EP2619251A1 - Lignine thermoplastique pour la fabrication de fibres de carbone - Google Patents
Lignine thermoplastique pour la fabrication de fibres de carboneInfo
- Publication number
- EP2619251A1 EP2619251A1 EP11752554.3A EP11752554A EP2619251A1 EP 2619251 A1 EP2619251 A1 EP 2619251A1 EP 11752554 A EP11752554 A EP 11752554A EP 2619251 A1 EP2619251 A1 EP 2619251A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lignin
- fiber
- fusible
- range
- precursor fiber
- 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.)
- Withdrawn
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 203
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 29
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 29
- 229920001169 thermoplastic Polymers 0.000 title claims description 11
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 11
- 239000000835 fiber Substances 0.000 claims abstract description 82
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000009826 distribution Methods 0.000 claims abstract description 28
- 230000009477 glass transition Effects 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 8
- 238000007707 calorimetry Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 74
- 230000008569 process Effects 0.000 claims description 57
- 238000003763 carbonization Methods 0.000 claims description 13
- 230000006641 stabilisation Effects 0.000 claims description 12
- 238000011105 stabilization Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000003039 volatile agent Substances 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 238000009987 spinning Methods 0.000 description 32
- 238000012360 testing method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 239000011122 softwood Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000000470 constituent Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000029087 digestion Effects 0.000 description 9
- 239000011121 hardwood Substances 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 6
- 241000018646 Pinus brutia Species 0.000 description 6
- 235000011613 Pinus brutia Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007857 degradation product Substances 0.000 description 6
- 238000005194 fractionation Methods 0.000 description 6
- 239000012978 lignocellulosic material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 244000166124 Eucalyptus globulus Species 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241001070947 Fagus Species 0.000 description 3
- 235000010099 Fagus sylvatica Nutrition 0.000 description 3
- 241000218652 Larix Species 0.000 description 3
- 235000005590 Larix decidua Nutrition 0.000 description 3
- 238000001212 derivatisation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 241000218657 Picea Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- -1 hydrogen sulfide ions Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical group COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000726818 Carpinus caroliniana Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 241001104043 Syringa Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 1
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940119526 coniferyl alcohol Drugs 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- D01F9/17—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 from lignin
Definitions
- the invention relates to a thermoplastic, fusible lignin, which is suitable for the production of carbon fibers.
- Lignin is the second most popular polymer in the group of renewable raw materials after cellulose. Lignin accumulates in large quantities in the paper and pulp industry. Lignin is a by-product of processes that industrially isolate cellulose from lignocellulosic materials.
- the lignins which occur in nature and are chemically bound to cellulose, are usually referred to as "proto-lignins". These proto-lignins are complex substances with a nonuniform polymer structure consisting of repeating basic building blocks such as cumaryl, sinapyl and coniferyl alcohol.
- softwood such as pine, larch, spruce, pine, etc.
- hardwoods such as willow, poplar Lime, beech, oak, ash, eucalyptus, etc.
- annual plants such as straw or bagasse in question.
- the cellulose fibers can be isolated.
- the dissolved lignin remains in solution.
- sulfate process also known as Kraft process.
- the lignin degradation takes place by hydrogen sulfide ions (HS " ) in a basic medium at about pH 13 through the use of sodium sulfide (Na 2 S) and sodium hydroxide (NaOH) or sodium hydroxide solution
- the waste liquor of this process also known as black liquor, contains about 45% of its solid substance when using softwoods and about 38% of hardwood or lignin with hardwoods.
- LignoBoost One way of recovering lignin from the black liquor of the Kraft process is the so-called LignoBoost technology, in which lignin is recovered by precipitation and filtration from the black liquor. In this process, the pH is lowered to precipitate the lignin by injecting CO2.
- LignoBoost so-called LignoBoost technology
- lignocellulosic materials after pretreatment with eg Na 2 S0 3 , NaHC0 3 and Na 2 C0 3 at high temperatures in the range of 170 to 250 ° C and below Pressure is hydrolytically split with superheated steam for a relatively short time, followed by an explosive one
- Another alternative is the cellulose digestion in the sulfite process, in which the lignin degradation is carried out by a sulfonation.
