fitted in the lid 28 under 28a 28b windows made therein openings 14a and 14b formed in the cover 14 of the susceptor .
- the use of several pyrometric sensors is not a necessity, but makes it possible to measure at different levels and to eliminate any aberrant measurements by comparison. Preference is given to using bichromatic type pyrometers producing a continuously exploitable continuous signal.
- the temperature measured by the sensors 64a 64b is transmitted to the control circuit 20 to supply the inductor to change this temperature according to a preset temperature rise profile.
- the sodium contained in the fibrous textures is released and is discharged with the gaseous effluent in a sublimated form, in the elemental state and optionally in the combined state, for example in the state of sodium oxide NaO 2 .
- CO 2 is injected into the pipe 44 with a controlled flow rate by opening the valve 49 in order to carry out a neutralization of Na (or NaO 2 ) as soon as it leaves the furnace and to avoid its deposition on the walls of the pipe 44.
- CO 2 injection can be started at a temperature below 900 ° C. This injection is also preferably continued at least until the end of the process.
- the sodium carbonate product is collected in particular in the tray columns 52, 54.
- the purified gaseous effluent of sodium is fed to the burner 60.
- the extraction device 40 or at least a part thereof comprising the tray columns 52, 54 and optionally the pipe 44 is cleaned periodically to eliminate in particular the deposited sodium carbonate.
- the cleaning can be carried out by rinsing with water in situ or by washing with water in a washing container after at least partial disassembly of the extraction device.
- the neutralization of sodium is carried out by hydration.
- the pipe 44 is provided with one or more injection devices 70 for example in the form of hollow rings 72 surrounding the pipe 44.
- the injection device 70 is placed immediately downstream of the bend 44a, with interposition an isolation valve 71 between the outlet 42 of the oven and the injection device 70.
- two rings are provided spaced apart from each other along the pipe 44.
- the rings injection 72 are fed in parallel through a pipe 74 connected on the one hand to a source of neutralizing agent, for example a source of water vapor via a pipe 76 provided with a valve 75 and, secondly, a source of neutral gas such as nitrogen or argon, via a pipe 78 provided with a valve 57.
- the pipe 44 Downstream of the injection device 70, in the flow direction of gaseous effluent, the pipe 44 has a purge port connected to a purge pipe 80 provided with a valve 81. Downstream of the connection with the pipe of purge, the pipe 44 can be connected directly to the pump 58 through the valve 57, the use of tray columns is not necessary here. The rest of the installation is identical to what was described above.
- Each injection ring 72 forms an O-ring surrounding the pipe 44 and communicating with it through holes 74 formed in the wall of the pipe.
- the holes 74 may be inclined relative to the normal to the wall of the pipe 44 to direct the flow of neutralization agent downstream.
- the injection of the mixture H 2 O + N 2 can be carried out during the heat treatment process, as described above with regard to the CO 2 injection, or after the end of the heat treatment process to hydrate the sodium deposited on the wall of the pipe 44.
- the pipe 44 may be insulated along its portion connecting the pipe. output 42 to this injection device. Insulation 43 prevents premature sodium condensation on the wall of pipe 44 by too rapid cooling of the gaseous effluent.
- the insulation 43 may be replaced or supplemented by heating means for example by electrical resistors.
- valves 75 and 81 are open, the valves 71, 57 and 77 are closed and water in liquid form is admitted into the pipe 76 and thence into the injection device 70.
- Several rinses consecutive lines of the line 44 can be carried out to remove the soda produced by neutralization of sodium.
- drying of the pipe 44 can be achieved by simply opening the valve 57 and turning on the pump 58, the valves 75 and 81 being closed.
- the dilution with nitrogen is preferred to avoid a too violent reaction with sodium, the amount of sodium to be neutralized being low.
- the injected CO 2 can also be diluted by mixing with nitrogen.
- the method and the installation which have just been described are particularly suitable for carbon products obtained from pre-oxidized PAN precursor, in particular for fibrous carbon textures intended for the manufacture of parts made of carbon / resin composite material C / C or C / ceramic, for example silicon carbide matrix (C / SiC) or ternary matrix silicon-boron-carbon (C / Si-BC).
- C / SiC silicon carbide matrix
- C / Si-BC ternary matrix silicon-boron-carbon
- the textures are made of fibers in the precursor state of carbon more capable of undergoing textile operations than carbon fibers.
