KR100514186B1 - Hairy nano carbon material - Google Patents
Hairy nano carbon material Download PDFInfo
- Publication number
- KR100514186B1 KR100514186B1 KR10-2003-0016242A KR20030016242A KR100514186B1 KR 100514186 B1 KR100514186 B1 KR 100514186B1 KR 20030016242 A KR20030016242 A KR 20030016242A KR 100514186 B1 KR100514186 B1 KR 100514186B1
- Authority
- KR
- South Korea
- Prior art keywords
- carbon
- surface area
- specific surface
- carbon material
- catalyst
- Prior art date
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 80
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000835 fiber Substances 0.000 claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 239000011148 porous material Substances 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000004438 BET method Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 81
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 75
- 239000003054 catalyst Substances 0.000 claims description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 66
- 239000000758 substrate Substances 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 18
- 239000001307 helium Substances 0.000 claims description 17
- 229910052734 helium Inorganic materials 0.000 claims description 17
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 238000009396 hybridization Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 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 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 9
- 239000003990 capacitor Substances 0.000 abstract description 7
- 239000003463 adsorbent Substances 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 43
- 239000004917 carbon fiber Substances 0.000 description 16
- 239000002041 carbon nanotube Substances 0.000 description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 description 14
- 238000002309 gasification Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000002134 carbon nanofiber Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- ICXADQHBWHLSCI-UHFFFAOYSA-N dubinine Natural products C1=CC=C2C(OC)=C(CC(O3)C(C)(O)COC(C)=O)C3=NC2=C1 ICXADQHBWHLSCI-UHFFFAOYSA-N 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 210000003746 feather Anatomy 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002109 single walled nanotube Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 steam Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MAJZZCVHPGUSPM-UHFFFAOYSA-N nitric acid nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.O[N+]([O-])=O MAJZZCVHPGUSPM-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 230000007704 transition 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
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 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
-
- 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
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/68—Crystals with laminate structure, e.g. "superlattices"
Abstract
본 발명은 탄소원소를 85 중량 % 이상 함유하고, 섬유경이 1000 - 50000nm의 섬유상 탄소재료 내지는 입경이 500 - 50000 nm 이상인 입상탄소재이며, 질소비이티법 (N2 BET Method)법으로 측정한 비표면적이 0.2 - 3000 m2/g인 탄소재의 표면내지는 세공의 내부에, 탄소원소의 함유율이 95중량 % 이상이며, 섬유경이 0.6 - 500 nm, 섬유의 에스펙트비(Aspect ratio, 섬유장/섬유경)가 5 이상인 섬유상 나노탄소를 성장시켜, 질소비이티법 (N2 BET Method)법으로 측정한 비표면적이 100 - 2000 m2/g인 신규 고비표면적의 탄소재 및 그 제조방법에 관한 것이다. 본 발명의 탄소재는 기상 및 액상 흡착재, 리튬2차전지의 음극재, 전기이중층원리를 이용한 캐파시터의 전극재, 전자파 차폐재 등 다양한 용도에 응용할 수 있다.The present invention is a fibrous carbon material having a carbon element of at least 85% by weight, a fibrous carbon material having a fiber diameter of 1000-50000nm, or a granular carbon material having a particle size of 500-50000nm or more, and the specific surface area measured by the N2 BET method. The surface-to-pores of the carbon material having 0.2 to 3000 m2 / g have a carbon content of 95% by weight or more, a fiber diameter of 0.6 to 500 nm, and an aspect ratio of the fiber (fiber length / fiber diameter). The present invention relates to a new high specific surface carbon material having a specific surface area of 100 to 2000 m 2 / g, and to a method for producing the same, wherein fibrous nanocarbon having 5 or more is grown and measured by the N2 BET Method. The carbon material of the present invention can be applied to various applications such as gaseous and liquid adsorbents, negative electrode materials for lithium secondary batteries, electrode materials for capacitors using electric double layer principles, and electromagnetic shielding materials.
