US20100047153A1 - Method of manufacturing carbon fibres - Google Patents
Method of manufacturing carbon fibres Download PDFInfo
- Publication number
- US20100047153A1 US20100047153A1 US12/546,128 US54612809A US2010047153A1 US 20100047153 A1 US20100047153 A1 US 20100047153A1 US 54612809 A US54612809 A US 54612809A US 2010047153 A1 US2010047153 A1 US 2010047153A1
- Authority
- US
- United States
- Prior art keywords
- fibres
- pan
- glycerol
- acrolein
- acrylonitrile
- 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.)
- Abandoned
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 37
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 34
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000013311 vegetables Nutrition 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 229920001519 homopolymer Polymers 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 150000003626 triacylglycerols Chemical class 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 230000000155 isotopic effect Effects 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003225 biodiesel Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- -1 fatty acid triglycerides Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- D01F9/20—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- 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
Definitions
- the present invention relates to a method of manufacturing carbon fibres from raw materials of renewable origin, and also to fibres capable of being obtained according to this method.
- Carbon fibres are materials composed of very fine fibres having a diameter of 5 to 10 microns, for which carbon is the main chemical element. Other atoms are generally present such as oxygen, nitrogen, hydrogen and less often sulphur. The carbon atoms are bonded together and form crystals of graphite type that are more or less aligned parallel to the axis of the fibre. Several thousand of these fibres are twisted together to form a strand. These strands may be used alone or made into the form of a fabric.
- Carbon fibres are one of the materials that are developing fastest at the current time. Used as reinforcements for thermosets such as crosslinked polyester resins and epoxy resins, or as agents for improving certain thermoplastics such as polyamides, they actually make it possible to obtain composites that are very strong relative to their weight and even that are often stronger than steel per unit weight.
- Carbon fibres also find applications in the filtration of high-temperature gases, as antistatic agents, as specialty electrodes due to their corrosion resistance, as reinforcement for pressurized gas tanks, especially for storing hydrogen.
- the synthesis of carbon fibres from PAN typically comprises a step of firing the fibre at about 300° C., in order to oxidize it slightly, after which the fibre is placed in an inert atmosphere under argon or nitrogen at a temperature of around 2000° C. in an electric furnace. After this step, the fibre contains around 95% carbon. A subsequent treatment at a higher temperature increases its thermal conductivity and its modulus.
- one subject of the present invention is a novel method of synthesizing carbon fibres from raw materials of renewable or biobased origin.
- one subject of the invention is a method of manufacturing carbon fibres, comprising:
- step (a) may comprise steps other than those mentioned above and in particular one or more steps prior to step (a), one or more steps after step (f) and/or one or more intermediate steps, as long as these steps do not negatively affect the entire method, in particular the yield and/or the quality of the carbon fibres obtained.
- acrolein is formed from glycerol of vegetable origin.
- the glycerol used in step (a) is obtained as a by-product of a transesterification of triglycerides of vegetable origin.
- a conventional transesterification reaction actually uses a linear C 1 -C 10 monoalcohol, such as methanol or ethanol, or a cyclic C 3 -C 6 monoalcohol, which is reacted with triglycerides to obtain alkyl esters of C 1 -C 10 alcohols and glycerol.
- Triglycerides are compounds of formula: R 1 —CO—O—CH 2 —CH(OCO—R 2 )—CH 2 —O—CO—R 3 , in which R 1 to R 3 denote saturated or (poly)unsaturated, linear or branched C 10 -C 30 , for example C 12 -C 18 , alkyl groups, which are an important constituent of vegetable oils and fats such as palm oil, linseed oil, groundnut oil, coconut oil, sunflower oil, soybean oil or rapeseed oil. The latter is especially transesterified in the manufacture of biodiesel recommended as a replacement fuel for fossil fuels.
- the glycerol used according to the invention may therefore be a by-product of the manufacture of biodiesel from vegetable oil. By way of indication, around 1 tonne of glycerol is obtained from 10 tonnes of fatty acid triglycerides.
- the transesterification step is generally carried out at a temperature of 20 to 150° C., preferably from 25 to 100° C., more preferably from 25 to 80° C., for example over a period of 4 to 8 hours, in the presence of acid or basic catalysts, preferably in the presence of a basic catalyst such as sodium or potassium methoxide, in a solvent such as methanol, in a stirred reactor (in particular under high shear) or a fixed or fluidized bed reactor.
- the transesterification may be carried out in the presence of supercritical methanol at high temperature and pressure. In general, all the reactants are dehydrated to prevent the saponification of the triglycerides and to enable an easier separation of the glycerol.
- step (a) of the method according to the invention the glycerol is dehydrated to acrolein in the liquid phase or in the gas phase.
- the dehydration of the glycerol to acrolein is carried out at 250-350° C. and 1 to 5 bar, in the presence of molecular oxygen and advantageously with an acidic solid catalyst, as described in Application WO 2006/087083, preferably in the presence of a catalyst of strong acid type having a Hammett acidity function H 0 of between ⁇ 9 and ⁇ 18, as described in Application WO 2006/087084.
- the dehydration of glycerol may be carried out as described in Application US 2008/119663, by heating at a temperature ranging from 250 to 400° C., preferably from 260 to 300° C.
- the pressure is adjusted, for example between 1 and 50 bar, so as to keep the reaction medium in the liquid state.
- a homogeneous or heterogeneous acid catalyst, and/or salts of mineral acids, such as potassium or sodium (hydrogen)sulphates, may be used to accelerate the reaction.
