EP3143187A1 - Procédé de production de fibres de carbone à partir de fibres de cellulose - Google Patents
Procédé de production de fibres de carbone à partir de fibres de celluloseInfo
- Publication number
- EP3143187A1 EP3143187A1 EP15721717.5A EP15721717A EP3143187A1 EP 3143187 A1 EP3143187 A1 EP 3143187A1 EP 15721717 A EP15721717 A EP 15721717A EP 3143187 A1 EP3143187 A1 EP 3143187A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- weight
- fibers
- parts
- additives
- 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.)
- Granted
Links
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 86
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 24
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920002678 cellulose Polymers 0.000 claims abstract description 22
- 239000001913 cellulose Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 238000009987 spinning Methods 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 229920000297 Rayon Polymers 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- -1 alkali metal salts Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 244000198134 Agave sisalana Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical compound OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002892 organic cations Chemical class 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
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- D01F9/16—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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
Definitions
- the invention relates to a process for the production of carbon fibers from cellulose fibers, which comprises contacting cellulose fibers having a water content of more than 20 parts by weight of water per 100 parts by weight of cellulose fiber with a solution of additives and then the additivated cellulose fibers containing at least 1 part by weight of additives per 100 parts by weight of cellulose are converted into carbon fibers.
- Carbon fibers can be made by pyrolysis of polyacrylonitrile fibers or cellulose fibers. As renewable raw materials, cellulose fibers are becoming increasingly important for the growing market for carbon fibers.
- Fanlong Zeng, Ding Pan and Ning Pan use viscose fibers to make carbon fibers (Journal of Inorganic and Organometallic Polymers and Materials, Vol.15, No.2 June 2005). Again, dried cellulose fibers are treated with solutions of additives and then converted into carbon fibers.
- Hui Li, Yonggang Yang, Yuefang Wen and Lang Liu (Composites Science and Technology 67 (2007) 2675-2682) impregnate the viscose fibers with an organic silicon compound before drying. After drying the fiber pretreated in this way, conventional treatment of the cellulose fiber with additives takes place, here with an aqueous solution of ammonium sulfate and ammonium chloride, and finally the carbonization.
- cellulose which has been dissolved in ionic liquid is used according to CN 101871 140 for the production of carbon fibers.
- the carbon yield should be as high as possible, that is, the carbon of the starting fiber is transferred as completely as possible into the carbon fiber.
- the carbon yield is not yet satisfactory. Part of the carbon in the cellulose is lost through degradation into ultimately carbon monoxide and carbon dioxide. Also, the mechanical properties of the carbon fibers obtained from cellulose fibers should be further improved.
- the object of the present invention was therefore an improved process for the production of carbon fibers from cellulose fibers. Accordingly, the method defined above was found.
- Cellulose fibers are the starting material of the process.
- Cellulosic fibers are here understood to mean fibers which consist of more than 60% by weight, in particular more than 80% by weight, particularly preferably more than 90% by weight, of cellulose or modified cellulose.
- the cellulosic fibers consist of more than 98% by weight, most preferably 100% by weight, of cellulose or modified cellulose.
- modified cellulose is meant cellulose in which hydroxyl groups are etherified or esterified, e.g., it may be cellulose acetate, cellulose formate, cellulose propionate, cellulose carbamate or cellulose allophanate.
- cellulose fibers which consist of cellulose in the minimum amounts specified above.
- the cellulose fibers which are brought into contact with the solution of an additive have a water content of more than 20 parts by weight of water, in particular more than 30 parts by weight of water, more preferably more than 50 parts by weight of water, most preferably more than 70 parts by weight of water per 100 parts by weight cellulose fiber.
- the water content is not higher than 500, especially not higher than 300 parts by weight of water per 100 parts by weight of cellulose fiber.
- the cellulose fiber having the above water content can be easily obtained by, for example, dipping a dried cellulose fiber in water. Both natural cellulose fibers and synthetic cellulose fibers are suitable for this purpose.
- Natural cellulose fibers are in particular cellulose fibers obtained from cotton.