Description
본 발명은 대기 중의SOx, NOx, 오존 및 다이옥신 수질 중의 중금속 및 클로로 화합물의 흡착재, 연료전지용 촉매의 담체, 유기 단위반응의 촉매의 담체, 메탄 및 수소의 가스 저장재 및 분리재, 리튬 2차 전지의 전극재 및 도전재, 고용량 전기 2중층 캐파시터의 전극재 및 전기탈염용 전극재 등으로 사용되어질 수 있는, 탄소의 육각망면 및 그 적층구조로 이루어진 것을 특징으로 하는 섬유상 내지는 입상탄소에 있어, (1) 탄소원자 85% 이상으로 구성된 물질로서 탄소원자의 sp2하이브리드(Hybridization) 결합으로 형성된 탄소육각망면(Carbon hexagonal plane)의 적층상으로 형성된 흑연과 유사한 구조를 지니면서 엑스선회절법으로 측정한 탄소육각망면간의 거리가 0.3360 나노미터 에서 0.3900나노미터를 지니며 (2) 섬유상의 경우 섬유경이 1000 - 50000nm이며 입상의 경우 입경이500 - 500000nm, (3) 질소비이티법 (N2 BET Method)법으로 측정한 비표면적이 0.2 - 3000 m2/g인 탄소재를 기질로 사용하여, 기질의 탄소재의 표면 또는 기질의 탄소재가 함유하고 있는 기공의 내부에 (1) 탄소원소의 함유율이 95중량 % 이상이며, (2) 섬유경이 0.6 - 500 nm, (3) 섬유의 에스펙트비(Aspect ratio, 섬유장/섬유경)가 5 이상인 섬유상 나노탄소를 성장시켜, 최종적으로 얻어진 고비표면적 탄소재의 질소비이티법 (N2 BET Method)법으로 측정한 비표면적이 100 - 2000 m2/g인 신규 고비표면적의 탄소재 및 그 제조방법에 관한 것이다.The present invention provides an adsorbent of heavy metals and chloro compounds in SOx, NOx, ozone and dioxin water in the atmosphere, a carrier of a catalyst for fuel cells, a carrier of a catalyst for organic unit reactions, a gas storage and separator of methane and hydrogen, a lithium secondary battery In the fibrous or granular carbon comprising a hexagonal mesh surface of carbon and a laminated structure thereof, which can be used as an electrode material and a conductive material, an electrode material of a high-capacity electric double layer capacitor, an electrode material for electric desalination, and the like, (1) Carbon hexagons measured by X-ray diffraction analysis, having a structure similar to graphite formed by lamination of carbon hexagonal planes formed by sp2 hybridization of carbon atoms, consisting of 85% or more carbon atoms. The distance between the mesh planes is 0.3360 nanometers to 0.3900 nanometers. (2) The fiber diameter is 1000-50000 nm for the fibrous shape, 500-500000nm, (3) Carbonaceous material with a specific surface area of 0.2-3000 m2 / g, measured by the N2 BET Method, is used as the substrate. Inside the pores, (1) the carbon content is 95% by weight or more, (2) the fiber diameter is 0.6-500 nm, and (3) the aspect ratio (fiber length / fiber diameter) of the fiber New high specific surface area carbon material having a specific surface area of 100-2000 m2 / g measured by the N2 BET method of a fibrous nanocarbon having a growth rate of 5 or more and finally obtained by a N2 BET method and a method for producing the same. It is about.