- These textures may be one-dimensional such as wires or cables, or two-dimensional, such as fabrics or webs formed of parallel son or cables, or three-dimensional, such as preforms obtained by filament winding, or by stacking, winding or draping fabrics or plies in superimposed layers and possibly linked together by needling or stitching, for example.
- fibrous preforms are nozzle preforms or divergent nozzles or brake disc preforms.
- the invention also applies to carbon products, obtained from carbon precursor materials other than preoxidized PAN, also containing sodium and optionally one or more other metals or metal impurities to be removed.
- carbon precursor materials other than preoxidized PAN, also containing sodium and optionally one or more other metals or metal impurities to be removed.
- Examples of such precursors are pitches, phenolic materials, or rayon.
- the process according to the invention is advantageous in that it makes it possible to eliminate sodium which is present at a very low content in the fibers, for example less than 80 ppm, which sodium would be impossible to remove by another method such as rinsing with water. 'water. It also makes it possible to eliminate sodium present in larger amounts in the fibers, for example at more than 3500 ppm.
- calcium and / or magnesium can be removed by sublimation.
- metals such as Fe, Ni and Cr may also have to be eliminated in addition to sodium. It is then necessary to perform the heat treatment to a temperature sufficient to ensure the sublimation of these metals, for example a temperature up to 2000 ° C or 2200 ° C, or 2500 ° C.
Landscapes
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Treatment Of Fiber Materials (AREA)
- Treating Waste Gases (AREA)
- Carbon And Carbon Compounds (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
- Muffle Furnaces And Rotary Kilns (AREA)
- Furnace Details (AREA)
- Inorganic Fibers (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
Claims (12)
- Verfahren zur Wärmebehandlung von natriumhaltigen Kohlenstoffprodukten, wonach die Produkte in einem Ofen unter vermindertem Druck sowie unter Spülen mit Neutralgas erhitzt werden und Abgase, die Natrium in sublimierter Form enthalten, über eine Rohrleitung zum Abführen der Abgase kontinuierlich aus dem Ofen abgezogen werden, dadurch gekennzeichnet, daß wenigstens ein Produkt zur Neutralisierung des Natriums in die Rohrleitung zum Abführen der Abgase, direkt nach dem Austritt der Abgase aus dem Ofen eingespritzt wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Produkt zur Neutralisierung des Natriums aus Kohlendioxid und Wasserdampf ausgewählt ist.
- Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß das Neutralisierungsprodukt im Bereich eines oder nach einem durch die Rohrleitung zum Abführen der Abgase aus dem Ofen gebildeten Krümmer(s) eingespritzt wird.
- Verfahren nach einem der Ansprüche 2 und 3, dadurch gekennzeichnet, daß das eingespritzte Neutralisierungsprodukt in einem Neutralgas verdünnt wird.
- Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Neutralgas Stickstoff oder Argon ist.
- Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Neutralisierungsprodukt in den während der Wärmebehandlung aus dem Ofen abgezogenen Abgasstrom kontinuierlich eingespritzt wird.
- Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Neutralisierungsprodukt nach dem Ende der Wärmebehandlung in die Abführrohrleitung eingespritzt wird, um Natrium, das sich an der Wand der Abführrohrleitung abgesetzt hat, vor deren Reinigung zu neutralisieren.
- Anlage zur Wärmebehandlung von natriumhaltigen Kohlenstoffprodukten, umfassend einen Ofen (10), Mittel (30) zum Beaufschlagen des Ofens mit Spülneutralgas sowie eine Rohrleitung (44) zum Abführen der Abgase aus dem Ofen, dadurch gekennzeichnet, daß sie ferner Mittel (50; 72) zum Einspritzen eines Produkts zum Neutralisieren des Natriums in die Abführrohrleitung (44), direkt nach dem Ausgang des Ofens umfaßt.
- Anlage nach Anspruch 8, dadurch gekennzeichnet, daß sie wenigstens eine in die Abführrohrleitung (44) eindringende Düse (50) zum Einspritzen eines Neutralisierungsprodukts umfaßt.
- Anlage nach Anspruch 9, dadurch gekennzeichnet, daß die Düse (50) in einen Krümmer (44a) der Abführrohrleitung (44) eindringt.
- Anlage nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß sie mehrere, entlang der Abführrohrleitung beabstandete Punkte zum Einspritzen eines Neutralisierungsmittels aufweist.
