TWI573905B - 製造碳奈米纖維及／或碳奈米管的方法 - Google Patents
製造碳奈米纖維及／或碳奈米管的方法 Download PDFInfo
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- TWI573905B TWI573905B TW099105582A TW99105582A TWI573905B TW I573905 B TWI573905 B TW I573905B TW 099105582 A TW099105582 A TW 099105582A TW 99105582 A TW99105582 A TW 99105582A TW I573905 B TWI573905 B TW I573905B
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- Prior art keywords
- carbon
- catalyst
- reaction
- compound
- pyrolysis
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052799 carbon Inorganic materials 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 23
- 239000002041 carbon nanotube Substances 0.000 title claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 46
- 239000002134 carbon nanofiber Substances 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 235000000346 sugar Nutrition 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 10
- -1 carbon compound Compounds Chemical class 0.000 claims description 10
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 8
- 235000010980 cellulose Nutrition 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 235000014633 carbohydrates Nutrition 0.000 claims description 6
- 150000001720 carbohydrates Chemical class 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 150000001722 carbon compounds Chemical class 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- SXPYJBMMMDEFGO-UHFFFAOYSA-N 2-hydroxy-3h-furan-2-carbaldehyde Chemical compound O=CC1(O)CC=CO1 SXPYJBMMMDEFGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000001785 cerium compounds Chemical class 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 2
- 229910052703 rhodium Inorganic materials 0.000 claims 2
- 239000010948 rhodium Substances 0.000 claims 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 2
- 229920001897 terpolymer Polymers 0.000 claims 2
- GPBBNPPLBQIADY-UHFFFAOYSA-N 4,4-dimethyloxane Chemical compound CC1(C)CCOCC1 GPBBNPPLBQIADY-UHFFFAOYSA-N 0.000 claims 1
- 239000012773 agricultural material Substances 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 239000005078 molybdenum compound Substances 0.000 claims 1
- 150000002752 molybdenum compounds Chemical class 0.000 claims 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 1