배경기술Background
고비표면적을 함유하는 활성탄 및 활성탄소섬유를 제조하는 방법 및 나노 및 수십나노의 섬유경을 지닌 섬유상 나노탄소 (Fibrous nano-carbon), 탄소 나노파이버(Carbon nanofiber or Graphite nanofiber) 탄소나노튜브(섬유경이 80 nm이하의 중공형 극세 탄소섬유)를 금속촉매를 이용하여 제조하는 방법에 관하여는 다수의 특허와 논문에 공지되어 있다. 활성탄 및 활성 탄소섬유는 일반적으로 탄소계 물질을 사용하여 이를 수증기, 공기, 이산화탄소 등의 분위기에서 300 - 1100도 사이의 온도에서 일정시간 열처리하여 제조하는 방법과 수산화칼륨, 수산화나트륨 등의 알칼리금속을 함유하는 염에 상기의 탄소계 물질을 300 -1100도 사이의 온도에서 일정시간 열처리한 후 이를 분리 세정 및 건조하여 제조하는 방법이 공지되어있다. 섬유상 나노탄소의 제조법도 촉매금속 위에 탄소원이 되는 일산화탄소 및 탄화수소가스를 열분해함으로써 제조하는 방법이 알려져 있다. 구체적인 예를 들면, 미국의 엑손엔드리서치회사는 일산화탄소 및 탄화수소류를 철산화물 또는 철 또는 니켈 등의 촉매를 사용하여 540도 내지 800도의 온도에서 열분해처리함으로써 생성된 섬유의 길이가1미크로미터 이상의 섬유상 탄소를 얻는 법을 발표하였다; 미국특허4,565,683) 또한 미국의 하이페리온 캐탈리틱 인터네셔널 회사(Hyperion Catalytic International Inc. ) 는 자사의 특허에서(예를 들면 일본 公開特許公報62-5000943) 다층 탄소나노튜브 즉 튜블라 구조의 카본 나노파이버에 관하여 섬유축 방향으로 평행으로 배향하며 섬유의 내부에 튜브의 구조(튜브의 직경 5나노미터)를 지닌 탄소망면의 층면이 8 에서 15층 정도로 이루어진 섬유경 3.5 에서 80 나노미터를 지니는 탄소육각망면이 동심원상으로 섬유의 축에 배열하고 있는 중공형의 튜블라 구조의 섬유상 나노탄소(탄소나노튜브)를 발표한 바 있다. 또한 미국의 베이커 및 로드리게즈 등은 철, 니켈, 코발트 등의 촉매를 주로 사용하여 500도에서 700도 사이의 온도에서 탄화수소를 열분해하여 표면적이 50 - 800 ㎡/g의 탄소나노파이버 및 그 제조법을 공표한 바 있다. 독일의 봄 교수 및 일본의 무라야마씨 그리고 미국의 로드리게즈 씨 등도 철, 코발트, 니켈의 천이금속 내지는 그 합금촉매를 사용하여 이를 열분해함으로써 섬유상의 나노탄소 및 탄소나노파이버의 제조에 관하여 발표한 바있다. (Boehm, Carbon, 11, 583 (1973), H.Murayama,T.Maeda, Nature, 245. 791. Rodriguez, N.M. 1993. J. Mater. Res. 8: 3233)).Method for producing activated carbon and activated carbon fibers containing high specific surface area and carbon nanofibers and carbon nanofibers with fiber diameters of nano and tens of nanometers Hollow microfine carbon fibers of 80 nm or less) are known in a number of patents and papers on the production of metal catalysts. Activated carbon and activated carbon fiber are generally manufactured by using carbon-based materials and heat-treating them at a temperature between 300-1100 degrees in an atmosphere such as steam, air, carbon dioxide, and alkali metals such as potassium hydroxide and sodium hydroxide. It is known to produce a salt containing the carbonaceous material by heat treatment at a temperature of between about 300-1100 degrees for a predetermined time, followed by separation, washing and drying. The manufacturing method of fibrous nanocarbon is also known by the pyrolysis of the carbon monoxide and hydrocarbon gas which become a carbon source on a catalyst metal. For example, Exxon Research, Inc., of the United States, is a fibrous product having a length of 1 micrometer or more that is produced by pyrolysing carbon monoxide and hydrocarbons at a temperature of 540 to 800 degrees using a catalyst such as iron oxide or iron or nickel. Announced how to obtain carbon; U.S. Patent 4,565,683) The U.S. Hyperion Catalytic International Inc., in its patent (e.g., Japanese Patent No. 62-5000943) is a multi-layered carbon nanotube, or tubular carbon nanofiber. Carbon hexagon mesh surface having a fiber diameter of 3.5 to 80 nanometers having 8 to 15 layers of carbon mesh layer having a tube structure (5 nanometer diameter) inside the fiber with respect to the fiber axis direction. It has announced a hollow tubular fibrous nanocarbon (carbon nanotube) arranged concentrically on the fiber axis. In addition, US Baker and Rodriguez have published carbon nanofibers with a surface area of 50-800 m2 / g by using pyrolysis of hydrocarbons at temperatures between 500 and 700 degrees, using catalysts such as iron, nickel and cobalt. I've done it. Spring professors in Germany, Murayama in Japan and Rodriguez in the United States also reported on the production of fibrous nanocarbon and carbon nanofibers by pyrolyzing them using transition metals of iron, cobalt and nickel, or their alloys. (Boehm, Carbon, 11, 583 (1973), H. Murayama, T. Maeda, Nature, 245. 791. Rodriguez, NM 1993. J. Mater. Res . 8: 3233).