- synthetic cellulose fibers are used
- synthetic cellulose fibers are used which were prepared immediately before by a spinning process.
- the cellulose fibers are then preferably through
- a spin bath is prepared by dissolving cellulose in a solvent. From this spinning bath, the cellulose fiber is obtained by coagulation of the cellulose in the form of a fiber.
- Viscose fibers produced by the viscose process are Viscose fibers produced by the viscose process
- Lyocell® fibers made from a spinning solution containing NMMO (N-methylmorpholine N-oxide) as a solvent and
- Cellulose fibers which are obtained from spinning solutions with ionic liquid as a solvent, as z. B. in WO 2007/076979 is described. In all the above cases, the obtained cellulose fibers are washed with water to remove adhering solvent or adhesive additives from the spinning bath.
- the contact with water is carried out so that the cellulose fiber absorbs water in the desired amount indicated above.
- the cellulose fiber can be immersed in water for a sufficient time or passed through a sufficiently long water bath in a continuous process.
- cellulose fibers In the production of the cellulose fibers preferably no process measures for drying take place.
- the cellulose fiber obtained in the spinning process is washed with water without prior drying and then, of course again without prior drying, brought into contact with the solution of the additive. It is therefore a so-called "never dried" cellulose fiber.
- the aqueous cellulose fibers are contacted with a solution of additives.
- hydrophilic solvent especially in water, hydrophilic organic solvents, e.g. Alcohols or ethers, or mixtures thereof.
- hydrophilic solvents are water or mixtures of water with other hydrophilic organic solvents which are immiscible with water indefinitely, with the water content in the solvent mixture in a preferred embodiment being at least 50% by weight in the latter case.
- the solution is a solution of additives in water.
- the solution may contain only a single additive or a mixture of different additives.
- Particularly suitable as additives are compounds which have a solubility in water of at least 10 parts by weight, preferably of at least 20 parts by weight, in particular of at least 30 parts by weight per 100 parts by weight of water under normal conditions (20 ° C., 1 bar).
- the additives are preferably low molecular weight compounds which have a maximum molecular weight of 1000 g / mol, particularly preferably not more than 500 g / mol, in particular not more than 300 g / mol.
- salts or acids are suitable, for.
- inorganic salts inorganic acids, organic salts or organic acids.
- Suitable organic acids are, in particular, carboxylic acids, sulfonic acids or phosphonic acids.
- Suitable organic salts are in particular salts of the above organic acids, which may be metal salts, in particular alkali metal salts, or salts with organic cations.
- Suitable organic acids are e.g. those which react with the cellulose and by a chemical reaction, for. B. a substitution reaction can be connected.
- phosphoric acid may be mentioned as the inorganic acid.
- Suitable inorganic salts are in particular those whose anions contain phosphorus atoms, sulfur atoms or nitrogen atoms, for.
- phosphate hydrogen phosphate, phosphite, hydrogen phosphite, sulfate or sulfite, or which contain chloride as anion.
- the cations of the above inorganic salts may in particular be metal cations, preferably alkali metal cations such as Na + or K + , or ammonium (NhV).
- additives are often additives which are also used as flame retardants. It may be assumed that these additives interact with the primary hydroxyl group of the glucose ring (ie the CH 2 OH group) and counteract degradation of the cellulose to volatile carbon compounds during pyrolysis.
- the total amount of all additives in the solution is z. B. 0.05 to 5 mol / per liter of solution, preferably 0.1 mol to 2 mol / per liter of solution.
- the contact with the solution of the additives is carried out so that the cellulose fiber absorbs additives in the desired amount.
- the cellulose fiber can be immersed in the solution for a sufficient time or be passed through a sufficiently long solution bath in a continuous process.
- the cellulose fiber is continuously passed through the solution of the additive.
- the contact time of the cellulose fiber with the solution of the additives is preferably at least 0.5 seconds, more preferably at least 2 and most preferably at least 10 seconds. In general, it is not longer than 100 seconds, preferably not longer than 30 seconds.