- 239000002121 nanofiber Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- YFKIWUQBRSMPMZ-UHFFFAOYSA-N methane;nickel Chemical compound C.[Ni] YFKIWUQBRSMPMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- 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
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Textile Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Inorganic Fibers (AREA)
Description
本發明係針對製造碳奈米纖維及/或碳奈米管的方法。
碳奈米纖維(CNF)、碳奈米管(CNT)及含彼之複合材料(在下文中共同稱為CNF)，由於其高強度，化學純度及化學惰性，該特徵使其理想地適合用作催化劑載體，在最近幾年受到愈來愈多注意。
CNF材料的適切性藉由其在各種催化方法諸如費雪-闕布希法(Fischer-Tropsch)與選擇氫化中作為載體之應用被展望。碳(石墨，活性碳)受載催化劑的催化性能可藉由改變載體的特徵而調整，像是含氧表面基團的量，載體的可達性及碳的級數。載體的類似影響存在於金屬/CNF催化劑的性能上。
對良好的催化劑載體材料而言，許多重要先決條件必須被滿足，諸如高體密度、高強度及高孔隙度。高載體密度使得更有效率地使用反應器容積並因此經濟上有利地高於低密度載體。在另一方面，為了避免質量輸送限制，孔隙度亦即可達性是很重要的。
CNF的性質有潛力超越習知的含氧化物載體的性質，尤其像是氧化矽與氧化鋁。碳奈米纖維是化學惰性的，純的及機械上強的並因此適合作為催化載體材料。CNF-主體由纏結的個別碳奈米纖維組成，其係在催化生長期間經由在以金屬為主之生長催化劑上，諸如以鎳、鈷、鐵、釕、其組合及/或合金及其類似物之催化劑上，將含有碳之氣體分解而形成，含有碳之氣體諸如CO/H2、CH4、C2H4或其他揮發性化合物，諸如甲苯及其類似物。適合的載體為氧化矽、氧化鋁、氧化鎂、碳、碳纖維及其類似物。
CNF的二種最常見的形式為魚骨形與平行形(亦稱為多壁碳奈米管)。在魚骨形纖維中，石墨平面係呈一角度朝向中心軸，因此使石墨暴露在邊緣位。如果石墨平面係平行朝向中心軸，像是在CNF的平行形中，則僅有基部的石墨平面被暴露。
從碳奈米纖維或奈米管製造該催化劑載體已被提出。在WO 93/24214中，提出使用碳奈米纖維或奈米管作為催化劑載體，其中石墨層基本上平行朝向纖絲軸。使用該相對長與直的碳纖絲作為具有可控制大小的主體是困難的。確實，對催化劑而言，大小與孔隙度具有很大的重要性。在固定催化劑床中，載體主體的大小決定了通過催化劑主體之壓力下降與反應物和反應產物的傳輸。在懸浮有催化劑之液體的情況下，反應物和反應產物的傳輸具有很大的重要性。催化劑主體的大小係已如上所述對傳輸以及對於主體的分離(例如藉由離心過濾)具有很大的重要性。
另一個缺點為以下事實，碳奈米纖維或奈米管必須從施加在諸如二氧化矽或氧化鋁之載體上之金屬粒子生長。這些載體經常會妨礙在液相反應中所獲得的碳載體的應用。分別藉由以鹼或酸處理將氧化矽或氧化鋁移除是很困難的。
在WO 2005/103348中，已提出製造具有非常高密度、具有至少800 kg/m3體密度之CNF材料。這是藉由以下而達成，藉由將碳水化合物分解，將碳奈米纖維於載在碳纖維上製造之金屬催化劑表面上生長，金屬催化劑諸如鎳、鈷、鐵和釕催化劑，經一段充足的時間以製造所需的體密度，視需要接著將生長催化劑移除。
這些CNF材料直到現在並非非常成功，主要因為製造具有對於作為催化劑載體材料或作為催化劑之應用而言足夠強度之成形主體是很困難的。
因此本發明的第一個目標為提供CNF/CNT材料，其可適當地加工成適合用於催化應用的形式。進一步的目標為從相對大量出現之天然材料製造這些材料，在某些情況下甚至不需要碳化合物(經常來自非可再生能源)之外部供應。
本發明因此關於製造碳奈米纖維及/或碳奈米管之方法，該方法包含在實質上不含氧、含有揮發性矽化合物之氛圍下，視需要在碳化合物的存在下，將分別經能夠形成碳化物之一或多種元素的化合物、金屬或合金含浸的微粒狀纖維素及/或碳水化合物基質熱解。
已驚訝地發現以此方法獲得CNF材料之非常令人感興趣及適合的形式，如同在實施例中所提及之EM照片中所見。
該方法包含以金屬化合物或金屬化合物之組合將基質含浸，接著將經含浸之基質熱解。金屬化合物較佳地為這些金屬化合物的鹽類及更尤其在水溶液中。該元素(金屬)具有能夠形成碳化物的性質。適合元素的例子為鎳、鈷、鐵、鉬。較佳為鐵及鎳。
進一步驚訝地發現從可選擇的含有纖維素及/或碳水化合物之材料，諸如大豆粉、糖、羥基乙基纖維素、纖維素及其衍生物與類似物，也提供當熱分解時機械上強的碳球之球可被製造。考慮到大豆粉相對於非常純之微晶纖維素便宜得多這一事實，這是一個重要優勢。這些碳球形成CNF材料的核心，其在這個過程中，在球的表面上生長。