일본전기(NEC)의 이이지마 씨가 탄소나노튜브 및 그 제조법을 공표한 이래 S.Iijima, Nature, 354, 56 (1991), S. Iijima, ) 탄소나노튜브를 필두로 한, 섬유상 나노탄소 및 탄소나노파이버의 제조 및 응용이 전세계적인 붐을 일으키고 있다.Since Iijima of NEC has published carbon nanotubes and their preparation methods, fibrous nanocarbons, including S.Iijima, Nature, 354, 56 (1991), S. Iijima,) carbon nanotubes, The manufacture and application of carbon nanofibers are creating a worldwide boom.
탄소나노튜브는 그 구조에서 탄소육각망면이 섬유축 방향에 평행으로 배열한 구조로서 내부에 0.4 나노미터 이상의 튜브형태의 공간을 지니고 있는 구조로 되어 있다. 탄소나노튜브는 탄소육각망면이 한장의 단막으로 구성되어 있는 단층탄소나노 튜브(Single wall carbon nanotube; SWNT)와 다층으로 이루어져 있는 다층탄소나노튜브(Multi wall carbon nanotube; MWNT)로 분류되며, 단층 나노튜브는 섬유경이 0.4 - 3.5 나노미터, 다층나노튜브는 섬유경이 2.5 - 50 나노미터 정도를 지니고 있는 것으로 알려져 있다. 현재까지 알려진 주된 탄소나노튜브의 제조법으로는, 단층탄소나노 튜브의 경우 주로 금속촉매를 함유한 탄소봉을 아크시켜 제조하는 카본 아크법(S.Iijima, Nature, 354, 56 (1991), S. Iijima), 최근에 미국의 R.E. Smalley교수의 힙코 프로세스(고압 일산화탄소 공정, Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide, Pavel Nikolaev, Michael J. Bronikowski, R. Kelley Bradley, Frank Rohmund, Daniel T. Colbert, K.A. Smith, Richard E. Smalley, Chemical Physics Letters, 313(1999), 91-97)에 의한 제조방법 및 기타 금속 촉매를 이용하여 메탄을 분해시켜 제조하는 방법 등이 알려져 있다. 또한 다층탄소나노튜브는 상기 이이지마씨와 같이 금속 함유 내지는 미함유의 탄소봉을 이용한 아크법과 주로 철, 코발트, 니켈 등의 천이금속을 촉매로 사용하여 일산화탄소, 아세틸렌, 메탄 등의 가스를 이용하여 열화학증착법(Thermal Chemical Vapor Deposition) 및 촉매열분해법으로 제조하는 것을 특징으로 하고 있다. (예를 들면 H. Zeng등, Carbon, 36, 259-261(1998); 미국 하이페리온 캐탈리틱 인터네셔날사의 WO 09007023 A1 등)Carbon nanotubes have a structure in which carbon hexagonal nets are arranged parallel to the fiber axis in the structure and have a space of 0.4 nanometer or more inside. Carbon nanotubes are classified into single wall carbon nanotubes (SWNTs) in which a carbon hexagonal network is composed of a single layer, and multiwall carbon nanotubes (MWNTs) in multiple layers. It is known that the tube has a fiber diameter of 0.4-3.5 nanometers and the multilayer nanotube has a fiber diameter of 2.5-50 nanometers. The main carbon nanotube production methods known to date include carbon arc methods (S.Iijima, Nature, 354, 56 (1991), S. Iijima, which are produced by arcing carbon rods containing metal catalysts in the case of single-walled carbon nanotubes). ), Recently in the US RE Prof. Smalley's hipco process (high pressure carbon monoxide process, gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide, Pavel Nikolaev, Michael J. Bronikowski, R. Kelley Bradley, Frank Rohmund, Daniel T. Colbert, KA Smith, Richard The production method according to E. Smalley, Chemical Physics Letters, 313 (1999), 91-97), and the method for decomposing methane using other metal catalysts are known. In addition, the multi-layered carbon nanotubes are thermally chemistry using carbon monoxide, acetylene, methane, etc. using the arc method using a metal-containing or non-containing carbon rod like Iijima seed, and a transition metal such as iron, cobalt and nickel as catalysts. It is characterized in that the production by the vapor deposition method (Thermal Chemical Vapor Deposition) and catalytic pyrolysis method. (E.g., H. Zeng et al., Carbon, 36, 259-261 (1998); WO 09007023 A1, etc., of Hyperion Cationic International, USA)