- lignosulfonic acid As a chemically not exactly defined reaction product of lignin with sulfurous acid is formed lignosulfonic acid. Calcium salts of lignosulfonic acid are formed by digesting the wood with calcium hydrogensulfite solutions.
- the waste liquor contains in its solid substance in the use of coniferous wood about 55% and at
- Hardwoods about 42% in the form of lignosulfonic acid. As mentioned, this leaching process does not produce lignin but lignosulfonic acid or its salt.
- the processes required to recover and isolate the lignin, depending on the digestion process, such as e.g. an acidic precipitate from the black liquor has an influence on the properties of the lignin obtained, e.g. on the purity, the structural uniformity, the molecular weight or the molecular weight distribution.
- lignins obtained after digestion have a pronounced heterogeneity with respect to their structure.
- Lignin as a byproduct of cellulose production has had limited commercial benefits so far and is mostly disposed of as waste or incinerated for energy.
- Various attempts are made to produce usable products from lignin For example, US 3 519 describes 581 the preparation of synthetic lignin polyisocyanate resins by reaction of alkali lignins with organic polyisocyanates.
- US 3,905,926 discloses lignin derivatives containing polymerizable oxirane groups. The lignin derivatives disclosed in this document can be polymerized and used for various industrial applications.
- DE 100 57 910 A1 describes a
- the derivatization is carried out by reacting the technical lignin with a spacer having at least one functional, nucleophilic group.
- the refined lignin obtained in this way can be obtained, for example, by injection molding or
- lignin u.a. for the production of fibers and in particular of carbon fibers.
- US Pat. No. 5,344,921 describes a process for producing a modified lignin which can be spun into carbon fibers.
- the modified lignin is obtained by reacting lignin with a phenol to give a phenolated lignin.
- the phenolated lignin is further heated under a non-oxidizing atmosphere, whereby polycondensation of the phenolated lignin occurs, resulting in an increase in the viscosity of the lignin solution, and a lignin suitable for spinning is obtained.
- Lignin derivatives in which the free hydroxyl groups of the starting lignin are derivatized with monovalent and divalent radicals.
- the thus derivatized lignin can be spun into fibers which are prepared by conventional methods in
- non-thermoplastic stabilized fibers and in a further step to
- US Pat. No. 3,461,082 discloses a process for producing carbon fibers in which a lignin fiber is spun by dry or wet spinning from a solution of alkali lignin, thiolignin or lignin sulphonate with the addition of relatively large amounts of polyvinyl alcohol, polyacrylonitrile or viscose and subsequently to a sufficiently high level Temperature is heated above 400 ° C, so that a graphitization of lignin fiber occurs.
- DE 2,118,488 also discloses a process for producing lignin fibers and carbon fibers obtainable therefrom by carbonization and optionally graphitization, in which the lignin fibers are spun from solutions.
- the spinning solutions are aqueous solutions of lignosulphonic acid or its salts, which in addition to the
- Ligninkomponente in proportions to 2 wt .-% contains high molecular weight components, namely polyethylene glycol or acrylic acid acrylamide with a
- US 2008/0317661 A1 relates to a process for the production of
- lignin acetate is extruded into a lignin fiber and the resulting fiber is subsequently thermally stabilized.
- the thermally stabilized softwood lignin acetate fiber is then subjected to carbonization.
- Production of carbon fibers from lignin is based on chemically modified or derivatized lignins and / or use lignin solutions or solutions of lignin derivatives for the production of fibers. If one
- Fiber production based on lignin raw materials from the melt is the addition of significant amounts of additives or solvent components required so as to obtain a mixture which is melt-processable and thread-forming via a melt.
- the known methods are complicated in terms of process control.
- the known methods are complicated in terms of process control.
- Derivatizations and / or the additives adversely affect the stabilization of the spun fibers based on lignin raw materials and the subsequent carbonization to carbon fibers.
