EP0966558B1 - Procede de realisation d'une texture activee en fibres de carbone - Google Patents
Procede de realisation d'une texture activee en fibres de carbone Download PDFInfo
- Publication number
- EP0966558B1 EP0966558B1 EP98914905A EP98914905A EP0966558B1 EP 0966558 B1 EP0966558 B1 EP 0966558B1 EP 98914905 A EP98914905 A EP 98914905A EP 98914905 A EP98914905 A EP 98914905A EP 0966558 B1 EP0966558 B1 EP 0966558B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fabric
- carbon
- fibers
- temperature
- heat treatment
- 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
- 239000000835 fiber Substances 0.000 title claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000004744 fabric Substances 0.000 claims description 63
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 30
- 229920002678 cellulose Polymers 0.000 claims description 27
- 235000010980 cellulose Nutrition 0.000 claims description 27
- 239000001913 cellulose Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 229920000297 Rayon Polymers 0.000 claims description 23
- 238000005470 impregnation Methods 0.000 claims description 18
- 239000002964 rayon Substances 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 13
- 239000004917 carbon fiber Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 9
- 239000007833 carbon precursor Substances 0.000 claims description 8
- 239000004753 textile Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 3
- 230000003381 solubilizing effect Effects 0.000 claims 1
- 239000000470 constituent Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- 210000001519 tissue Anatomy 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000009434 installation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- -1 fibrane Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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- 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
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
-
- 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
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
Definitions
- the present invention relates to the production of activated textures in carbon fibers.
- Such textures are especially usable for the filtration of fluids, for example the treatment of gaseous or liquid effluents.
- cellulose flame retardants These constituents which promote the dehydration of cellulose are also known as cellulose flame retardants. They allow carbonization of the cellulosic precursor with better yield and faster kinetics.
- Achieving an activated carbon fiber texture includes then a treatment to activate the carbon fiber texture by the action of an oxidizing gas, for example carbon dioxide, water vapor or air, to a temperature above 500 ° C, typically 600 ° C to 1000 ° C, i.e. a temperature higher than that of charring.
- an oxidizing gas for example carbon dioxide, water vapor or air
- An activation technique of carbon fabric in an oven is described in the document FR-A-2 741 363.
- n ° 38 (C-004) (JP-A-55-010472) which describe the activation of fiber textures carbon previously obtained by carbonization of a cellulosic precursor to which a cellulose dehydration promoter (chloride ammonium, phosphoric acid and zinc chloride, for example).
- a cellulose dehydration promoter chloride ammonium, phosphoric acid and zinc chloride, for example.
- activation techniques require heat treatment specific. They have a relatively low overall mass yield, by compared to the texture of cellulosic fibers, the activation treatment having for effect of creating a microporous network by elimination of carbon. The price of returns is very high, the carbon fiber textures activation supports being themselves expensive. In addition, activation significantly affects the mechanical qualities of carbon fibers, and we observe that the documents cited above do not, in general, state the properties mechanics of activated carbon fibers.
- the present invention aims to provide a method for obtaining activated textures in carbon fibers, from fibers in carbon precursor of the cellulosic type more economically and with a much higher yield than in the prior art.
- the invention also aims to provide a method for to obtain activated textures in carbon fibers having good hold mechanical and retaining high flexibility allowing them to be shaped, for example by draping.
- a process for producing an activated texture of carbon fibers comprising the steps which consist in providing a texture in fibers of cellulosic material, carbon precursor, impregnating the texture with a composition containing at least one constituent mineral having a function of promoter of the dehydration of the cellulose, and carrying out a heat treatment of the impregnated texture at a temperature sufficient to cause the transformation of the cellulose precursor essentially into carbon and to obtain a texture in carbon fibers, is characterized in that the carbon precursor cellulosic material is chosen from rayon, fibrane, solvent celluloses, cotton and bast fibers, and the heat treatment is carried out under an inert or partially oxidizing atmosphere, consists of a rise in temperature at an average speed between 1 and 15 ° C / min followed by a plateau at a temperature between 350 ° C and 500 ° C, and is followed by a step of removing residual phases of the impregnation composition and of degradation products of the cellulosic material by washing the texture, so
- the invention is remarkable in that the phases of carbonization and activation are carried out in a single heat treatment, at a temperature moderate and result in an activated texture with a very specific surface high.