- a homogeneous acid catalyst such as sulphuric acid, phosphoric acid, toluenesulphonic acid or methanesulphonic acid or a heterogeneous catalyst such as a zeolite of HZSM-5 or MCM-22 type, metal oxides, such as aluminium oxide, covered by an inorganic acid such as phosphoric acid, or an ion exchange resin.
- a homogeneous acid catalyst such as sulphuric acid, phosphoric acid, toluenesulphonic acid or methanesulphonic acid or a heterogeneous catalyst such as a zeolite of HZSM-5 or MCM-22 type, metal oxides, such as aluminium oxide, covered by an inorganic acid such as phosphoric acid, or an ion exchange resin.
- biocatalysts such as lipases or esterases.
- the present description does not exclude the glycerol from being dehydrated to acrolein at the same time as it is formed from triglycerides, in the presence of a dehydration catalyst as described above, as taught in document US 2008/0119663. It will then be advisable, in this case, to then carry out a separation of the acrolein from the reaction medium by any suitable means, for example by distillation, extraction, phase separation or membrane separation. It is preferred however that the transesterification and dehydration steps are carried out separately, in order to optimize the yield of acrolein. In order to do this, the glycerol is advantageously extracted from the transesterification reaction medium by distillation, membrane separation or phase separation. It may optionally then be purified to remove the soaps, salts, and bases that it contains in a small amount, before being converted to acrolein.
- step (a) of the method according to the invention is then subjected, in step (b), to an ammoxidation in order to obtain acrylonitrile, according to the following reaction scheme:
- This ammoxidation step is well known to a person skilled in the art and may in particular be carried out at 200-450° C. by passing a mixture of acrolein, ammonia, air and inert gas over a catalyst formed from one or more oxygenated salts of arsenic and of less electronegative elements.
- a method of this type is described in Application FR 1 410 967. As a variant, it may be carried out as described in document DE-1 070 170, by using a molybdenum-based catalyst, at a temperature of 250-350° C., or as described in document U.S. Pat. No.
- the acrylonitrile thus obtained is polymerized, in step (c) of the method according to the invention.
- the acrylonitrile may be homopolymerized or, according to a preferred embodiment of the invention, copolymerized with at least one other monomer, preferably an acrylic monomer, that is to say a monomer of (meth)acrylic acid or of an alkyl ester of (meth)acrylic acid, such as methyl acrylate, methyl methacrylate or acrylic acid.
- an acrylic monomer that is to say a monomer of (meth)acrylic acid or of an alkyl ester of (meth)acrylic acid, such as methyl acrylate, methyl methacrylate or acrylic acid.
- this comonomer allows a better control of the thermal effects in the subsequent step (e) (Gupta, A. K.
- This comonomer may itself be of renewable origin.
- the acrylic acid may be obtained from glycerol and the methyl methacrylate may incorporate, via its synthesis, acetone and methanol of renewable origin.
- Methyl acrylate is preferred for use in the present invention, since it is very close in polarity to acrylonitrile.
- the (co)polymerization of the acrylonitrile may be carried out in a conventional manner, by radical solution polymerization, using a solvent of dimethylsulphoxide (DMSO) or dimethylformamide (DMF) type, optionally in the presence of an activator such as azobisisobutyronitrile (AIBN) or of an azocarboxylic acid ester, as described in the Patent Application US 2004/068069.
- DMSO dimethylsulphoxide
- DMF dimethylformamide
- an activator such as azobisisobutyronitrile (AIBN) or of an azocarboxylic acid ester, as described in the Patent Application US 2004/068069.
- the (co)polymerization of the acrylonitrile may be carried out in aqueous dispersion in the presence of sodium thiocyanate, zinc chloride or sodium perchlorate, for example.
- This PAN is then formed into fibres in step (d) of the method according to the invention.
- This step may be carried out in several ways.
- the PAN is mixed with at least one plasticizer such as an alkyl carbonate, in particular ethylene carbonate (ester of ethylene glycol and of carbonic acid), it is heated at 110-160° C. in order to soften it and it is injected through a fine die, so that it falls into a bath, composed for example of water, where it coagulates and solidifies in the form of fibres.
- an alkyl carbonate in particular ethylene carbonate (ester of ethylene glycol and of carbonic acid)
- ethylene carbonate ester of ethylene glycol and of carbonic acid
- the PAN in dissolved in a solvent (DMSO, DMF, DMA or aqueous solution of inorganic salts) and it is injected through a fine die into a receiving chamber or drying oven where, after evaporation of the solvent, the polymer forms a solid fibre.
- a solvent DMSO, DMF, DMA or aqueous solution of inorganic salts
- the fibres thus obtained are washed and drawn until the desired fibre diameter is obtained. Drawing also makes it possible to align the molecular species, which will subsequently facilitate, during the carbonization, a correct formation of the carbon-carbon bonds and will provide the fibre with great solidity.
- step (e) of the method according to the invention constitutes step (e) of the method according to the invention.
- This operation is carried out by heating the PAN fibres at 200-300° C. for a few tens of minutes in the presence of air.
- the fibre modifies its atomic arrangement and polar surface functions are created; it changes from a plastic state to a thermally stable infusible state. Since this reaction is exothermic, it is advisable to ensure that the heat transfers are controlled since thermal runaway could occur.
- step (f) of the method according to the invention is carried out by heating the fibres from step (e) at a temperature between 1200 and 1500° C. in a furnace purged with an inert gas and maintained at a pressure above atmospheric pressure in order to prevent air from re-entering the furnace.