- Carbon fibers are suitable.
- the present invention therefore relates to a fusible lignin, which
- a glass transition temperature in the range between 90 and 160 ° C determined by dynamic difference calorimetry (DSC) according to DIN 53765-1994,
- lignin from hardwoods such as B. beech, oak, ash or eucalyptus or conifers, such as pine, larch spruce, etc. (Softwood lignin) are used.
- the lignins can be different
- the lignins can be obtained via sulfate processes, also known as kraft processes, also in combination with the LignoBoost process, the soda AQ, the Organosolv process or the steam explosion process.
- sulfate processes also known as kraft processes
- LignoBoost process the soda AQ
- Organosolv process the Organosolv process
- steam explosion process not as a lignin in the
- lignin sulfonates are to be understood, as obtained, for example, in sulfite processes.
- lignin and partly relatively volatile degradation products of lignin such as Cumaryl, coniferyl and Sinapinalkohol, their derivatives, such as the syringa or guaiacyl aldehyde, syringol, guaiacol; short chain condensation products, such as esters, ethers or hemiacetals, and degradation products of the lignocellulosic material, such as
- lignin in the context of the present invention is understood to mean a lignin which is obtained as the product from the abovementioned digestion processes. This lignin is also called free lignin.
- lignin does not include lignin salts, e.g. Lignosulfonates, as obtained in sulfite processes.
- lignin in the sense of the present invention does not include lignin derivatives in which lignins have been modified by chemical reactions on the lignin, e.g. via acetylation, acylation, esterification, etc., or e.g. by reaction with
- the lignin according to the invention can be prepared from the lignins digested by methods such as Kraft, the soda AQ or the Organosolv method by extraction with suitable solvents or by fractionation by means of a mechanical separation process, which also includes ultrafiltration or
- Nanofiltration membrane processes include, are obtained.
- the solvents to be used in an extraction with solvents depend on the
- composition of the fractions depends on the particular starting lignin, ie, for example, whether it is a hardwood or a coniferous lignin. It is also possible to use suitable fractions of hardwood lignin and
- the fusible lignin according to the invention has a glass transition temperature T G in the range between 90 and 160 ° C. At the same time, they have a molecular weight distribution or molecular weight distribution with a dispersivity of less than 28.
- T G glass transition temperature
- portions of very high molecular weight lignins are disruptive to the spinning process. Thus, in melt spinning processes with increasingly high molecular weight fraction in the lignin spinning fracture is observed, possibly caused by unmelted areas, ie by inhomogeneities in the melt.
- too high a content of low-molecular constituents in the melt may indeed improve the spinnability, but lead to a strong reduction of the glass transition temperature of the lignin and thus to
- the glass transition temperature is in the range between 1 10 and 150 ° C. It is also preferred if the dispersity of the molecular weight distribution is less than 15, and more preferably if it is less than 8.
- the molecular weight distribution is determined in the context of the present invention by means of gel permeation chromatography (GPC) on pullulan standards of sulfonated polystyrene with dimethyl sulfoxide (DMSO) / 0.1 M LiBr as eluent and at a flow rate of 1 ml / min.
- the sample concentration is 2 mg / ml, the injection volume 100 pm.
- the oven temperature is set to 80 ° C, the detection was carried out with UV light of a wavelength of 280 nm.
- Molar mass distribution are determined by conventional methods, the number average M N and the weight average M w of the molecular weight distribution. The dispersivity then results as the ratio of the weight average M w to the number average M N , M W / M N.
- the molecular weight distribution is preferably monomodal.
- the lignin of the present invention it has been found that it may be unfavorable with respect to the spinnability of the lignin when the lignin is e.g. is composed of two fractions with widely different average molecular weight and narrow molecular weight distribution. Here it can happen that the fractions at different temperatures
- the lignin of the invention should therefore preferably to a
- the molecular weight distribution of the lignin according to the invention is monomodal. Particularly preferred is a monomodal molecular weight distribution, which also has no shoulder.