- the yield measured by the ratio between the texture mass activated and the starting texture mass of cellulosic fibers is greater than 30%, typically between 35% and 45%, therefore high.
- the duration of the stage of the heat treatment is preferably at most equal at 1 a.m.
- the liquid composition for impregnating the texture in fibers of cellulosic material contains at least one mineral constituent and solid fillers, these being for example chosen from antimony, iron, titanium and silicon.
- the heat treatment and washing steps are carried out continuously, thanks to the good mechanical strength of the texture
- the process can be implemented on different fibrous textures, in particular wires, cables, fabrics, unidirectional layers of wires or multidirectional, felts, mats, knits, sheets and films.
- the initial fibrous texture is made of carbon precursor fibers of cellulosic type, for example in rayon multifilaments, in yarn of viscose (fibranne), of cellulose fibers or filaments containing solvent, of cotton or even bast fibers.
- the texture of cellulosic fibers is impregnated with a composition containing at least one constituent having a function of promoting the dehydration of cellulose.
- constituents are well known in themselves and are at least, for some, also used as flame retardants for cellulose.
- One or more mineral constituents may be used chosen from phosphoric acid (H 3 PO 4 ), sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCI), diammonic phosphate ((NH 4 ) 2 HPO 4 ), sodium phosphate (Na 3 PO 4 ), potassium sulfate (K 2 SO 4 ), ammonium chloride (NH 4 CI), zinc chloride (ZnCl 2 ), any phosphorus salt or boron, and generally Lewis or Brönsted acids.
- a mixture of several constituents may have a beneficial effect on the mechanical strength of the final texture obtained, if they are chosen for promote the dehydration of cellulose at different times of the treatment thermal and therefore make the reaction less violent.
- Different solid fillers can be added to the composition impregnation in order to constitute impurities which favor the development of the microporous network during heat treatment.
- catalyst component (s) in the dehydration of the cellulose depends on the nature of the constituents. She is chosen, in a way general, high enough to generate a large specific surface in the activated texture, but without being excessive, which would lead to a texture fragile (brittle) and rigid.
- the heat treatment includes a first phase of rise progressive in temperature, followed by a plateau.
- the temperature rise must be fast enough to obtain a large specific surface, but without excessive speed for achieve controlled degradation of the cellulose and obtain an activated texture final with good mechanical strength.
- the average rate of climb in temperature is between 1 and 15 ° C / min, the temperature increase not necessarily being linear over time.
- the plateau at the final heat treatment temperature allows complete the degradation of cellulose. It is important, however, not to exceed a maximum value beyond which a risk of closure of microporosities has been observed.
- Final processing temperature is understood between 350 ° C and 500 ° C.
- the heat treatment (temperature rise and level) is carried out under an inert atmosphere, for example under nitrogen, or partially inert.
- an inert atmosphere for example under nitrogen, or partially inert.
- oxygen from the air, dioxide of carbon, water vapor or other oxidizing agents especially generated by the decomposition of the constituent (s) of the impregnation composition.
- the final washing of the activated texture is preferably carried out immediately after heat treatment to avoid blockage of microporosities created, an obstruction that can result from the crystallization of a excess of constituents of the impregnation composition in the micropores, the kinetics of dissolution of these crystals being very slow.
- Washing with water can include a first phase of solubilization of the constituent (s) of the impregnating composition present in excess on the final texture, then a second rinsing phase. Washing eliminates not only residual phases of the composition impregnation, but also degradation products of the cellulosic material carbon precursor.
- Rayon fabric samples consisting of a multifilament viscose, containing less than 0.03% size.
- the fabric is obtained from 190 tex threads woven in 15 x 15 texture (15 threads per cm in chain and weft).
- the fabric is steamed at 120 ° C for 1 hour in a ventilated oven and then cooled 1/2 hour in a desiccator.
- the surface mass of the fabric is then equal to 530 g / m 2 .
- a tissue sample is then soaked in an aqueous solution phosphoric acid at 200 g / l, for 2 h, then drained flat on a grid for at least 24 hours.
- the acid content on the fabric is 17%, measured by the ratio between the mass of pure phosphoric acid on the tissue and the mass of dry fabric before impregnation.
- the impregnated fabric is wound on itself and arranged in a ceramic nacelle which is introduced into a quartz tube of an oven heat treatment.
- a heat treatment is carried out under a nitrogen flow of 10 l / h at atmospheric pressure.