另一種適合用於碳球之製造的起始材料為糖或糖與微晶纖維素的混合物或大豆粉。根據較佳的步驟，我們從藉由農業製造材料的水熱處理製造的碳質主體開始，農業製造材料諸如糖、澱粉、大豆粉，(半)纖維素，以及上述化合物之脫水產物，諸如，糠醛與2-羥基糠醛。較佳地，上述化合物的脫水係如Bo Hu、Shu-Hong Yu、Kan Wang、Lei Liu及Xue-Wei Xu Dalton Trans. 2008,5414-5423中所述執行且參考其中所述。在將經水熱處理之主體含浸後，執行根據本發明步驟之熱處理。或者，金屬化合物的溶液亦可混合在用在水熱處理中的水中。在主要或完全包含糖之球的熱分解期間，應當注意，在加熱期間，在糖融化的溫度如此快速地通過而使得糖將在融化過程開展之前分解。在將溫度提高到分解溫度之前糖的脫水也已被發現是有效的。鑑於糖與其他含有纖維素之材料的低價格，本發明對於具有機械上強的碳粒子的技術應用具有很大的重要性。
一般而言，纖維素或碳水化合物起始材料將包含有機材料，一般為可再生能源，其具有在惰性條件下熱解時獲得具有還原性質之氣體的性質。
驚訝地發現碳奈米纖維及/或奈米管可藉由在惰性靜止氛圍下，在含有揮發性矽化合物的存在下，較佳地不存在外部碳原子供應氣體，將含有經鐵及/或鎳化合物含浸之纖維素及/或碳水化合物的球加熱而生長。當纖維素熱解時釋放的氣體會形成用於碳奈米管之生長的碳供應源。
因為CNF由碳組成，為了合成這些材料需要含碳氣體。在較佳的具體實例中，該氣體係藉由將碳球熱解而產生，但在可選的具體實例中，額外的氣體可從外部來源供應。
在CNF之製造中的另外的含碳氣體可為任何適合的含碳氣體，諸如在先前技藝中已使用過的。例子為CO、CO/H2混合物、CH4、C2H4及其他氣體，例如低烷類、醇類、烯類、炔類、芳族化合物，例如苯與甲苯，及其類似物。較佳係使用甲烷、甲苯或CO/H2。甲醇可被用來代替高毒性之CO。氣體視需要可以諸如氮氣之惰性氣體稀釋。
熱解發生於適合製造CNF的反應器中，例如流體床反應器、固定床反應器，上升管反應器。反應器中之溫度係維持在適合熱解與製造纖維之程度。溫度視催化劑之本性與含碳氣體之本性而定。溫度的下限一般為400℃。對諸如甲烷與CO/H2之氣體而言，溫度一般在400℃與925℃之間。溫度上限一般為1250℃。
在CNF-複合物已被製造之後，其可如此用於各種應用，諸如聚合物添加劑、儲氫、微電子、同相催化劑或酶之固定，更尤其作為催化劑載體。當沒有分開的受載催化劑被使用時，與先前技藝之方法相反，不需要移除(一般為含氧化物的)載體。根據本發明，鐵或鎳化合物之載體材料亦被熱解及轉化成碳。
在CNF被製造之後，進一步將其改質是可能的，例如甚至進一步將金屬移除，及/或將含氧基引入到CNF表面上製造經氧化之CNF。這些處理一般包括使用HCl及/或H2SO4/HNO3(以不同比例)或以根據技術現況之氣態氧化物氧化。
本發明亦關於CNF材料作為催化劑或催化劑載體之用途。該複合物可如此被用於由碳催化之反應，視需要已藉由氧化接受表面改質。然而，將適合的催化活性材料施加在CNF的表面上係較佳的。適合的催化活性材料可為金屬或氧化基之金屬，諸如鎳、銅、鎢、鐵、錳、鋅、釩、鉻、鉬、銠、銥、釕及其類似物與其組合。亦可能使用CNF作為貴重金屬催化劑之載體，貴重金屬催化劑例如以鉑、鈀、金或銀及其組合為主者。亦有可能將有機金屬或金屬-膦催化劑固定在CNF的表面上。
當製備以CNF作為載體之催化劑時，較佳使用經氧化之CNF，因為其改良了在CNF上之活性前驅物的分散性，因此提高了最終催化劑抗燒結的穩定度，更尤其是鎳催化劑的穩定度。
催化材料可以習知方式施加到CNF-載體，諸如初濕法或同相沉積沉澱。對金屬而言，較佳使用同相沉積沉澱，諸如在藉由同相沉積沉澱在碳奈米纖維上高負載高分散鎳之合成(Synthesis of highly loaded highly dispersed nickel on carbon nanofibers by homogeneous deposition-precipitation)Bitter,J.H.,M.K. van der Lee,A.G.T. Slotboom,A.J. van Dillen及K.P. de Jong,Cat. Lett. 89(2003) 139-142中所述。
其中載在CNF上之催化劑可被使用之在液相與氣相皆適合的反應為費雪-闕布希法、氫化反應、脫氫反應、加氫-處理，諸如加氫-脫硫、甲烷化反應、低溫氧化反應及其類似反應。
實施例1
MCC球係以檸檬酸鐵銨於水中之溶液濕含浸。接著，使MCC球在真空下乾燥。將經含浸之MCC球在矽氧橡膠黏合劑層的幫助下施加到鐵網上。鐵網因此塗覆有稀矽氧橡膠溶液。在矽氧橡膠固化之前，經含浸之MCC球係黏著到矽氧橡膠黏合劑層。接著，具有含浸球的網被帶進惰性靜止的氮氣氛圍並加熱到高達800℃。這使得短直碳奈米管的密實層在碳球表面上生長。在圖1中展示所產生材料的EM照片。圖2給出圖1的放大圖。
實施例2
MCC球係以硝酸鎳於水中之溶液濕含浸。接著，使MCC球在真空下乾燥。經鎳含浸之球係在流化床在惰性氮氣氛圍(流)下加熱到高達800℃。具有小元素鎳粒子之熱解碳球係冷卻低至500℃。接著，氣體組成係變成90體積%的N2與10體積%的H2。將甲苯在飽和器的幫助下計量供給二小時。這使得具有魚骨結構的碳奈米纖維在碳球表面上生長。在圖3中展示所產生材料的EM照片。圖4給出圖3的放大圖。
圖1係顯示實施例1所產生材料的EM照片。
圖2係顯示圖1的放大圖。
圖3係顯示實施例2所產生材料的EM照片。
圖4係顯示圖3的放大圖。
Claims (22)
- 一種製造碳奈米纖維及/或碳奈米管的方法，該方法包含在實質上不含氧、含有揮發性矽化合物之氛圍下，視需要在碳化合物的存在下，將分別經能夠形成碳化物之一或多種元素的化合物、金屬或合金含浸的微粒狀纖維素及/或碳水化合物基質熱解。
- 根據申請專利範圍第1項之方法，其中該基質係選自微晶纖維素、糖或糖與微晶纖維素的混合物或大豆粉。