- Ingredients which include, for example, hemicelluloses, short-chain
- the lignin according to the invention therefore has a proportion of volatile constituents, determined on the basis of
- thermal aftertreatment the lignin is exposed to a temperature of 180 ° C under vacuum for 2 h.
- separation processes may also be carried out by ultrafiltration or nanofiltration membranes, e.g. in the form of ceramic membranes.
- the lignin according to the invention therefore has an ash content, determined in accordance with DIN EN ISO 3451 -1, of less than 1% by weight.
- an ash content of less than 0.2 wt .-% and particularly preferably less than 0, 1 wt .-%.
- the adjustment of the required ash content can be achieved, for example, by washing the lignin with acids such as hydrochloric acid and then with deionized water. Alternatively, a cleaning, for example by means of ion exchange is possible.
- the lignin of the invention is fusible and has thermoplastic
- a molded article comprising the lignin of the present invention is also part of the present invention.
- Such shaped bodies can be made from the lignin according to the invention
- Processing methods such as e.g. Kneading, extruding, melt spinning or injection molding at temperatures ranging from 30 ° C to 250 ° C and may be of any shape, e.g. the shape of films, membranes, fibers, etc .. In the range of higher processing temperatures of preferably about 150 ° C to 250 ° C, the processing of the
- Lignins according to the invention are carried out to the molding under an inert gas atmosphere.
- the fiber of the invention is a multifilament yarn.
- this fiber is a precursor fiber for carbon fibers, i. to a fiber, which as
- Such a carbon fiber precursor fiber is produced according to one aspect of the present invention by a process comprising the following steps:
- the lignin fiber is one consisting of a multiplicity of filaments
- Multifilament yarn in which the diameter of the filaments is in the range of 5 to 100 ⁇ m, and more preferably in the range of 10 to 60 ⁇ m.
- the lignin fiber is subjected to drawing after exiting the spinneret.
- the invention further relates to a method for producing a
- Carbon fiber comprising the steps of:
- Precursorfasern for carbon fibers is generally the conversion of the fibers via chemical stabilization reactions, in particular cyclization and dehydrogenation reactions of a
- thermoplastic state in an oxidized, infusible and flame-resistant state is understood thermoplastic state in an oxidized, infusible and flame-resistant state.
- the stabilization is carried out today usually in conventional convection ovens at temperatures between 150 and 400 ° C, preferably between 180 and 300 ° C, in a suitable process gas (see, for example, F. Fourne: "Synthetic fibers", Carl Hanser Verlag Kunststoff Vienna 1995, Chapter 5.7).
- a stepwise reaction takes place via an exothermic reaction
- Inertgasatmospreheat preferably under nitrogen.
- the carbonation can be carried out in one or more stages.
- the stabilized fiber is heated at a heating rate which is in the range of 10 K / s to 1 K / min, preferably in the range of 5 K / s to 1 K / min.
- the carbonation takes place at a temperature between 400 and 2000 ° C
- the carbonization end temperature is up to 1800 ° C.
- the carbonization process step converts the stabilized precursor fiber of the invention into a carbonized fiber of the invention, i. into a fiber whose fiber-forming material
- the carbonized fiber according to the invention can be further refined in the process step of graphitization.
- the graphitization can be carried out in one stage, wherein the carbonized fiber according to the invention in an atmosphere consisting of a monatomic inert gas, preferably of argon, at a heating rate in the range of preferably 5 K / s to 1 K / min to a temperature of for example heated up to 3000 ° C.
- the process step of graphitization converts the carbonized fiber of the present invention into a graphitized fiber of the present invention.
- Carrying out the graphitization while stretching the carbonized fiber according to the invention leads to a significant increase in the modulus of elasticity of the resulting graphitized fiber according to the invention. Therefore, the graphitization of the carbonized fiber of the present invention is preferably carried out while simultaneously stretching the fiber.
- Hardwood lignin (eucalyptus) used.