- the treatment includes a rise in temperature to a speed of approximately 10 ° C / min up to 400 ° C followed by a 30 min plateau at this temperature.
- the fabric is washed in order to remove products of degradation of the celluloses phases of the initial precursor and / or excess of additive acid. Washing is carried out by circulating distilled water for 5 h and the fabric washed is dried in air at 160 ° C for 2 h.
- Example 2 The procedure is as in Example 1, but by varying the concentration of the phosphoric acid solution, or the conditions of the heat treatment (temperature rise speed, bearing temperature, duration of the stage, possible addition of water vapor to the atmosphere under which heat treatment is carried out).
- Examples 2 to 12 are given in rows B to L of Table 1.
- the "acid content” is the ratio between the mass of pure acid fixed on the fabric after impregnation and the mass of dry fabric before impregnation
- the “yield” is the weight of the activated carbon fabric washed and dried compared to by weight of the steamed and dried rayon fabric, and the tensile strength is that measured in the weft or warp direction on the activated carbon fabric obtained.
- the level of acid fixed on the rayon fabric must preferably remain within a certain limit, otherwise the resistance of the activated carbon fabric becomes low, or even zero.
- the heat treatment must be relatively moderate, in terms of rate of temperature rise, as well as temperature and bearing time.
- the bearing temperature must not exceed 500 ° C if we want to guarantee a relatively high specific surface, in any case greater than 600 m 2 / g.
- a semi-continuous treatment is carried out on a rayon fabric at means of the installation shown very diagrammatically in FIGS. 1A, 1B and 1 C.
- FIG. 1A A strip of textile rayon fabric 10 (FIG. 1A) based on viscose unwound from a spool 12.
- the fabric contains less than 0.03% of size, has a width of 1000 mm and a surface mass dry of about 530 g / m 2 .
- the fabric After drying by passing over heating rollers 14 to one temperature of about 120 ° C, the fabric is impregnated, using the technique of padding, with a composition containing a mixture of phosphoric acid pure (18% by weight), sodium phosphate (2% by weight) and borate sodium (1.5% by weight), the remainder being water.
- the fabric is conveyed in a tray 16 containing this composition, then is expressed between two rolls 18 applied against each other with a pressure set at approximately 2 bars.
- the running speed of the fabric strip is approximately 0.5 m / min.
- the fabric impregnated is dried at a temperature of 30 ° C to 85 ° C, for example by passing over heating rollers 20, in order to remove the water from the composition impregnation then passes through a traction system 21 of omega type before to be wound on a reel 22 to be stored for about 24 hours.
- the impregnated fabric is taken from the reel 22 by means of a system omega type pulling device 24 (FIG. 1B) and passes through a puppet 26 allowing to guarantee constant tension during the whole process.
- a system omega type pulling device 24 FIG. 1B
- the fabric passes through a sealing box 32 and a drainage box effluents 34 located in front of the entrance to a heat treatment oven 30. In out of the oven, the fabric passes through an effluent discharge box 36 and a box seal 38.
- the sealing boxes 32, 38 are crossed by a transverse flow of nitrogen under pressure.
- the effluent discharge box 34 is fixed to the upstream wall of the oven and to its wall traversed by a rod 35 allowing in particular the supply of the internal volume of the oven with nitrogen, the heat treatment being carried out in a neutral atmosphere .
- the effluent discharge box 36 is fixed to the downstream wall of the furnace 30.
- the boxes 34 and 36 have outlets 34 a , 36 a for the evacuation of gaseous effluents.
- Screens 40 allowing passage to the strip of fabric, are provided at the entrance and at the exit of the oven 30 to limit the thermal radiation towards the outside.
- the fabric passes inside a quartz tube 30 a while resting on a scale 30 b also made of quartz.
- the useful length of the quartz tube is approximately 1.3 m.
- the oven 30 has several heating zones, for example four successive zones I, II, III, IV and the heating is controlled so that the fabric reaches a temperature of approximately 400 ° C., approximately 40 min after entering the the oven, after gradual rise in temperature, and remains at this temperature for about 30 min before leaving the oven.
- Figure 2 shows the temperature profile in the oven as a function of the residence time. The rate of temperature rise up to the 400 ° C plateau is approximately 10 ° C / min.
- the fabric passes over a roller 42 (figure 1C) associated with a strain gauge, allowing to measure the tension on the fabric.
- the fabric then reaches a washing station comprising a tank 50 divided into two upstream and downstream compartments 50 a , 50 b .