- Anlage nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß die Abführrohrleitung (44) mit einer Entlüftungsvorrichtung (80, 81) ausgestattet ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0208818 | 2002-07-12 | ||
FR0208818A FR2842191B1 (fr) | 2002-07-12 | 2002-07-12 | Procede et installation de traitement thermique de produits en carbonne contenant du sodium |
PCT/FR2003/002204 WO2004007819A2 (fr) | 2002-07-12 | 2003-07-11 | Procede et installation de traitement thermique de produits en carbone contenant du sodium |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1525342A2 EP1525342A2 (de) | 2005-04-27 |
EP1525342B1 true EP1525342B1 (de) | 2009-04-22 |
Family
ID=29763803
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03748208A Expired - Lifetime EP1525342B1 (de) | 2002-07-12 | 2003-07-11 | Verfahren und anlage zur thermischen behandlung von natrium-enthaltenden kohlenstoffprodukten |
Country Status (11)
Country | Link |
---|---|
US (1) | US7351390B2 (de) |
EP (1) | EP1525342B1 (de) |
JP (1) | JP4327086B2 (de) |
CN (1) | CN1329566C (de) |
AT (1) | ATE429533T1 (de) |
AU (1) | AU2003267517A1 (de) |
CA (1) | CA2492218C (de) |
DE (1) | DE60327321D1 (de) |
FR (1) | FR2842191B1 (de) |
MX (1) | MXPA05000569A (de) |
WO (1) | WO2004007819A2 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8771623B2 (en) * | 2009-10-30 | 2014-07-08 | Goodrich Corporation | Methods and apparatus for residual material management |
FR2953826B1 (fr) * | 2009-12-16 | 2019-10-11 | Safran Landing Systems | Procede de fabrication d'une piece de friction a base de materiau composite c/c |
US11236021B2 (en) | 2017-12-22 | 2022-02-01 | Goodrich Corporation | Mitigating pyrophoric deposits in exhaust piping during SIC CVI/CVD processes by introducing water vapor into an outlet portion of a reaction chamber |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3179605A (en) * | 1962-10-12 | 1965-04-20 | Haveg Industries Inc | Manufacture of carbon cloth |
US3413094A (en) * | 1966-01-24 | 1968-11-26 | Hitco | Method of decreasing the metallic impurities of fibrous carbon products |
GB1284399A (en) * | 1968-11-27 | 1972-08-09 | Courtalds Ltd | Filamentary carbon |
GB1600640A (en) * | 1977-05-26 | 1981-10-21 | Hitco | Method of removing alkali and alkaline earth impurities from carbonizable polyacrylonitrile material |
US4507272A (en) * | 1983-05-09 | 1985-03-26 | Hitco | Method of purifying partially carbonized pan material prior to carbonization |
GB8703323D0 (en) * | 1987-02-13 | 1987-03-18 | British Petroleum Co Plc | Separation process |
US5154776A (en) * | 1989-05-18 | 1992-10-13 | Bloch Christopher J | Method for decontamination of vessels and other equipment polluted with metallic sodium and other reactive metals |
FR2842193B1 (fr) * | 2002-07-12 | 2004-10-01 | Messier Bugatti | Procede et installation pour le traitement thermique a haute temperature et la densification par infiltration chimique en phase vapeur de textures en carbone |
-
2002
- 2002-07-12 FR FR0208818A patent/FR2842191B1/fr not_active Expired - Fee Related
- 2002-09-26 US US10/256,224 patent/US7351390B2/en not_active Expired - Lifetime
-
2003
- 2003-07-11 DE DE60327321T patent/DE60327321D1/de not_active Expired - Lifetime
- 2003-07-11 AT AT03748208T patent/ATE429533T1/de active
- 2003-07-11 CA CA2492218A patent/CA2492218C/en not_active Expired - Fee Related
- 2003-07-11 EP EP03748208A patent/EP1525342B1/de not_active Expired - Lifetime
- 2003-07-11 AU AU2003267517A patent/AU2003267517A1/en not_active Abandoned
- 2003-07-11 WO PCT/FR2003/002204 patent/WO2004007819A2/fr active Application Filing
- 2003-07-11 JP JP2004520775A patent/JP4327086B2/ja not_active Expired - Fee Related
- 2003-07-11 MX MXPA05000569A patent/MXPA05000569A/es active IP Right Grant
- 2003-07-11 CN CNB038165880A patent/CN1329566C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO2004007819A2 (fr) | 2004-01-22 |
DE60327321D1 (de) | 2009-06-04 |
JP2005533193A (ja) | 2005-11-04 |
CA2492218A1 (en) | 2004-01-22 |
ATE429533T1 (de) | 2009-05-15 |
CN1668789A (zh) | 2005-09-14 |
AU2003267517A1 (en) | 2004-02-02 |
JP4327086B2 (ja) | 2009-09-09 |
US20040009116A1 (en) | 2004-01-15 |
CN1329566C (zh) | 2007-08-01 |
FR2842191B1 (fr) | 2004-10-01 |
WO2004007819A3 (fr) | 2004-04-08 |
MXPA05000569A (es) | 2005-04-28 |
FR2842191A1 (fr) | 2004-01-16 |
CA2492218C (en) | 2010-10-26 |
US7351390B2 (en) | 2008-04-01 |