- the lignin had one
- the lignin was examined for its spinnability by means of a standard spinning test machine (type LME, SDL Atlas). Although the lignin could be melted at temperatures above 170 ° C, it could not be spun into fibers.
- the starting lignin was heated under vacuum of less than 100 mbar for 2 hours at 180 ° C.
- the post-treated lignin had a glass transition temperature T G of 130 ° C, an average molecular weight M w of 3070 g / mol, a molecular weight distribution with a dispersivity of 10.8 and an ash content of 0.33 wt .-%.
- the proportion of volatile constituents of the aftertreated lignin was below 1% by weight.
- the lignin was examined for its spinnability by means of a standard spinning test machine (LME type, SDL Atlas), with a rotor temperature of 185 ° C. and a spinning head temperature of 200 ° C. being set on the spinning test machine. The spinning speed was 1 14 m / min. From the aftertreated lignin were so monofilaments with a
- This beechwood lignin was subjected to a spinning test. No monofilaments could be produced, a stable spinning process was not achieved.
- the lignin of Comparative Example 2 was subjected to purification and fractionation, ie, separation of high molecular weight components.
- the lignin was dissolved in a solvent in the ratio 1:10 over 30 min with constant stirring.
- the solvent used was a 20:80 propanol / dichloromethane mixture.
- the solution was filtered under vacuum through a filter (S & S type 595, 4-7 pm, Schleicher s Schull) to separate insoluble matter. Subsequently, the solvent was removed via a rotary evaporator.
- the thus purified and fractionated lignin was then subjected to a thermal aftertreatment under vacuum of less than 100 mbar and with heating for 2 hours at 180 ° C.
- the thermally treated lignin had a glass transition temperature T G of 142 ° C, an average molecular weight M w of 9970 g / mol and a dispersity of the molecular weight distribution of 27.5.
- the proportion of volatile constituents was 0.58 wt .-%, the ash content was below 0.2 wt .-%.
- the thus prepared lignin was spun by means of a standard spinning test machine (type LME, SDL Atlas) to monofilaments usable as precursor fibers with a filament diameter of 87 pm.
- a rotor temperature 180 ° C and a.
- the purified and fractionated lignin had a glass transition temperature T G of 132 ° C, an average molecular weight M w of 1902 g / mol, a
- the purified lignin was used to remove volatiles
- thermal aftertreatment under vacuum of less than 100 mbar and under heating for 2 hrs.
- T G glass transition temperature
- dispersivity of the molecular weight distribution of 2.3
- a volatile content 0.71 wt .-%.
- the ash content was also below 0.2% by weight.
- the lignin prepared in this way could be used as a precursor fiber by means of a standard spinning test machine (type LME, SDL Atlas)
- a rotor temperature of 185 ° C. and a spinning head temperature of 195 ° C. were set on the spinning test machine.
- the lignin taken from the LignoBoost process had a glass transition temperature T G of 173 ° C, an average molecular weight M w of 7170 g / mol and a molecular weight distribution with a dispersivity of 17.6.
- the content of volatile constituents was above 2.0% by weight.
- the starting material was first subjected to purification and fractionation, proceeding as in Example 3.
- the purified lignin was also subjected to a thermal aftertreatment under vacuum of less than 100 mbar and with heating for 2 hours at 180 ° C. to remove volatile constituents.
- the thus treated lignin had a glass transition temperature T G of 1 18 ° C, a dispersivity of
- the starting material was first subjected to purification and fractionation as described in Example 2, with methanol being used as solvent unlike Example 2.
- the thus prepared lignin was
- the lignin had a glass transition temperature T G of 145 ° C, a dispersivity of the molecular weight distribution of 10.3 and a volatiles content of less than 0.3 wt .-%.
- the ash content was below 0.7% by weight.
- the lignin could easily be spun into monofilaments in a spinning test.
- a rotor temperature 180 ° C and a Spinner head temperature of 210 ° C and a spinning speed of 1 14 m / min set.