- a washing station comprising a tank 50 divided into two upstream and downstream compartments 50 a , 50 b .
- the fabric is watered by permuted water by means of nozzles 52 with flat jet, which feed the compartment 50 a , in which the excess of constituents of the impregnation composition still present on the tissue can be dissolved.
- the fabric then passes into compartment 50 b where it is rinsed with demineralized water sprayed onto the fabric by means of nozzles 54 located at the outlet of compartment 50 b , above the latter.
- the washed fabric passes through a traction system 56 of the omega type, in which it is also expressed, before being dried at a temperature about 120 ° C by passage between two radiant plates 58.
- the speed drive by the traction system 56 is chosen slightly greater than that imposed by the traction system 24, to take account of the shrinkage of the fabric during charring.
- Example 13 We proceed as in Example 13, but by varying different parameters: phosphoric acid content, rate of rise temperature and duration of the stage of heat treatment.
- Examples 14 to 16 are shown in rows N to P of Table 2.
- the phosphoric acid content is the ratio between the mass of pure acid fixed on the fabric after impregnation and the mass of dry fabric before impregnation and the tensile strength expresses the tensile breaking strength in the chain direction.
- Phosphoric acid in addition to its low cost, has the advantage of having three acid functions to promote the dehydration of cellulose and, in relation to NH 4 Cl and (NH 4 ) 2 HPO 4 , to require a lower content in view obtaining the desired porosity.
- phosphoric acid possibly as a mixture with other constituents, will be preferred, without excluding others mineral constituents known to promote dehydration of the cellulose.
- Example 13 The procedure is as in Example 13, but using different cellulosic precursors, respectively: a textile type rayon I which naturally contains additives such as aluminum and titanium dioxide in its structure, the latter being a very disoriented crystal structure, a rayon II intermediate between textile and technical rayon, a technical rayon III, of the type used for tire reinforcements, a rayon IV of "solvent cellulose” type and a fibranne V commonly used in the 'textile industry.
- a textile type rayon I which naturally contains additives such as aluminum and titanium dioxide in its structure, the latter being a very disoriented crystal structure
- a rayon II intermediate between textile and technical rayon a technical rayon III, of the type used for tire reinforcements
- a rayon IV of "solvent cellulose” type of "solvent cellulose” type
- fibranne V commonly used in the 'textile industry.
Description
- figures 1A, 1B, 1C : une représentation très schématique d'une installation industrielle permettant la mise en oeuvre du procédé ; et
- figure 2 : une courbe illustrant le profil de température du four de traitement thermique de la figure 1B.
- une surface spécifique élevée : environ 1 000 m2/g,
- une masse surfacique d'environ 350 g/cm2 après séchage,
- une résistance mécanique à la rupture en traction de bon niveau, environ 1 daN/cm, tant en sens trame qu'en sens chaíne,
- un diamètre moyen de pores égal à environ 0,6 nm,
- un volume total de pores d'environ 0,6 cm3/g,
- un taux de carbone de 80 % environ, et
- un rendement moyen de 40%, obtenu par mesure du rapport entre le poids de tissu activé en fibres de carbone obtenu et le poids du tissu de rayonne étuvé et séché (un tel rendement est plus du double de celui obtenu avec des procédés de l'art antérieur évoqué en tête de la description dans lesquels une activation à température élevée est réalisée après carbonisation).