- the obtained, additivated cellulose fiber contains in a preferred embodiment at least 5 parts by weight of additives per 100 parts by weight of cellulose.
- the additivated cellulose fiber particularly preferably contains at least 1 part by weight, very particularly preferably at least 3 parts by weight of additives per 100 parts by weight of cellulose fiber.
- the cellulose fiber contains no more than 30 parts by weight of additives, in particular not more than 10 or not more than 5 parts by weight of additives per 100 parts by weight of cellulose fiber.
- the production of the cellulose fiber in the spinning process, followed by the further processing by washing the cellulose fiber and contacting the cellulose fiber with the solution of the additives, are preferably components of a continuous overall process.
- the cellulose fiber is generally fed to the individual steps of further processing after their production via movable rollers.
- excess solvent can be removed from the solution of additives by squeezing and rolled up the additivated cellulose fiber.
- the additiviere cellulose fiber can be dried, z. B. at temperatures of 50 to 300 ° C. Drying of this type is recommended when the additized cellulose sebase is first to be stored or transported before it is converted into a carbon fiber.
- the additivated cellulose fiber is converted by pyrolysis in a carbon fiber.
- the pyrolysis is generally carried out at temperatures of 500 to 1600 ° C. It can, for example, under air or under inert gas, for. As nitrogen or helium are performed. Preferably, it is carried out under a protective gas.
- the cellulose fiber can be dried. For already dried and stored cellulose fibers, the drying may optionally be repeated. It is possible to use a multi-stage process in which the cellulose fiber is dried at temperatures in the range from 50 to 300 ° C. and then the pyrolysis is carried out at temperatures in the range from 500 to 1600 ° C., preferably 700 to 1500 ° C.
- the temperature can be increased gradually or continuously.
- drying may take place in two or more stages, for example at 50 to 100 ° C in a first stage and at 100 to 200 ° C in a second stage.
- the contact time in the individual stages can be, for example, 5 to 300 seconds and 10 to 500 seconds in total during the drying.
- pyrolysis may be considered, in which the temperature is continuously increased, e.g. Starting from 200 ° C until finally reaching 1600 or 1400 or 1200 ° C.
- the temperature increase can take place, for example, at 1 to 20 Kelvin / minute.
- the cellulose fiber should preferably be exposed to a temperature in the range of 900 to 1600 ° C. for a period of 10 to 60 minutes.
- the carbon yield in the pyrolysis is generally 20 to 95% by weight; that is, the carbon fiber contains 20 to 95 percent by weight of the carbon contained in the cellulose fiber.
- the carbon yield is in particular from 70 to 95, particularly preferably from 70 to 90, very particularly preferably from 70 to 85,% by weight.
- the resulting carbon fiber has very good mechanical properties, in particular good strength and elasticity.
- cellulose fiber in the example and comparative example a synthetic, tear-resistant cellulose fiber used for the production of car tires is used. Such cellulose fibers are known as tire cord fibers.
- the cellulose fiber in the example has not been dried since its production, hence the term "never-dried tire cord fiber.”
- the cellulose fiber in the comparative example was dried, but cellulose fibers usually contain bound residual water, therefore, the water content of dried cellulose fibers can be e.g. up to 20 wt.%.
- the equipment and drying of the fiber takes place in a continuous process on godets.
- Godets are rollers that allow the continuous flow of fiber along the system. There are 4 of these godets used.
- the loading of the fiber with the additives takes place via a dip bath.
- a hot air duct Between the third and fourth galette is a hot air duct, in which a drying takes place.
- a tension controlled winder winds up the finished and dried fiber material.
- the first galette serves as the unwinding unit of the never-dried tire cord fibers stored in water.
- the fiber is wound twice around the godet, which corresponds to a contact time of 10 seconds.
- the fiber is passed through an immersion bath with an ammonium dihydrogen phosphate solution (concentration of the ammonium hydrogenphosphate of 0.54 mol / l).
- the residence time is about one second.