- the thermally treated lignin had a glass transition temperature T G of 132 ° C, an average molecular weight M w of 6640 g / mol and a dispersity of the molecular weight distribution of 18.7.
- the proportion of volatile constituents was 0.75 wt .-%, the ash content was below 0.05 wt .-%.
- the spinning test produced monofilaments with filament diameters in the range of 21-43 ⁇ m.
- the spinning test machine was set at a rotor temperature of 180 ° C., a spinning head temperature of 195 ° C. and a spinning speed of 91 m / min.
- the softwood lignin had a dispersivity of 2.61, an ash content of 4.08 wt%, and a volatiles content of 2.5 wt%. This softwood lignin could not be spun into threads in the spinning test machine.
- a lignin obtained from annual plants was obtained, which was obtained by a soda process.
- the lignin from annual plants had a glass transition temperature T G of 155 ° C, an average molecular weight M w of 2435 g / mol, a dispersivity of 2.35, an ash content of 1.29 wt .-% and a volatile content of 2 , 6 wt .-%.
- Example 2 The monofilament obtained in Example 2 was used under
- the monofilaments obtained were subjected to a thermal treatment under an air atmosphere in an oven without tension, the oven temperature being raised from 25 ° C to 170 ° C at 2 ° C / min and from 170 ° C to 250 ° C at 0.2 ° C / min. After reaching 250 ° C oven temperature, the monofilament was further treated for 4 hrs at 250 ° C.
- Example 8a the
- Example 8b Monofilament for 4 hours at 250 ° C further treated.
- the oven temperature was increased from 25 ° C to 170 ° C at 2 ° C / min and then from 170 ° C to 300 ° C at 0.2 ° C / min. After reaching 300 ° C oven temperature, the monofilament was further treated for 2 hours at 300 ° C.
- Precursorfaser had a density of 1.409 g / cm 3 , a tensile strength of
- Precursor fiber had a density of 1.559 g / cm 3 , a tensile strength of
- Example 9a Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Example 8a Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Example 8a Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Example 9b Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Precursor fiber had a density of 1.414 g / cm 3 , a tensile strength of 1 18.6 MPa and an elongation of 6.9%.
- Precursorfaser had a density of 1, 531 g / cm 3 , a tensile strength of
- Example 10a Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Example 8a Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Example 8a Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Example 8b Air exposure of an oxidation treatment for producing a stabilized Precursor Anlagen subjected.
- Example 8b Air exposure of an oxidation treatment for producing a stabilized Precursortura subjected.
- Example 8a and Example 10b were also set in Example 8b
- Precursor fiber had a density of 1, 425 g / cm 3 , a tensile strength of 129 MPa and an elongation of 4.8%.
- the stabilized precursor fiber resulting from the application of the process conditions according to example 10b had a density of 1.448 g / cm 3 , a tensile strength of 213 MPa and an elongation of 5.0%.
- a stabilized precursor fiber produced according to Example 8b was used.
- a section of the stabilized precursor fiber was in a
- Carbonizing furnace fixed at its ends and held under a tension of 0.5 cN.
- the carbonization furnace with the fiber section was first purged with nitrogen for 1 h. After rinsing, the carbonator was heated from 25 ° C to 800 ° C at 3 ° C / min. This was the stabilized
- Precursor fiber carbonized under a nitrogen atmosphere.
- the carbon fiber had a tensile strength of 599 MPa and an elongation at break of 1.1%.
- a stabilized precursor fiber produced according to Example 10b was used.
- the carbonization of the stabilized precursor fiber was carried out as in Example 1 1.
- the result was a carbon fiber with a density of 1, 502 g / cm 3 , with a tensile strength of 331 MPa and obtained with an elongation at break of 0.7%.
- the carbon content in the fiber was well above 70% by weight.