- the carbonization During the carbonization, most of the atoms, apart from the carbon, are expelled in the form of water vapour for oxygen and hydrogen, ammonia and hydrogen cyanide for nitrogen atoms, gaseous nitrogen, carbon monoxide and carbon dioxide originating from the polar surface functions. The expulsion of these atoms allows the carbon to be organized in microcrystalline form by creating strong bonds.
- the carbonization may optionally be carried out in two steps, at two different temperatures, for a better control of the entire process.
- the first carbonization step may thus be carried out at 400-800° C., the fibre optionally being stretched during this step.
- fibres known as “high strength” or “intermediate modulus” fibres are obtained, depending on the treatment temperature.
- a subsequent graphitization step between 2000 and 3000° C. optionally makes it possible to obtain fibres known as “high modulus” fibres.
- the fibres may also be subjected to a sizing or oiling treatment that aims to protect them during the transport, weaving or winding thereof.
- This treatment consists in applying a coating material to the fibres, this coating material being chosen to be compatible with adhesion agents used in the manufacture of the composites and which may, for example, be selected from epoxide resins, polyesters or polyurethanes.
- Another subject of the present invention is the carbon fibres capable of being obtained according to the method described previously.
- carbon fibres are characterized in that they comprise a not insignificant amount of carbon of renewable or biobased origin or still contemporary origin, that is to say of 14 C.
- all carbon samples taken from living organisms, and in particular from the vegetable matter used in the first step of the method according to the invention are a mixture of three isotopes: 12 C, 13 C and 14 C in a 14 C/ 12 C ratio that is kept constant by continuous exchange of carbon with the environment and that is equal to 1.2 ⁇ 10 ⁇ 12 .
- 14 C is radioactive and although its concentration therefore decreases over time, its half-life is 5730 years, so that the 14 C content is considered to be constant from the extraction of the vegetable matter up to the manufacture of the fibres and even up to the end of their use.
- the carbon fibres according to the invention have an isotopic ratio of their 14 C content to their 12 C content which is greater than 10 ⁇ 12 but no more than 1.2 ⁇ 10 ⁇ 12 , where 14 C represents the isotope having 6 protons and 8 neutrons whereas 12 C represents the stable isotope having 6 protons and 6 neutrons.
- a carbon fibre containing 100% of renewable carbon contains at the most 1.2 ⁇ 10 ⁇ 12 of 14 C.
- the 14C content of the carbon fibres may be measured according to well-known techniques for dating archaeological remains, old woods, bones, peat or even seashells. It may, for example, be measured according to the following techniques:
- Another subject of the present invention is therefore carbon fibres that have an isotopic ratio of their 14 C content to their 12 C content which is greater than 2 ⁇ 10 ⁇ 11 , for example greater than 5 ⁇ 10 ⁇ 11 , and preferable greater than 10 ⁇ 12 and at the most equal to 1.2 ⁇ 10 ⁇ 12 .
- the carbon fibres according to the invention can be employed in all the applications where they are customarily used, especially for reinforcing composites, in particular in the manufacture of aircraft or spacecraft parts, sports equipment (tennis rackets and golf clubs) and wind turbines; in the filtration of high-temperature gases; as antistatic agents; as specialty electrodes; or as reinforcement for pressurized gas tanks, especially for storing hydrogen.
- Another subject of the present invention is therefore these uses of the carbon fibres described previously.
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Abstract
The present invention relates to a method of manufacturing carbon fibres from raw materials of renewable origin, comprising:
-
- a) synthesis of acrolein from glycerol of vegetable origin;
- b) ammoxidation of the acrolein to obtain acrylonitrile;
- c) polymerization of the acrylonitrile to a homopolymer or copolymer of acrylonitrile (PAN);
- d) conversion of the PAN to PAN fibres;
- e) partial oxidation of the PAN fibres; and
- f) carbonization of the partially oxidized PAN fibres. It also relates to the fibres capable of being obtained according to this method, and also to the uses thereof.
Description
- Method of manufacturing carbon fibres The present invention relates to a method of manufacturing carbon fibres from raw materials of renewable origin, and also to fibres capable of being obtained according to this method.
- Carbon fibres are materials composed of very fine fibres having a diameter of 5 to 10 microns, for which carbon is the main chemical element. Other atoms are generally present such as oxygen, nitrogen, hydrogen and less often sulphur. The carbon atoms are bonded together and form crystals of graphite type that are more or less aligned parallel to the axis of the fibre. Several thousand of these fibres are twisted together to form a strand. These strands may be used alone or made into the form of a fabric.
- Carbon fibres are one of the materials that are developing fastest at the current time. Used as reinforcements for thermosets such as crosslinked polyester resins and epoxy resins, or as agents for improving certain thermoplastics such as polyamides, they actually make it possible to obtain composites that are very strong relative to their weight and even that are often stronger than steel per unit weight.
- These composites thus have very good tensile moduli, very high tensile strength and a low thermal expansion coefficient. They can replace metals in many applications, for example aircraft or spacecraft parts, in sports equipment (tennis rackets and golf clubs) and in the structural resins used in wind turbines. Carbon fibres also find applications in the filtration of high-temperature gases, as antistatic agents, as specialty electrodes due to their corrosion resistance, as reinforcement for pressurized gas tanks, especially for storing hydrogen.