이런 탄소나노튜브에 비하여 섬유상 나노탄소 혹은 탄소나노파이버(Carbon nanofiber, Graphite nanofiber)는 탄소육각망면이 섬유축에 대하여 직각으로 배열하여 있는 구조 (칼럼나구조 혹은 플레이트리트 구조) 및 섬유축에 대하여 20도 이상 80도 미만의 일정한 경사를 지니고 있는 구조 (깃털구조 혹은 헤링본구조, 출처: Rodriguez, N.M. 1993. J. Mater. Res. 8: 3233))를 지니고 있으며, 섬유의 내부에 나노튜브와 같은 튜브의 공간을 나타내지 않는 것을 특징으로 들 수 있다. 섬유상 나노탄소의 제조는 일반적으로 철, 니켈, 코발트 등의 VIB 족의 천이금속을 주촉매로 사용하여 일산화탄소 및 탄화수소류를 촉매열분해 시켜 생성하는 것을 특징으로 하고 있다.Compared to these carbon nanotubes, fibrous nanocarbon or carbon nanofibers (Carbon nanofiber, Graphite nanofiber) have a structure (column structure or platelet structure) in which the carbon hexagonal net surface is arranged at right angles to the fiber axis and the fiber axis 20 It has a structure with a constant inclination above 80 degrees (feather or herringbone structure, source: Rodriguez, NM 1993. J. Mater. Res . 8: 3233) and has a tube like nanotube inside the fiber. It is characterized by not showing the space of. In general, the production of fibrous nanocarbon is characterized in that the carbon monoxide and hydrocarbons are catalytically pyrolyzed using a transition metal of VIB group such as iron, nickel, and cobalt as a main catalyst.
이러한 섬유상의 나노탄소 즉 탄소나노섬유 및 탄소나노튜브는 서브나노 흑은 수십 나노미터의 직경을 가짐을 특징으로 하여 많은 신규의 응용, 예를 들면 투명성을 지닌 전도성 도료 (ITO 대체 도료) 및 복합재료 원료, 전자방출원, 나노소자, 수소 및 메탄 저장재, 바이오, 가스 분리막, 캐파시터 및 리튬이온전지, 전기탈염 등의 전극에의 응용을 기대하고 있다. 그러나, 이런 섬유상 탄소재는 형태적으로 극세의 입자와 유사하므로, 상업적으로 응용하여 사용하기 위해서는 나노사이즈의 탄소재를 효과적으로 지지하여 사용할 필요가 있다. 복합재료 및 전지, 캐파시터 등의 경우는 고분자 및 세라믹 바인더를 효과적으로 혼합하여 원하는 성형체를 만들어 실제 사용에 응용하고 있으나, 가스 흡착제 및 전기탈염의 경우는 고분자를 사용할 경우, 섬유상 나노탄소의 표면이 이용될 확율이 급격히 저하되는 단점을 지니고 있다.These fibrous nanocarbons, i.e. carbon nanofibers and carbon nanotubes, are characterized by subnano blacks having diameters of several tens of nanometers, so that many new applications such as transparent conductive paints (ITO replacement paints) and composite materials It is expected to be applied to electrodes such as raw materials, electron emission sources, nano devices, hydrogen and methane storage materials, bio, gas separators, capacitors and lithium ion batteries, and electrodesalination. However, since the fibrous carbon material is similar in shape to the ultrafine particles, it is necessary to effectively support and use the nano-sized carbon material in order to use it commercially. In the case of composite materials, batteries, and capacitors, polymers and ceramic binders are effectively mixed to form a desired molded body and applied in actual use. However, in the case of gas adsorbent and electrodesalting, polymer surface is used for the surface of fibrous nanocarbon. It has the disadvantage that the probability of falling rapidly decreases.