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Abstract
L'invention concerne une lignine fusible, qui présente une température de transition vitreuse calculée par calorimétrie à balayage différentiel (DSC) dans la plage comprise entre 90 et 160 °C, une distribution des masses molaires calculée par chromatographie par perméation de gel (GPC) avec une dispersivité inférieure à 28, une teneur en cendres inférieure à 1 % en poids et une proportion de constituants volatils d'au plus 1 % en poids. L'invention concerne également une fibre de précurseur à base de la lignine fusible selon l'invention et son procédé de fabrication. L'invention concerne enfin également un procédé de fabrication d'une fibre de carbone à partir de la fibre de précurseur selon l'invention.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP11752554.3A EP2619251A1 (fr) | 2010-09-23 | 2011-09-08 | Lignine thermoplastique pour la fabrication de fibres de carbone |
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Application Number | Priority Date | Filing Date | Title |
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EP10178760 | 2010-09-23 | ||
PCT/EP2011/065513 WO2012038259A1 (fr) | 2010-09-23 | 2011-09-08 | Lignine thermoplastique pour la fabrication de fibres de carbone |
EP11752554.3A EP2619251A1 (fr) | 2010-09-23 | 2011-09-08 | Lignine thermoplastique pour la fabrication de fibres de carbone |
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EP2619251A1 true EP2619251A1 (fr) | 2013-07-31 |
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EP11752554.3A Withdrawn EP2619251A1 (fr) | 2010-09-23 | 2011-09-08 | Lignine thermoplastique pour la fabrication de fibres de carbone |
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US (1) | US20130183227A1 (fr) |
EP (1) | EP2619251A1 (fr) |
JP (1) | JP2013542276A (fr) |
KR (1) | KR20130117776A (fr) |
CN (1) | CN103140539A (fr) |
AR (1) | AR083086A1 (fr) |
AU (1) | AU2011304512A1 (fr) |
BR (1) | BR112013006492A2 (fr) |
CA (1) | CA2812685A1 (fr) |
TW (1) | TW201219457A (fr) |
WO (1) | WO2012038259A1 (fr) |
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IL206678A0 (en) | 2010-06-28 | 2010-12-30 | Hcl Cleantech Ltd | A method for the production of fermentable sugars |
RU2591939C2 (ru) | 2011-02-14 | 2016-07-20 | Иннвентиа Аб | Способ изготовления лигнинового волокна |
US9512495B2 (en) | 2011-04-07 | 2016-12-06 | Virdia, Inc. | Lignocellulose conversion processes and products |
TWI589741B (zh) * | 2012-01-23 | 2017-07-01 | 茵芬提亞公司 | 穩定木質素纖維以進一步轉換成碳纖維之方法 |
WO2013144123A1 (fr) | 2012-03-28 | 2013-10-03 | Toho Tenax Europe Gmbh | Dérivé de lignine fusible et fibre produite à partir de ce dérivé de lignine |
EP2644758B1 (fr) * | 2012-03-29 | 2014-12-10 | Honda R&D Europe (Deutschland) GmbH | Stabilisation de fibres de carbone de lignine avec des agents de réticulation |
US9493851B2 (en) | 2012-05-03 | 2016-11-15 | Virdia, Inc. | Methods for treating lignocellulosic materials |
GB2517338B (en) | 2012-05-03 | 2020-03-25 | Virdia Inc | A method for fractionating a liquid sample |
FI127816B (en) * | 2012-06-06 | 2019-03-15 | Upm Kymmene Corp | Process for fractionating lignin |
KR101336465B1 (ko) | 2012-09-07 | 2013-12-04 | 김동관 | 열가소성 리그닌축중합체 및 이의 제조방법 |
WO2014046826A1 (fr) * | 2012-09-20 | 2014-03-27 | Graftech International Holdings Inc. | Fibres de carbone dérivées de lignine |