- The origin of carbon fibres dates back to 1958, the date when they were proposed by Union Carbide. The first fibres were of mediocre quality but rapid improvements were obtained using polyacrylonitrile (PAN) as a precursor. Depending on the precursor, the fibres are not identical: those obtained from PAN are fairly turbostratic, with graphitic planes that have a non-zero angle with one another and which are randomly folded. The fibres obtained from pitch are graphitic after heat treatment at more than 2200° C. The fibres obtained from these various precursors therefore also have different properties. Thus, those obtained from PAN have, in general, a better tensile strength.
- The synthesis of carbon fibres from PAN typically comprises a step of firing the fibre at about 300° C., in order to oxidize it slightly, after which the fibre is placed in an inert atmosphere under argon or nitrogen at a temperature of around 2000° C. in an electric furnace. After this step, the fibre contains around 95% carbon. A subsequent treatment at a higher temperature increases its thermal conductivity and its modulus.
- It is therefore understood that carbon fibres are very energy-intensive products, due to the high temperatures necessary during their fabrication. This energy consumption is not compensated for by their ability to allow the manufacture of lighter vehicles and to consequently reduce the energy consumption in transport applications.
- In the countries where the electricity production comes predominantly from the consumption of fossil resources, this energy expenditure is accompanied by an increase in the emission of greenhouse gases, which are particularly harmful for the environment. In order to reduce this emission, it is not easy to act on the method of synthesizing carbon fibres. On the other hand, it seems possible to use raw materials that have a lower environmental impact than the PAN conventionally used in the synthesis of carbon fibres, in particular renewable or biobased raw materials.
- In this context, one subject of the present invention is a novel method of synthesizing carbon fibres from raw materials of renewable or biobased origin.
- More specifically, one subject of the invention is a method of manufacturing carbon fibres, comprising:
- a) synthesis of acrolein from glycerol of vegetable origin;
- b) ammoxidation of the acrolein to obtain acrylonitrile;
- c) polymerization of the acrylonitrile to a homopolymer or copolymer of acrylonitrile (PAN);
- d) conversion of the PAN to PAN fibres;
- e) partial oxidation of the PAN fibres; and
- f) carbonization of the partially oxidized PAN fibres.
- This method will now be described in greater detail. It should be noted, by way of introduction, that it may comprise steps other than those mentioned above and in particular one or more steps prior to step (a), one or more steps after step (f) and/or one or more intermediate steps, as long as these steps do not negatively affect the entire method, in particular the yield and/or the quality of the carbon fibres obtained.
- In the first step of the method according to the invention, acrolein is formed from glycerol of vegetable origin.
- According to one preferred embodiment of the invention, the glycerol used in step (a) is obtained as a by-product of a transesterification of triglycerides of vegetable origin. A conventional transesterification reaction actually uses a linear C1-C10 monoalcohol, such as methanol or ethanol, or a cyclic C3-C6 monoalcohol, which is reacted with triglycerides to obtain alkyl esters of C1-C10 alcohols and glycerol. Triglycerides are compounds of formula: R1—CO—O—CH2—CH(OCO—R2)—CH2—O—CO—R3, in which R1 to R3 denote saturated or (poly)unsaturated, linear or branched C10-C30, for example C12-C18, alkyl groups, which are an important constituent of vegetable oils and fats such as palm oil, linseed oil, groundnut oil, coconut oil, sunflower oil, soybean oil or rapeseed oil. The latter is especially transesterified in the manufacture of biodiesel recommended as a replacement fuel for fossil fuels. The glycerol used according to the invention may therefore be a by-product of the manufacture of biodiesel from vegetable oil. By way of indication, around 1 tonne of glycerol is obtained from 10 tonnes of fatty acid triglycerides.
- The transesterification step is generally carried out at a temperature of 20 to 150° C., preferably from 25 to 100° C., more preferably from 25 to 80° C., for example over a period of 4 to 8 hours, in the presence of acid or basic catalysts, preferably in the presence of a basic catalyst such as sodium or potassium methoxide, in a solvent such as methanol, in a stirred reactor (in particular under high shear) or a fixed or fluidized bed reactor. As a variant, the transesterification may be carried out in the presence of supercritical methanol at high temperature and pressure. In general, all the reactants are dehydrated to prevent the saponification of the triglycerides and to enable an easier separation of the glycerol.
- In step (a) of the method according to the invention, the glycerol is dehydrated to acrolein in the liquid phase or in the gas phase. According to one preferred embodiment of the invention, the dehydration of the glycerol to acrolein is carried out at 250-350° C. and 1 to 5 bar, in the presence of molecular oxygen and advantageously with an acidic solid catalyst, as described in Application WO 2006/087083, preferably in the presence of a catalyst of strong acid type having a Hammett acidity function H0 of between −9 and −18, as described in Application WO 2006/087084.
- As a variant, the dehydration of glycerol may be carried out as described in Application US 2008/119663, by heating at a temperature ranging from 250 to 400° C., preferably from 260 to 300° C. In the case of a reaction in the liquid phase, the pressure is adjusted, for example between 1 and 50 bar, so as to keep the reaction medium in the liquid state. A homogeneous or heterogeneous acid catalyst, and/or salts of mineral acids, such as potassium or sodium (hydrogen)sulphates, may be used to accelerate the reaction. It is thus possible to use a homogeneous acid catalyst such as sulphuric acid, phosphoric acid, toluenesulphonic acid or methanesulphonic acid or a heterogeneous catalyst such as a zeolite of HZSM-5 or MCM-22 type, metal oxides, such as aluminium oxide, covered by an inorganic acid such as phosphoric acid, or an ion exchange resin. As a variant, it is possible to use biocatalysts such as lipases or esterases.