- 根據申請專利範圍第1或2項之方法，其中基質包含藉由農業材料的水熱處理而製造的碳質主體，農業材料諸如糖、澱粉、大豆粉，(半)纖維素，以及上述化合物之脫水產物，諸如，糠醛與2-羥基糠醛。
- 根據申請專利範圍第1或2項之方法，其中基質係以鎳、鈷、鐵及/或鉬化合物含浸，接著乾燥及熱解。
- 根據申請專利範圍第4項之方法，其中基質係以鎳及/或鐵鹽水溶液含浸，接著乾燥及熱解。
- 根據申請專利範圍第1或2項之方法，其中該基質係在矽橡膠化合物的存在下熱解。
- 根據申請專利範圍第1或2項之方法，其中該矽化合物為烷基矽氧烷。
- 根據申請專利範圍第7項之方法，其中該矽化合物為氣態的矽氧烷三聚物。
- 根據申請專利範圍第7項之方法，其中該矽氧烷化合物為二甲基矽氧烷的三聚物。
- 根據申請專利範圍第1或2項之方法，其中熱解係在介於500與1000℃之間的溫度下。
- 根據申請專利範圍第10項之方法，其中熱解係在介於500與1000℃之間的溫度下經介於5分鐘與5小時之間的時間。
- 根據申請專利範圍第1或2項之方法，其中該氛圍實質上不含碳化合物。
- 根據申請專利範圍第1或2項之方法，其中該氛圍進一步含有至少一種碳化合物，諸如選自甲苯、CO、CO/H2混合物、CH4、C2H4及其他氣體，例如低烷類、烯類、醇類、炔類、芳族化合物，例如苯與甲苯，及其類似物。
- 一種以碳奈米管及/或奈米纖維提供之碳粒子，其可藉由申請專利範圍第1-13項中任一項之方法獲得。
- 一種催化劑，其包含載體材料與至少一種催化活性材料或其前驅物，該載體材料為根據申請專利範圍第14項之以碳奈米管及/或奈米纖維提供之碳粒子。
- 根據申請專利範圍第15項之催化劑，該催化活性材料已被選自貴金屬、銠、鎳、鐵、銅或其組合之群。
- 一種催化劑前驅物，其包含載體材料與至少一種催化活性材料或其前驅物，該載體材料為根據申請專利範圍第14項之以碳奈米管及/或奈米纖維提供之碳粒子。
- 根據申請專利範圍第17項之催化劑前驅物，該催化活性材料已被選自貴金屬、銠、鎳、鐵、銅或其組合之群。
- 一種在受載催化劑的存在下執行至少一種化學反應 之方法，該受載催化劑包含根據申請專利範圍第15或16項任一項之催化劑。
- 根據申請專利範圍第19項之方法，其中化學反應係選自費雪-闕布希(Fischer-Tropsch)反應、氫化反應、脫氫反應、甲烷化反應、低溫氧化反應之群。
- 一種在受載催化劑的存在下執行至少一種化學反應之方法，該受載催化劑包含根據申請專利範圍第17或18項任一項之催化劑前驅物。
- 根據申請專利範圍第21項之方法，其中化學反應係選自費雪-闕布希(Fischer-Tropsch)反應、氫化反應、脫氫反應、甲烷化反應、低溫氧化反應之群。
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| RU (1) | RU2538584C2 (zh) |
| TW (1) | TWI573905B (zh) |
| WO (1) | WO2010098669A1 (zh) |
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| TWI794050B (zh) * | 2022-03-14 | 2023-02-21 | 英業達股份有限公司 | 電子裝置的組裝方法 |
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| US8729117B2 (en) | 2004-06-02 | 2014-05-20 | Pharmacyclics, Inc. | Factor VIIa inhibitor |
| US10793515B2 (en) | 2008-03-19 | 2020-10-06 | Aurimmed Pharma, Inc. | Compounds advantageous in the treatment of central nervous system diseases and disorders |
| US9206143B2 (en) | 2008-03-19 | 2015-12-08 | Aurimmed Pharma, Inc. | Compounds advantageous in the treatment of central nervous system diseases and disorders |
| US9212155B2 (en) | 2008-03-19 | 2015-12-15 | Aurimmed Pharma, Inc. | Compounds advantageous in the treatment of central nervous system diseases and disorders |
| CN103889895B (zh) | 2011-10-12 | 2016-07-13 | 旭化成株式会社 | 碳纳米纤维聚集体、热塑性树脂组合物和热塑性树脂组合物的制造方法 |
| RU2490378C1 (ru) * | 2012-03-23 | 2013-08-20 | Общество с ограниченной ответственностью Научно-производственный центр "УВИКОМ" (ООО НПЦ "УВИКОМ") | Способ получения углеродного волокнистого материала |