Tissu activé | Teneur acide % | Traitement thermique | Rendement % | Surface spécifique m2/g | Résistance en traction daN/cm |
A | 17 | 10°C/min 400°C, 1/2 h | 40,7 | 1040 | 0,9 |
B | 17 | 10°C/min 500°C,1/2 h | 39,5 | 690 | 0,8 |
C | 17 | 10°C/min 600°C, 1/2 h | 42,3 | 260 | 1 |
D | 17 | 10°C/min 400°C, 1/2 h + vapeur d'eau à 31 % vol. | 39,4 | 985 | 0,45 |
E | 17 | 10°C/min 500°C, 1/2 h + vapeur d'eau à 31 % vol. | 36,5 | 930 | 0,85 |
F | 17 | 1°C/min 400°C, 1/2 h | 42,5 | 870 | 2,6 |
G | 17 | 6°C/min 400°C, 1/2 h | 41,6 | 910 | 0,55 |
H | 17 | 15°C/min 400°C, 1/2 h | 33,7 | 1070 | 0,3 |
I | 17 | 20°C/min 400°C, 1/2 h | 40,4 | 1065 | (cassant) |
J | 25,5 | 10°C/min 400°C, 1 h | 40,3 | 1280 | (cassant) |
K | 25,5 | 1°C/min 400°C, 1 h | 41,6 | 1095 | 0,76 |
L | 34 | 10°C/min 400°C, 1 h | 39,7 | 1660 | (très cassant) |
Tissu activé | Teneur en H3PO4 % | Traitement thermique | Surface spécifique m2/g | Résistance en traction daN/cm |
M | 17 | 10°C/min 400°C, 1/2 h | 1 000 | 1 |
N | 1 à 7 | 10°C/min 400°C, 1/2 h | 150 à 250 | 5,2 |
O | 17 | 0,01 à 0,1°C/min 400°C, 1/2 h | 200 | 1,1 |
P | 17 | 10°C/min 400°C, 2 à 12 h | 170 à 130 | 0,9 |
Tissu activé | Constituant de la composition d'imprégnation | Surface spécifique m2/g | Résistance en traction daN/cm |
Q | H3PO4 (17 %) | 1 005 | 0,7 |
R | H3PO4(17%)+ Na2B4O7(1,5%) | 1 020 | 2,7 |
S | NH4CI (25 %) | 350 | 3,1 |
T | (NH4)2HPO4 (20 %) | 540 | 0,9 |
Tissu activé | Type de précurseur | Surface spécifique m2/g | Résistance en traction daN/cm |
U | Rayonne I | 1 310 | 1,5 |
V | Rayonne II | 1 010 | 3,1 |
W | Rayonne III | 1 145 | (rigide et cassant) |
X | Rayonne IV | 750 | (cassant) |
Y | Fibranne V | 1 030 | 0,2 (souple) |
Claims (8)
- Procédé de réalisation d'une texture activée en fibres de carbone, comprenant les étapes qui consistent à fournir une texture en fibres de matériau cellulosique précurseur de carbone, imprégner la texture par une composition contenant au moins un constituant minéral ayant une fonction de promoteur de la déshydratation de la cellulose, et effectuer un traitement thermique de la texture imprégnée à une température suffisante pour provoquer la transformation du précurseur cellulosique essentiellement en carbone, et obtenir une texture en fibres de carbone, caractérisé en ce que :le matériau cellulosique précurseur de carbone est choisi parmi les rayonnes, la fibranne, les celluloses à solvant, le coton et les fibres libériennes, etle traitement thermique est réalisé sous atmosphère inerte ou partiellement oxydante, consiste en une montée en température à une vitesse moyenne comprise entre 1 et 15°C/min suivie d'un palier à une température comprise entre 350°C et 500°C, et est suivi d'une étape d'élimination de phases résiduelles de la composition d'imprégnation et de produits de dégradation du matériau cellulosique par lavage de la texture, de sorte que l'on obtient directement une texture activée en fibres de carbone ayant une surface spécifique au moins égale à 600 m2/g, sans traitement ultérieur d'activation à température plus élevée.
- Procédé selon la revendication 1, caractérisé en ce que la durée du palier du traitement thermique est au plus égale à 1 h.
- Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le matériau cellulosique précurseur de carbone est choisi parmi les rayonnes textiles et la fibranne:
- Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la composition liquide d'imprégnation de la texture en fibres de matériau cellulosique contient au moins un constituant minéral et des charges solides.
- Procédé selon la revendication 4, caractérisé en ce que les charges solides sont choisies parmi l'antimoine, le fer, le titane et le silicium.
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les étapes de traitement thermique et de lavage sont réalisées sur la texture fibreuse en continu.
- Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le lavage est réalisé à l'eau et comprend une première phase de solubilisation d'un excès éventuel de constituant de la composition d'imprégnation et une deuxième phase de rinçage.
- Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'imprégnation de la texture en fibres de matériau cellulosique est réalisée avec une composition contenant au moins de l'acide phosphorique, de manière que la masse d'acide phosphorique pur fixée sur la texture soit comprise entre 10 % et 22 % de la masse de la texture à l'état sec.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9703083 | 1997-03-14 | ||
FR9703083A FR2760759B1 (fr) | 1997-03-14 | 1997-03-14 | Procede de realisation de textures activees en fibres de carbone |
PCT/FR1998/000504 WO1998041678A1 (fr) | 1997-03-14 | 1998-03-12 | Procede de realisation d'une texture activee en fibres de carbone |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0966558A1 EP0966558A1 (fr) | 1999-12-29 |
EP0966558B1 true EP0966558B1 (fr) | 2002-11-27 |
Family
ID=9504776
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98914905A Expired - Lifetime EP0966558B1 (fr) | 1997-03-14 | 1998-03-12 | Procede de realisation d'une texture activee en fibres de carbone |
Country Status (7)
Country | Link |
---|---|
US (1) | US6120841A (fr) |
EP (1) | EP0966558B1 (fr) |
JP (1) | JP3357080B2 (fr) |
DE (1) | DE69809718T2 (fr) |
ES (1) | ES2185159T3 (fr) |
FR (1) | FR2760759B1 (fr) |
WO (1) | WO1998041678A1 (fr) |
Cited By (3)
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US7354475B2 (en) | 2004-05-13 | 2008-04-08 | Blucher Gmbh | Adsorption filter material and its use |
US7582578B2 (en) | 2004-07-05 | 2009-09-01 | BLüCHER GMBH | Textile composite material comprising activated carbon fibres and production thereof |
DE102010044794A1 (de) | 2009-09-09 | 2011-03-17 | BLüCHER GMBH | Brennstoffzelle |
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FR2788168A1 (fr) * | 1998-12-30 | 2000-07-07 | Messier Bugatti | Electrode a diffusion gazeuse supportant un catalyseur de reaction electrochimique |
FR2794117B1 (fr) * | 1999-05-25 | 2001-08-24 | Messier Bugatti | Procede et installation pour la separation de metaux lourds contenus dans des effluents liquides |
FR2801908B1 (fr) * | 1999-12-06 | 2002-03-01 | Snecma | Procede pour l'obtention de tissu en fibres de carbone par carbonisation en continu d'un tissu en fibres cellulosiques |
FR2801907B1 (fr) * | 1999-12-06 | 2002-03-01 | Snecma | Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie |
FR2806640B1 (fr) * | 2000-03-22 | 2002-10-18 | Messier Bugatti | Procede de fabrication d'une piece filtrante en forme en fibres de carbone active et piece de revetement de protection telle qu'obtenue par le procede |
FR2819420A1 (fr) * | 2001-01-12 | 2002-07-19 | Manuf De Vetements Paul Boye | Application d'une texture activee en fibres de carbone a la protection contre les effets des agents biologiques, et produit de protection |
KR100398062B1 (ko) * | 2001-05-11 | 2003-09-19 | 한국과학기술연구원 | 고기능성 비스코스레이온계 활성 탄소섬유 및 이의 제조방법 |
DE10318054B3 (de) * | 2003-04-17 | 2004-12-23 | BLüCHER GMBH | Luftfiltereinheit mit mehreren Filterelementen und deren Verwendung |
EP1622830A2 (fr) * | 2003-05-09 | 2006-02-08 | McGill University | Procede de production de charbon actif |
WO2007122721A1 (fr) * | 2006-04-21 | 2007-11-01 | Therath Medico, Inc. | Fibres et produits dérivés pour le soulagement des symptômes de douleurs fibromusculaires |
DE202015004713U1 (de) | 2015-07-02 | 2015-07-17 | Plamen Kravaev | Endlosfaserverstärkte Vliesstoffe aus aktivierten Kohlenstofffasern |
DE202016001344U1 (de) | 2016-03-02 | 2016-03-16 | Plamen Kravaev | Vorlagematerialien für die Produktion von Halbzeugen aus aktivierten Kohlenstofffasern |