- The present description does not exclude the glycerol from being dehydrated to acrolein at the same time as it is formed from triglycerides, in the presence of a dehydration catalyst as described above, as taught in document US 2008/0119663. It will then be advisable, in this case, to then carry out a separation of the acrolein from the reaction medium by any suitable means, for example by distillation, extraction, phase separation or membrane separation. It is preferred however that the transesterification and dehydration steps are carried out separately, in order to optimize the yield of acrolein. In order to do this, the glycerol is advantageously extracted from the transesterification reaction medium by distillation, membrane separation or phase separation. It may optionally then be purified to remove the soaps, salts, and bases that it contains in a small amount, before being converted to acrolein.
- The acrolein produced in step (a) of the method according to the invention is then subjected, in step (b), to an ammoxidation in order to obtain acrylonitrile, according to the following reaction scheme:
- This ammoxidation step is well known to a person skilled in the art and may in particular be carried out at 200-450° C. by passing a mixture of acrolein, ammonia, air and inert gas over a catalyst formed from one or more oxygenated salts of arsenic and of less electronegative elements. A method of this type is described in Application FR 1 410 967. As a variant, it may be carried out as described in document DE-1 070 170, by using a molybdenum-based catalyst, at a temperature of 250-350° C., or as described in document U.S. Pat. No. 3,094,552, by passing the reaction mixture over a catalyst based on tin and antimony, at a temperature of 300-550° C., or else as described in Patent GB-709 337, in the presence of a catalyst formed from a mixture of silica, molybdenum oxide and phosphoric acid, at a temperature of 250-600° C.
- The acrylonitrile thus obtained is polymerized, in step (c) of the method according to the invention. The acrylonitrile may be homopolymerized or, according to a preferred embodiment of the invention, copolymerized with at least one other monomer, preferably an acrylic monomer, that is to say a monomer of (meth)acrylic acid or of an alkyl ester of (meth)acrylic acid, such as methyl acrylate, methyl methacrylate or acrylic acid. Indeed, as long as it does not represent more than 10% by weight relative to the total weight of the monomers to be polymerized, this comonomer allows a better control of the thermal effects in the subsequent step (e) (Gupta, A. K. et al., JMS-Rev. Macromol. Chem. Phys. C31, 1991). This comonomer may itself be of renewable origin. Thus, the acrylic acid may be obtained from glycerol and the methyl methacrylate may incorporate, via its synthesis, acetone and methanol of renewable origin. Methyl acrylate is preferred for use in the present invention, since it is very close in polarity to acrylonitrile.
- The (co)polymerization of the acrylonitrile may be carried out in a conventional manner, by radical solution polymerization, using a solvent of dimethylsulphoxide (DMSO) or dimethylformamide (DMF) type, optionally in the presence of an activator such as azobisisobutyronitrile (AIBN) or of an azocarboxylic acid ester, as described in the Patent Application US 2004/068069. As a variant, the (co)polymerization of the acrylonitrile may be carried out in aqueous dispersion in the presence of sodium thiocyanate, zinc chloride or sodium perchlorate, for example. Polymerization methods that can be used are in particular described in “Polymerization of acrylic fibers”, Encyclopedia of Polymer Science, Vol. 1, pp. 334-338, 1985. The homopolymer or copolymer obtained, denoted by PAN, in general has a weight-average molecular weight of around 80 000 to 120 000 g/mol.
- This PAN is then formed into fibres in step (d) of the method according to the invention. This step may be carried out in several ways.
- According to one method, the PAN is mixed with at least one plasticizer such as an alkyl carbonate, in particular ethylene carbonate (ester of ethylene glycol and of carbonic acid), it is heated at 110-160° C. in order to soften it and it is injected through a fine die, so that it falls into a bath, composed for example of water, where it coagulates and solidifies in the form of fibres. This method is quite similar to that used for manufacturing textile acrylic fibres.
- According to another method, the PAN in dissolved in a solvent (DMSO, DMF, DMA or aqueous solution of inorganic salts) and it is injected through a fine die into a receiving chamber or drying oven where, after evaporation of the solvent, the polymer forms a solid fibre.
- In all cases, the fibres thus obtained are washed and drawn until the desired fibre diameter is obtained. Drawing also makes it possible to align the molecular species, which will subsequently facilitate, during the carbonization, a correct formation of the carbon-carbon bonds and will provide the fibre with great solidity.
- Before the actual carbonization, the fibres need to be modified chemically slightly in order to convert their atomic arrangement to a more crosslinked structure. This operation known as a stabilization or partial oxidation operation constitutes step (e) of the method according to the invention.
- This operation is carried out by heating the PAN fibres at 200-300° C. for a few tens of minutes in the presence of air. In this manner, the fibre modifies its atomic arrangement and polar surface functions are created; it changes from a plastic state to a thermally stable infusible state. Since this reaction is exothermic, it is advisable to ensure that the heat transfers are controlled since thermal runaway could occur.
- After the stabilization operation the actual carbonization, which constitutes step (f) of the method according to the invention, is carried out by heating the fibres from step (e) at a temperature between 1200 and 1500° C. in a furnace purged with an inert gas and maintained at a pressure above atmospheric pressure in order to prevent air from re-entering the furnace.