- the material is now wound six times around the second godet. This step is to drain unnecessary equipment and cause a homogeneous distribution of the ammonium hydrogen phosphate in the fiber.
- the contact time here is 72 seconds.
- the drying is carried out on the heated with 80 ° C third galette.
- 10 windings correspond here to a contact time of 100 sec.
- the fiber is now passed through a 150 ° C hot air duct.
- the dwell time is 12 sec.
- the dry thread is then wound 4 times around the last godet (contact time 24 sec) before a tension-controlled winder winds the material with a pretension of 0.1 cN / tex.
- the cellulose fiber equipped with the additive is then carbonized under protective gas in two stages. In the first stage, 2 ° K / min is heated to 260 ° C for me and after a residence time of 10 min at 10k / min heated to 1400 ° C and then cooled.
- the carbon yield is 80% by weight, the strength of the fiber is 1.4 gpa and the elongation at break is 3.1%. Comparative example with drying before the additization
- Example 1 For the equipment with additives, a dried tire cord fiber with a water content of less than 20% by weight and a single filament titer of 2.2 dtex with 1000 filaments is presented. The experimental procedure corresponds to Example 1.
- the carbon yield is 65 wt.%, The strength of the fiber 1, 1 Gpa and the elongation at break 2.2%.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14168572 | 2014-05-16 | ||
PCT/EP2015/060479 WO2015173243A1 (fr) | 2014-05-16 | 2015-05-12 | Procédé de production de fibres de carbone à partir de fibres de cellulose |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3143187A1 true EP3143187A1 (fr) | 2017-03-22 |
EP3143187B1 EP3143187B1 (fr) | 2020-11-11 |
Family
ID=50771083
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15721717.5A Active EP3143187B1 (fr) | 2014-05-16 | 2015-05-12 | Procédé de production de fibres de carbone à partir de fibres de cellulose |
Country Status (4)
Country | Link |
---|---|
US (1) | US20170081787A1 (fr) |
EP (1) | EP3143187B1 (fr) |
EA (1) | EA201692291A1 (fr) |
WO (1) | WO2015173243A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE212015000267U1 (de) | 2014-11-20 | 2017-07-24 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Carbonfasern aus Phosphor enthaltenden Cellulosefasern |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017133995A1 (fr) | 2016-02-01 | 2017-08-10 | Basf Se | Procédé de production lactames c4-c15 |
US10995429B2 (en) * | 2016-02-11 | 2021-05-04 | Deutsche Institute Furtextil-Und Faserforschung Denkendorf | Method for producing carbon fibers from cellulose fibers treated with sulfonic acid salts |
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 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1455531A (en) * | 1975-01-02 | 1976-11-10 | Toyo Boseki | Process for preparing active carbon fibres machine for attaching components to a printed circuit board |
ATE361383T1 (de) * | 2004-12-07 | 2007-05-15 | Snecma Propulsion Solide | Verfahren zur herstellung von garnen oder faserblättern aus kohlenstoff ausgehend von einem cellulosematerial |
RU2429316C1 (ru) * | 2010-03-26 | 2011-09-20 | Юрий Васильевич Карасев | Способ непрерывного получения из гидратцеллюлозы углеродного волокна в виде однонаправленного жгута |
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2015
- 2015-05-12 EA EA201692291A patent/EA201692291A1/ru unknown
- 2015-05-12 US US15/311,033 patent/US20170081787A1/en not_active Abandoned
- 2015-05-12 EP EP15721717.5A patent/EP3143187B1/fr active Active
- 2015-05-12 WO PCT/EP2015/060479 patent/WO2015173243A1/fr active Application Filing
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE212015000267U1 (de) | 2014-11-20 | 2017-07-24 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Carbonfasern aus Phosphor enthaltenden Cellulosefasern |
Also Published As
Publication number | Publication date |
---|---|
EA201692291A1 (ru) | 2017-04-28 |
WO2015173243A1 (fr) | 2015-11-19 |
US20170081787A1 (en) | 2017-03-23 |
EP3143187B1 (fr) | 2020-11-11 |
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