| EP2932513B1 (en) | 2012-12-13 | 2020-04-22 | BASF Corporation | Ferromagnetic carbon bodies |
| WO2015011760A1 (ja) * | 2013-07-22 | 2015-01-29 | 村田機械株式会社 | 糸製造装置 |
| WO2017084542A1 (zh) * | 2015-11-20 | 2017-05-26 | 济南圣泉集团股份有限公司 | 一种功能性再生纤维素纤维及其制备方法和应用 |
| EP3648970A4 (en) * | 2017-08-08 | 2021-03-31 | Lintec Of America, Inc. | CHANGING THE DENSITY OF A NANOFIBER SHEET USING A TRIMMED SURFACE |
| SG11202002828YA (en) * | 2017-09-27 | 2020-04-29 | Agency Science Tech & Res | Processes for production of carbon nanotubes from natural rubber |
| CN114229833B (zh) * | 2020-09-09 | 2023-04-07 | 哈尔滨金纳科技有限公司 | 一种易分散、高导电碳纳米管材料的制备方法 |
| CN112604680A (zh) * | 2020-12-14 | 2021-04-06 | 陕西科技大学 | 一种甲醛分解材料及其制备方法和应用 |
| CN113332984B (zh) * | 2021-05-20 | 2023-02-28 | 济南大学 | 一种聚合反应制备钴碳催化剂的制备方法及其应用 |
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- 2010-03-01 US US13/203,581 patent/US20120157298A1/en not_active Abandoned
- 2010-03-01 RU RU2011139333/05A patent/RU2538584C2/ru active
- 2010-03-01 BR BR122019000151-0A patent/BR122019000151B1/pt active IP Right Grant
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- 2010-03-01 KR KR1020117022647A patent/KR101747977B1/ko active IP Right Grant
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| TWI794050B (zh) * | 2022-03-14 | 2023-02-21 | 英業達股份有限公司 | 電子裝置的組裝方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2753794C (en) | 2017-04-18 |
| BRPI1011517B1 (pt) | 2019-09-10 |
| RU2538584C2 (ru) | 2015-01-10 |
| EP2401426B1 (en) | 2014-07-23 |
| KR20110122862A (ko) | 2011-11-11 |
| WO2010098669A1 (en) | 2010-09-02 |
| EP2224045A1 (en) | 2010-09-01 |
| JP2012519241A (ja) | 2012-08-23 |
| CN102333911B (zh) | 2014-07-02 |
| KR101747977B1 (ko) | 2017-06-27 |
| AR075706A1 (es) | 2011-04-20 |
| JP5572642B2 (ja) | 2014-08-13 |
| CN102333911A (zh) | 2012-01-25 |
| TW201038784A (en) | 2010-11-01 |
| BRPI1011517A2 (pt) | 2016-03-29 |
| DK2401426T3 (da) | 2014-10-06 |
| BR122019000151B1 (pt) | 2020-01-07 |
| RU2011139333A (ru) | 2013-04-10 |
| EP2401426A1 (en) | 2012-01-04 |
| US20120157298A1 (en) | 2012-06-21 |
| MX2011009035A (es) | 2011-09-15 |
| PL2401426T3 (pl) | 2015-01-30 |
| EP2754740B1 (en) | 2015-10-21 |
| EP2754740A1 (en) | 2014-07-16 |
| ES2509221T3 (es) | 2014-10-17 |
| CA2753794A1 (en) | 2010-09-02 |
| HRP20140941T1 (en) | 2015-01-30 |
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