EP1525342A2 (de) | 2005-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1527031B1 (de) | Verfahren und vorrichtung zur hochtemperaturwärmebehandlung und verdichtung von kohlenstofftexturen mittels chemischer dampfinfiltration | |
EP0256073B1 (de) | Vorrichtung zur chemischen infiltration in der gasphase eines feuerfesten materials anders als kohlenstoff | |
EP0797689B1 (de) | Gasextraktionsvorrichtung | |
FR2520352A1 (fr) | Structure composite de type refractaire-refractaire et son procede de fabrication | |
EP1844179B1 (de) | Verdichtung von porösen substraten mit kohlenstoff mittels chemischen gasphaseninfiltration | |
EP1521731B1 (de) | Verfahren und vorrichtung zur herstellung von kohlenstoffprodukten aus kohlenstoffvorläuferprodukten | |
WO2021156549A1 (fr) | Procédé de fabrication de composites à matrice céramique comprenant une interphase spécifique | |
EP1525342B1 (de) | Verfahren und anlage zur thermischen behandlung von natrium-enthaltenden kohlenstoffprodukten | |
EP0820424B1 (de) | Verfahren zur chemischen dampfinfiltration eines aus kohlenstoff und silicium und/oder bor zusammengesetzten materials | |
EP0730564B1 (de) | Verfahren zur verdichtung einer porösen struktur mit bornitrid | |
FR3112797A1 (fr) | Procédé de traitement d’une phase gazeuse résiduelle issue d’une technique CVI | |
EP0966413B1 (de) | Verfahren und vorrichtung zur verdichtung einer porösen struktur mit einem strömenden vorprodukt | |
FR3114329A1 (fr) | Procédé de traitement d’une phase gazeuse résiduelle issue d’une technique CVI | |
WO2023105139A1 (fr) | Installation d'infiltration chimique en phase gazeuse a double chambre de reaction | |
FR2463819A1 (fr) | Reacteur de depot chimique en phase vapeur fonctionnant sous basse pression |
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 |
|
17P | Request for examination filed |
Effective date: 20041216 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
DAX | Request for extension of the european patent (deleted) | ||
RBV | Designated contracting states (corrected) |
Designated state(s): AT DE FR GB |
|
111L | Licence recorded |
Free format text: 0100 MESSIER-BUGATTI S.A. Effective date: 20060720 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAC | Information related to communication of intention to grant a patent modified |
Free format text: ORIGINAL CODE: EPIDOSCIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT DE FR GB |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REF | Corresponds to: |
Ref document number: 60327321 Country of ref document: DE Date of ref document: 20090604 Kind code of ref document: P |
|
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 |
Effective date: 20100125 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 60327321 Country of ref document: DE Representative=s name: CBDL PATENTANWAELTE, DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 60327321 Country of ref document: DE Representative=s name: CBDL PATENTANWAELTE, DE Effective date: 20130114 Ref country code: DE Ref legal event code: R081 Ref document number: 60327321 Country of ref document: DE Owner name: HERAKLES, FR Free format text: FORMER OWNER: SNECMA PROPULSION SOLIDE, LE HAILLAN, FR Effective date: 20130114 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20130221 AND 20130227 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP Owner name: HERAKLES, FR Effective date: 20130513 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: PC Ref document number: 429533 Country of ref document: AT Kind code of ref document: T Owner name: HERAKLES, FR Effective date: 20140311 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20170721 Year of fee payment: 15 Ref country code: DE Payment date: 20170713 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20170623 Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 16 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60327321 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 429533 Country of ref document: AT Kind code of ref document: T Effective date: 20180711 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20180711 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180711 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190201 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180711 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20210727 Year of fee payment: 19 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220731 |