DE102016003400A1 (de) | 2016-03-19 | 2017-09-21 | Plamen Kravaev | Verfahren zur Herstellung von aktivierten textilen Halbzeugen aus recycelten Kohlenstofffasern |
JP6568328B1 (ja) * | 2018-06-19 | 2019-08-28 | 日本製紙株式会社 | 自動車キャニスタ用活性炭素繊維シート |
DE102020113807A1 (de) * | 2020-05-22 | 2021-11-25 | centrotherm international AG | Endlosfasern auf Basis von Cellulose und/oder Cellulosederivaten, Verfahren zu deren Herstellung sowie deren Verwendung |
CN114293364B (zh) * | 2022-01-28 | 2023-09-26 | 华北电力大学(保定) | 碳纤维活化方法及设备 |
CN115058793B (zh) * | 2022-05-30 | 2024-01-23 | 河北科技大学 | 一种碳纤维、碳纤维负极材料及制备方法 |
CN115385709B (zh) * | 2022-08-23 | 2023-09-29 | 湖南博云新材料股份有限公司 | 一种碳碳复合材料快速致密的方法 |
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US3479151A (en) * | 1966-01-03 | 1969-11-18 | Hitco | Method of carbonizing fibrous cellulosic materials |
US3441378A (en) * | 1966-05-10 | 1969-04-29 | Union Carbide Corp | Process for the manufacture of carbon textiles |
GB1222881A (en) * | 1967-01-06 | 1971-02-17 | Nippon Carbon Company Ltd | Process for the preparation of carbon fibers |
GB1301101A (en) * | 1969-01-08 | 1972-12-29 | Secr Defence | Improvements in the manufacture of carbon |
US3661503A (en) * | 1969-05-29 | 1972-05-09 | Union Carbide Corp | Process for dehydrating cellulosic textile material |
JPS506821A (fr) * | 1973-06-02 | 1975-01-24 | ||
JPS5225120A (en) * | 1975-08-20 | 1977-02-24 | Toyobo Co Ltd | Preparation of active carbon fibers |
JPS6025528B2 (ja) * | 1975-12-04 | 1985-06-19 | 東洋紡績株式会社 | 活性炭素繊維 |
JPS5314831A (en) * | 1976-07-21 | 1978-02-09 | Toyobo Co Ltd | Preparation of carbon fiber |
JPS5510472A (en) * | 1978-07-10 | 1980-01-24 | Takeda Chem Ind Ltd | Production of activated carbon fiber |
JPS57167716A (en) * | 1982-03-18 | 1982-10-15 | Toyobo Co Ltd | Adsorbing filter-sheet |
JPS60198166A (ja) * | 1984-03-21 | 1985-10-07 | 東洋紡績株式会社 | 呼吸具吸収缶 |
JPS62133124A (ja) * | 1985-11-30 | 1987-06-16 | Toho Rayon Co Ltd | 活性炭素繊維織物の製造方法 |
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CN1034133C (zh) * | 1994-07-28 | 1997-02-26 | 刘智仁 | 高吸附性活性炭纤维的制备方法 |
TW274567B (en) * | 1994-08-25 | 1996-04-21 | Jyi-Shyang Wang | Method of preparing active carbon fiber fabric |
-
1997
- 1997-03-14 FR FR9703083A patent/FR2760759B1/fr not_active Expired - Fee Related
-
1998
- 1998-03-12 DE DE69809718T patent/DE69809718T2/de not_active Expired - Lifetime
- 1998-03-12 WO PCT/FR1998/000504 patent/WO1998041678A1/fr active IP Right Grant
- 1998-03-12 EP EP98914905A patent/EP0966558B1/fr not_active Expired - Lifetime
- 1998-03-12 JP JP54019098A patent/JP3357080B2/ja not_active Expired - Fee Related
- 1998-03-12 ES ES98914905T patent/ES2185159T3/es not_active Expired - Lifetime
- 1998-03-12 US US09/381,060 patent/US6120841A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7354475B2 (en) | 2004-05-13 | 2008-04-08 | Blucher Gmbh | Adsorption filter material and its use |
US7582578B2 (en) | 2004-07-05 | 2009-09-01 | BLüCHER GMBH | Textile composite material comprising activated carbon fibres and production thereof |
DE102010044794A1 (de) | 2009-09-09 | 2011-03-17 | BLüCHER GMBH | Brennstoffzelle |
DE202010012377U1 (de) | 2009-09-09 | 2011-08-04 | BLüCHER GMBH | Brennstoffzelle |
Also Published As
Publication number | Publication date |
---|---|
DE69809718D1 (de) | 2003-01-09 |
DE69809718T2 (de) | 2003-12-18 |
JP2001516404A (ja) | 2001-09-25 |
WO1998041678A1 (fr) | 1998-09-24 |
FR2760759B1 (fr) | 1999-06-11 |
EP0966558A1 (fr) | 1999-12-29 |
US6120841A (en) | 2000-09-19 |
ES2185159T3 (es) | 2003-04-16 |
FR2760759A1 (fr) | 1998-09-18 |
JP3357080B2 (ja) | 2002-12-16 |
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