SE537712C2 (sv) | 2012-11-13 | 2015-10-06 | Stora Enso Oyj | Termiskt reaktiv termoplastisk mellanprodukt innefattande barrträdslignin samt förfarande för framställning av denna |
EP2920344B1 (fr) * | 2012-11-16 | 2024-01-03 | GrafTech International Holdings Inc. | Fibres de carbone dérivées de résidu de lignine/carbone |
US9657146B2 (en) | 2013-03-14 | 2017-05-23 | Virdia, Inc. | Methods for treating lignocellulosic materials |
US20140271443A1 (en) * | 2013-03-15 | 2014-09-18 | University Of Tennessee Research Foundation | High Glass Transition Lignins and Lignin Derivatives for the Manufacture of Carbon and Graphite Fibers |
JP6114081B2 (ja) * | 2013-03-22 | 2017-04-12 | 横浜ゴム株式会社 | 加硫ブラダー用ゴム組成物およびそれを用いたタイヤ用加硫ブラダー |
CN105377958B (zh) | 2013-05-03 | 2019-01-01 | 威尔迪亚公司 | 用于处理木质纤维素材料的方法 |
WO2014179777A1 (fr) * | 2013-05-03 | 2014-11-06 | Virdia, Inc. | Procédé de préparation de fractions de lignine stable de façon thermique |
DE102014004797A1 (de) | 2013-05-24 | 2014-11-27 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Precursor-Fasern von Lignin-basierten Carbonfasern, deren Herstellung und Verwendung |
CN105121386B (zh) | 2013-09-05 | 2018-06-01 | 格拉弗技术国际控股有限公司 | 从木质素/炭渣得到的碳产物 |
FI126737B (en) | 2013-11-26 | 2017-04-28 | Upm Kymmene Corp | Process for treating lignin and preparing a binder composition |
EP3166954B1 (fr) | 2014-07-09 | 2019-03-27 | Virdia, Inc. | Procédés de séparation et de raffinage de la lignine provenant de liqueur noire et compositions associées |
CN104085890B (zh) * | 2014-07-15 | 2016-05-11 | 李文军 | 玉米秸秆碳纤维生产方法 |
CN104695059A (zh) * | 2015-02-03 | 2015-06-10 | 北京林业大学 | 一种具有大比表面积的木质素基活性碳纤维的制备方法 |
CN109518308B (zh) * | 2018-11-29 | 2021-02-19 | 青岛大学 | 一种木质素的扩链改性及其熔纺纤维的制备方法 |
CN115595691B (zh) * | 2022-11-08 | 2024-04-19 | 哈尔滨体育学院 | 一种具有优异电化学性能的木质纤维素基碳纤维及其制备方法与应用 |
CN117482947B (zh) * | 2023-12-29 | 2024-04-09 | 中国林业科学研究院林产化学工业研究所 | 一种负载单原子金属木质素基碳材料的制备方法及其应用 |
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- 2011-09-08 KR KR1020137010274A patent/KR20130117776A/ko not_active Application Discontinuation
- 2011-09-08 US US13/823,987 patent/US20130183227A1/en not_active Abandoned
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- 2011-09-08 AU AU2011304512A patent/AU2011304512A1/en not_active Abandoned
- 2011-09-08 BR BR112013006492A patent/BR112013006492A2/pt not_active IP Right Cessation
- 2011-09-08 CN CN201180045695XA patent/CN103140539A/zh active Pending
- 2011-09-08 JP JP2013529607A patent/JP2013542276A/ja not_active Withdrawn
- 2011-09-08 EP EP11752554.3A patent/EP2619251A1/fr not_active Withdrawn
- 2011-09-08 WO PCT/EP2011/065513 patent/WO2012038259A1/fr active Application Filing
- 2011-09-16 TW TW100133316A patent/TW201219457A/zh unknown
- 2011-09-22 AR ARP110103464A patent/AR083086A1/es unknown
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CA2812685A1 (fr) | 2012-03-29 |
BR112013006492A2 (pt) | 2016-07-26 |
AU2011304512A1 (en) | 2013-04-11 |
WO2012038259A1 (fr) | 2012-03-29 |
AR083086A1 (es) | 2013-01-30 |
KR20130117776A (ko) | 2013-10-28 |
JP2013542276A (ja) | 2013-11-21 |
US20130183227A1 (en) | 2013-07-18 |
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TW201219457A (en) | 2012-05-16 |
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