본 발명은 이런 나노탄소재를 가스 및 액상의 흡착제, 전기탈염의 전극재 등으로 효과적으로 사용할 수 있는 혁신적인 방법으로서, 고분자 등의 바인더를 사용하지 않고 (1) 탄소원자 85% 이상으로 구성된 물질로서 탄소원자의 sp2하이브리드(Hybridization) 결합으로 형성된 탄소육각망면(Carbon hexagonal plane)의 적층상으로 형성된 흑연과 유사한 구조를 지니면서 엑스선회절법으로 측정한 탄소육각망면간의 거리가 0.3360 나노미터 에서 0.3900나노미터를 지니며 (2) 섬유상의 경우 섬유경이 1000 - 50000nm이지 입상의 경우 입경이500 - 500000nm, (3) 질소비이티법 (N2 BET Method)법으로 측정한 비표면적이 0.2 - 3000 m2/s인 탄소재를 기질로 사용하여, 기질의 탄소재의 표면 또는 기질의 탄소재가 함유하고 있는 세공의 내부에 (1) 탄소원소의 함유율이 95중량 % 이상이며, (2) 섬유경이 0.6 - 500 nm, (3) 섬유의 에스펙트비(Aspect ratio, 섬유장/섬유경)가 5 이상인 섬유상 나노탄소를 성장시켜, 최종적으로 얻어진 고비표면적 탄소재의 질소비이티법 (N2 BET Method)법으로 측정한 비표면적이 100 - 2000 m2/g인 신규 고비표면적의 탄소재 및 그 제조방법에 관한 것이다. 제조한 고비표면적 탄소재는 섬유상의 경우 섬유경이1000 - 50000nm이며 입상의 경우 입경이 500 - 500000nm의 탄소재의 표면 및 세공의 내부에 탄소나노섬유를 성장시킨 복합재이므로, 기존의 섬유상 나노탄소 자체에 비교하여 흡착재, 캐파시터, 전기탈염의 전극으로 사용하기 편한 장점을 지니고 있으며, 칼럼에 충전하여 사용할 경우에도 압력저하의 염려없이 흡착재로서의 성능을 충분히 발휘할 수 있다The present invention is an innovative method that can effectively use the nano-carbon material as a gas and liquid adsorbent, electrodesalting electrode material, etc., without using a binder such as a polymer (1) a carbon material as a material consisting of 85% or more carbon atoms It has a structure similar to graphite formed in a stack of carbon hexagonal planes formed by sp2 hybridization of pores, and the distance between carbon hexagonal planes measured by X-ray diffraction method is 0.3360 nanometers to 0.3900 nanometers. (2) a carbonaceous material having a fiber diameter of 1000-50000 nm, a grain size of 500-500000 nm, and (3) a carbon material having a specific surface area of 0.2-3000 m2 / s measured by the N2 BET Method. Is used as a substrate, and the content of carbon elements is 95% by weight or more in the surface of the carbon material of the substrate or in the pores contained in the carbon material of the substrate, and (2) fiber diameter (N2 BET Method) of the high specific surface area carbon material finally obtained by growing fibrous nanocarbon having an aspect ratio (fiber length / fiber diameter) of 0.6 to 500 nm and (3) fibers of 5 or more. The present invention relates to a new high specific surface area carbon material having a specific surface area of 100 to 2000 m 2 / g and a method for producing the same. The high specific surface area carbon material produced is a composite material in which carbon nanofibers are grown on the surface and pores of a carbon material having a fiber diameter of 1000 to 50000 nm and a particle size of 500 to 500000 nm for a granular material, and thus compared with conventional fibrous nanocarbon itself. Therefore, it has the advantage of being easy to use as an adsorbent, capacitor, and electrode for desalination, and even when it is used in a column, it can fully exhibit its performance as an adsorbent without fear of pressure drop.