- During the carbonization, most of the atoms, apart from the carbon, are expelled in the form of water vapour for oxygen and hydrogen, ammonia and hydrogen cyanide for nitrogen atoms, gaseous nitrogen, carbon monoxide and carbon dioxide originating from the polar surface functions. The expulsion of these atoms allows the carbon to be organized in microcrystalline form by creating strong bonds. The carbonization may optionally be carried out in two steps, at two different temperatures, for a better control of the entire process. The first carbonization step may thus be carried out at 400-800° C., the fibre optionally being stretched during this step.
- At the end of this carbonization step, fibres known as “high strength” or “intermediate modulus” fibres are obtained, depending on the treatment temperature. A subsequent graphitization step between 2000 and 3000° C. optionally makes it possible to obtain fibres known as “high modulus” fibres.
- After the carbonization/graphitization, other steps may be carried out, with a view to improving the contact of the fibre with the matrix into which it will be incorporated. It is thus possible to slightly oxidize its surface, either by treatment in the presence of air or carbon dioxide, or by treatment in the liquid phase with sodium hypochlorite, nitric acid or a solution of sulphuric acid, of sodium hydroxide and of ammonium bicarbonate, for example. All these operations must be well controlled to avoid the creation of surface defects which could cause defective adhesions to the matrices.
- The fibres may also be subjected to a sizing or oiling treatment that aims to protect them during the transport, weaving or winding thereof. This treatment consists in applying a coating material to the fibres, this coating material being chosen to be compatible with adhesion agents used in the manufacture of the composites and which may, for example, be selected from epoxide resins, polyesters or polyurethanes.
- Another subject of the present invention is the carbon fibres capable of being obtained according to the method described previously.
- These carbon fibres are characterized in that they comprise a not insignificant amount of carbon of renewable or biobased origin or still contemporary origin, that is to say of 14C. Indeed, all carbon samples taken from living organisms, and in particular from the vegetable matter used in the first step of the method according to the invention, are a mixture of three isotopes: 12C, 13C and 14C in a 14C/12C ratio that is kept constant by continuous exchange of carbon with the environment and that is equal to 1.2×10−12. Although 14C is radioactive and although its concentration therefore decreases over time, its half-life is 5730 years, so that the 14C content is considered to be constant from the extraction of the vegetable matter up to the manufacture of the fibres and even up to the end of their use.
- More specifically, it is considered that the carbon fibres according to the invention have an isotopic ratio of their 14C content to their 12C content which is greater than 10−12 but no more than 1.2×10−12, where 14C represents the isotope having 6 protons and 8 neutrons whereas 12C represents the stable isotope having 6 protons and 6 neutrons. A carbon fibre containing 100% of renewable carbon contains at the most 1.2×10−12 of 14C.
- The 14C content of the carbon fibres may be measured according to well-known techniques for dating archaeological remains, old woods, bones, peat or even seashells. It may, for example, be measured according to the following techniques:
-
- by liquid scintillation spectrometry: this method consists in counting “beta” particles resulting from the disintegration of 14C. The beta radiation resulting from a sample of known mass (known number of carbon atoms) is measured over a certain time. This “radioactivity” is proportional to the number of 14C atoms, that it is thus possible to determine. The 14C present in the sample emits beta radiation, which, in contact with the scintillation liquid (scintillator) gives rise to photons. These photons have different energies (between 0 and 156 keV) and form what is known as a 14C spectrum. According to two variants of this method, the analysis focuses either on the CO2 previously produced by the carbon-based sample in a suitable absorbent solution, or on benzene after prior conversion of the carbon-based sample to benzene.
- by mass spectrometry: the sample is reduced to graphite or to gaseous CO2, then analysed in a mass spectrometer. This technique uses an accelerator and a mass spectrometer to separate the 14C ions from the 12C ions and therefore to determine the ratio of the two isotopes.
- These methods for measuring the 14C content of materials are described precisely in the ASTM D 6866 standards (especially D6866-06) and in the ASTMD 7026 standards (especially 7026-04). These methods measure the 14C/12C ratio of a sample and compare it to the 14C/12C ratio of a reference sample of 100% renewable origin, to give a relative percentage of carbon of renewable origin in the sample.
- Another subject of the present invention is therefore carbon fibres that have an isotopic ratio of their 14C content to their 12C content which is greater than 2×10−11, for example greater than 5×10−11, and preferable greater than 10−12 and at the most equal to 1.2×10−12.
- The carbon fibres according to the invention can be employed in all the applications where they are customarily used, especially for reinforcing composites, in particular in the manufacture of aircraft or spacecraft parts, sports equipment (tennis rackets and golf clubs) and wind turbines; in the filtration of high-temperature gases; as antistatic agents; as specialty electrodes; or as reinforcement for pressurized gas tanks, especially for storing hydrogen.
- Another subject of the present invention is therefore these uses of the carbon fibres described previously.
Claims (13)
1. Method of manufacturing carbon fibres, comprising:
a) synthesising acrolein from glycerol of vegetable origin;
b) ammoxidizing the acrolein to obtain acrylonitrile;
c) polymerizing the acrylonitrile to a homopolymer or copolymer of acrylonitrile (PAN);
d) converting the PAN to PAN fibres;
e) partially oxidizing the PAN fibres; and
f) carbonizing the partially oxidized PAN fibres.
2. Method according to claim 1 , characterized in that the glycerol used in step (a) is obtained as a by-product of a transesterification of triglycerides of vegetable origin.
3. Method according to claim 2 , characterized in that the glycerol is obtained as a by-product in the manufacture of biodiesel from vegetable oil.
4. Method according to claim 1 , characterized in that the glycerol is dehydrated to acrolein, in step (a), by heating at a temperature ranging from 250 to 400° C.
5. Method according to claim 1 , characterized in that the acrylonitrile is copolymerized, in step (c), with at least one acrylic comonomer selected from the group consisting of methyl acrylate, methyl methacrylate and acrylic acid.
6. Method according to claim 5 , characterized in that the comonomer does not represent more than 10% by weight relative to the total weight of the monomers to be polymerized.
7. Method according to claim 1 , characterized in that, in step (e), is carried out by heating the fibres at 200-300° C. in the presence of air.
8. Method according to claim 1 , characterized in that, in step (f), is carried out by heating the fibres at a temperature between 1200 and 1500° C. in a furnace purged with an inert gas and maintained at a pressure above atmospheric pressure.
9. Carbon fibres obtained following the method according to claim 1 .
10. Carbon fibres having an isotopic ratio of their 14C content to their 12C content which is greater than 5×10−11.
11. (canceled)
12. Method according to claim 1 , characterized in that the glycerol is dehydrated to acrolein, in step (a), by heating at a temperature ranging from 260 to 300° C.
13. Carbon fibres having an isotopic ratio of their 14C content to their 12C co×ntent which is greater than 10−12.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0855703A FR2935148B1 (en) | 2008-08-25 | 2008-08-25 | PROCESS FOR PRODUCING CARBON FIBERS |
FR08.55703 | 2008-08-25 |
Publications (1)
Publication Number | Publication Date |
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US20100047153A1 true US20100047153A1 (en) | 2010-02-25 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US12/546,128 Abandoned US20100047153A1 (en) | 2008-08-25 | 2009-08-24 | Method of manufacturing carbon fibres |
Country Status (11)
Country | Link |
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US (1) | US20100047153A1 (en) |
EP (1) | EP2159309B1 (en) |
JP (1) | JP2012500910A (en) |
KR (1) | KR20110044922A (en) |
CN (1) | CN102131969A (en) |
AT (1) | ATE512239T1 (en) |
BR (1) | BRPI0916918A2 (en) |
ES (1) | ES2367095T3 (en) |
FR (1) | FR2935148B1 (en) |
PL (1) | PL2159309T3 (en) |
WO (1) | WO2010023403A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US20130273381A1 (en) * | 2008-11-27 | 2013-10-17 | Kolja Kuse | Co2 emission-free construction material made of co2 |
WO2015142929A1 (en) * | 2013-03-15 | 2015-09-24 | Advanced Green Technologies, Llc | Carbon-based manufacturing of fiber and graphene materials |
WO2018095559A1 (en) * | 2016-11-01 | 2018-05-31 | Kolja Kuse | Carbon fibers which can be produced regeneratively or part-regeneratively from co2 using combined production methods |
RU2776076C2 (en) * | 2016-11-01 | 2022-07-13 | Коля КУЗЕ | Carbon fibers produced of renewable or partially renewable carbon dioxide sources using combined production methods |
US11535957B2 (en) * | 2016-11-23 | 2022-12-27 | Lg Chem, Ltd. | Method for producing polyacrylonitrile-based fiber and polyacrylonitrile-based copolymer used therein |
WO2023143856A3 (en) * | 2022-01-29 | 2024-05-16 | Kolja Kuse | Construction materials made of carbon fibres produced from co2 |
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FR2950333B1 (en) | 2009-09-23 | 2011-11-04 | Arkema France | METHOD FOR FUNCTIONALIZING NANOTUBES |
US20110104041A1 (en) * | 2009-10-30 | 2011-05-05 | Goodrich Corporation | Methods and systems for hcn removal |
CN102996257A (en) * | 2011-09-13 | 2013-03-27 | 金涌 | Integral combined cycle power generation system for direct combustion of pulverized coal |
CN113646472B (en) * | 2019-03-29 | 2023-11-28 | 塞特工业公司 | Method for producing homogeneous solutions of polyacrylonitrile-based polymers |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3094552A (en) * | 1959-10-28 | 1963-06-18 | Distillers Co Yeast Ltd | Production of unsaturated aliphatic nitriles |
US3976746A (en) * | 1974-06-06 | 1976-08-24 | Hitco | Graphitic fibers having superior composite properties and methods of making same |
US5804108A (en) * | 1996-10-31 | 1998-09-08 | Wilkinson; Kenneth | Process for the preparation of carbon fiber |
US20040068069A1 (en) * | 2000-04-29 | 2004-04-08 | Atofina, S.A. | Method for making acrylonitrile fibers |
US20080119663A1 (en) * | 2006-11-20 | 2008-05-22 | Evonik Degussa Gmbh | Process for preparing fatty acid alkyl esters and acrolein from triglycerides |
US7396962B1 (en) * | 2005-02-15 | 2008-07-08 | Arkema France | Process for dehydrating glycerol to acrolein |
FR2912742A1 (en) * | 2007-02-16 | 2008-08-22 | Arkema France | Preparation of acrylonitrile, comprises ammoxidation reaction of glycerol in gas phase |
US20080214880A1 (en) * | 2005-02-15 | 2008-09-04 | Arkema France | Process for Dehydrating Glycerol to Acrolein |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1070170B (en) | 1959-12-03 | The Distillers Company Limited, Edinburgh (Großbritannien) | Process for the production of unsaturated nitriles | |
GB709337A (en) | 1950-12-30 | 1954-05-19 | Distillers Co Yeast Ltd | Manufacture of nitriles |
NL123126C (en) | 1963-02-19 | |||
DE3037582A1 (en) * | 1980-10-04 | 1982-05-19 | Verseidag-Industrietextilien Gmbh, 4150 Krefeld | Active carbon fabric - is of fibres which can be converted to active carbon |
JP4360233B2 (en) * | 2004-03-11 | 2009-11-11 | 東レ株式会社 | Golf shaft |
FR2884818B1 (en) * | 2005-04-25 | 2007-07-13 | Arkema Sa | PROCESS FOR THE PREPARATION OF ACRYLIC ACID FROM GLYCEROL |
-
2008
- 2008-08-25 FR FR0855703A patent/FR2935148B1/en not_active Expired - Fee Related
-
2009
- 2009-08-24 BR BRPI0916918A patent/BRPI0916918A2/en not_active IP Right Cessation
- 2009-08-24 WO PCT/FR2009/051622 patent/WO2010023403A1/en active Application Filing
- 2009-08-24 KR KR1020117006781A patent/KR20110044922A/en not_active Application Discontinuation
- 2009-08-24 CN CN200980132923XA patent/CN102131969A/en active Pending
- 2009-08-24 EP EP09168453A patent/EP2159309B1/en active Active
- 2009-08-24 US US12/546,128 patent/US20100047153A1/en not_active Abandoned
- 2009-08-24 AT AT09168453T patent/ATE512239T1/en not_active IP Right Cessation
- 2009-08-24 PL PL09168453T patent/PL2159309T3/en unknown
- 2009-08-24 JP JP2011524435A patent/JP2012500910A/en not_active Withdrawn
- 2009-08-24 ES ES09168453T patent/ES2367095T3/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3094552A (en) * | 1959-10-28 | 1963-06-18 | Distillers Co Yeast Ltd | Production of unsaturated aliphatic nitriles |
US3976746A (en) * | 1974-06-06 | 1976-08-24 | Hitco | Graphitic fibers having superior composite properties and methods of making same |
US5804108A (en) * | 1996-10-31 | 1998-09-08 | Wilkinson; Kenneth | Process for the preparation of carbon fiber |
US20040068069A1 (en) * | 2000-04-29 | 2004-04-08 | Atofina, S.A. | Method for making acrylonitrile fibers |
US7396962B1 (en) * | 2005-02-15 | 2008-07-08 | Arkema France | Process for dehydrating glycerol to acrolein |
US20080214880A1 (en) * | 2005-02-15 | 2008-09-04 | Arkema France | Process for Dehydrating Glycerol to Acrolein |
US20080119663A1 (en) * | 2006-11-20 | 2008-05-22 | Evonik Degussa Gmbh | Process for preparing fatty acid alkyl esters and acrolein from triglycerides |
FR2912742A1 (en) * | 2007-02-16 | 2008-08-22 | Arkema France | Preparation of acrylonitrile, comprises ammoxidation reaction of glycerol in gas phase |
US20100048850A1 (en) * | 2007-02-16 | 2010-02-25 | Arkema France | Method for the synthesis of acrylonitrile from glycerol |
Non-Patent Citations (1)
Title |
---|
Guerrero-Perez et al, "New Reaction: Conversion of Glycerol into Acrylonitrile", ChemSusChem 2008, 7, 577 - 573 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130273381A1 (en) * | 2008-11-27 | 2013-10-17 | Kolja Kuse | Co2 emission-free construction material made of co2 |
US9802862B2 (en) * | 2008-11-27 | 2017-10-31 | Kolja Kuse | CO2 emission-free construction material made of CO2 |
WO2015142929A1 (en) * | 2013-03-15 | 2015-09-24 | Advanced Green Technologies, Llc | Carbon-based manufacturing of fiber and graphene materials |
WO2018095559A1 (en) * | 2016-11-01 | 2018-05-31 | Kolja Kuse | Carbon fibers which can be produced regeneratively or part-regeneratively from co2 using combined production methods |
US20220081806A1 (en) * | 2016-11-01 | 2022-03-17 | Kolja Kuse | Carbon fibers which can be produced regeneratively or part-regeneratively from co2 using combined production methods |
RU2776076C2 (en) * | 2016-11-01 | 2022-07-13 | Коля КУЗЕ | Carbon fibers produced of renewable or partially renewable carbon dioxide sources using combined production methods |
US11898275B2 (en) * | 2016-11-01 | 2024-02-13 | Kolja Kuse | Carbon fibers which can be produced regeneratively or part-regeneratively from CO2 using combined production methods |
US11535957B2 (en) * | 2016-11-23 | 2022-12-27 | Lg Chem, Ltd. | Method for producing polyacrylonitrile-based fiber and polyacrylonitrile-based copolymer used therein |
WO2023143856A3 (en) * | 2022-01-29 | 2024-05-16 | Kolja Kuse | Construction materials made of carbon fibres produced from co2 |
Also Published As
Publication number | Publication date |
---|---|
KR20110044922A (en) | 2011-05-02 |
ES2367095T3 (en) | 2011-10-28 |
CN102131969A (en) | 2011-07-20 |
WO2010023403A1 (en) | 2010-03-04 |
FR2935148B1 (en) | 2010-08-27 |
EP2159309A1 (en) | 2010-03-03 |
BRPI0916918A2 (en) | 2015-11-24 |
JP2012500910A (en) | 2012-01-12 |
EP2159309B1 (en) | 2011-06-08 |
PL2159309T3 (en) | 2011-10-31 |
ATE512239T1 (en) | 2011-06-15 |
FR2935148A1 (en) | 2010-02-26 |
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