고비표면적 탄소재의 제조방법Manufacturing method of high specific surface area carbon material
이런 특수한 고표면적 탄소재의 제조는 기존의 방법과는 다른 방법으로 제조된다. 이하 상기의 고표면적 탄소재의 제조방법을 기술한다. 고표면적 탄소재 제조를 위해 비표면적이 100-3000m2/g의 PAN(Polyacrylonitrile)계, 피치계 및 셀룰로즈계 활성 탄소섬유 및 일반의 코코낫셀, 코크스계 등의 활성탄을 기질로 사용한다. 기질의 활성 탄소섬유 및 활성탄은 섭씨 80도에서 섭씨 200도, 바람직하기는 섭씨 85도에서 섭씨 120도에서 80토르 이하, 보다 바람직하기는 40토르 이하의 압력에서 탈기하면서 1시간이상 건조하여 사용한다. 본 발명의 예에서는 비표면적 1014m2/g의 오오사카 가스제의 피치계 활성탄소섬유 OG15A를 기질로 사용하였다.This special high surface area carbon material is manufactured by a method different from the existing method. Hereinafter, the manufacturing method of the said high surface area carbon material is described. In order to manufacture a high surface area carbonaceous material, activated carbon such as polyacrylonitrile (PAN), pitch-based and cellulose-based activated carbon fibers having a specific surface area of 100-3000 m 2 / g, and general coconacell and coke-based materials are used as a substrate. Activated carbon fiber and activated carbon of the substrate is used after drying for at least one hour while degassing at a pressure of 80 to 200 degrees Celsius, preferably 85 to 120 degrees Celsius or less, 80 Torr or less, more preferably 40 Torr or less. . In the example of the present invention, a pitch-based activated carbon fiber OG15A made from Osaka Gas having a specific surface area of 1014 m 2 / g was used as a substrate.
기질의 활성탄소섬유를 2토르이하의 압력으로 탈기하면서 섭씨85도의 온도에서 8시간 건조한다. 탄소나노섬유 제조용 촉매인 니켈과 철이 고용체 및 고용체에 가까운 합금을 유지할 수 있도록 질산니켈, 아세트니켈 등과 질산철, 아세트철 등의 수용액을 일정량씩 제조하여 혼합하여 용액을 만든 후, 기질의 활성탄소에 첨가하여 니켈 및 철의 화합물 용액이 활성탄소섬유에 일정량 흡착되도록 담지를 시킨다. 이 때, 활성탄소 섬유의 양은 니켈 및 철의 화합물이 니켈과 철의 금속만으로 계산할 경우에 니켈 및 철의 합금 또는 니켈의 단일 금속이 0.1 - 60 중량 %, 보다 바람직하기는 1 중량%에서 30 중량%가 바람직하다. 제조한 금속 화합물이 담지된 활성탄소섬유는 산소의 함량이 5 체적%에서 40체적%, 보다 바람직하기는 10체적%에서 30체적% 와 질소, 알곤 또는 헬륨이 혼합된 가스를 사용하여 섭씨 150도 이상 섭씨550도 이하 보다 바람직하기는 섭씨 250도 이상 섭씨 450도 미만의 온도에서 활성탄소섬유의 잔류량이 85중량% 이상이 되도록 산화 가스화 처리하여 니켈 및 철의 산화물이 활성탄소섬유의 세공 및 표면에 균일하게 분산될 수 있도록 산화처리한다. 제조한 금속 산화물 담지 활성탄소섬유는 산화 가스화에 의해 대부분의 금속 산화물이 활성탄소섬유의 세공 및 표면에 균일하게 분산된 형태를 형성하고 있다. 이런 금속 산화물을 금속으로 환원하기 위해 수소가 5 체적%에서 40체적%, 보다 바람직하기는 8체적%에서 25체적%가 함유된 질소, 알곤, 헬륨 등의 가스의 혼합물을 사용하여 섭씨 400도에서 섭씨 800도 보다 바람직하기는 섭씨 450도에서 섭씨 700도의 범위에서 1시간에서 48시간 보다 바람직하기는 1시간 30분에서 24시간 1회에서 3회, 보다 바람직하기는 1회에서 2회 환원하여 니켈과 철의 합금 또는 니켈의 금속입자가 세공 및 표면에 균일하게 분산한 촉매 담지 활성탄소섬유를 제조한다. 제조한 촉매담지 활성탄소섬유는 산화가스화 처리를 하지 않을 경우, 질소 비이티법으로 측정한 비표면적이 50m2/g이하였으나, 산화가스화 처리 후에는 온도 및 시간에 따라 측정치는 다르나, 100 - 2000m2/g의 비표면적을 나타내었다.The activated carbon fibers of the substrate are dried for 8 hours at a temperature of 85 degrees Celsius while degassing at a pressure of 2 torr or less. Nickel and iron, which are catalysts for producing carbon nanofibers, are prepared by mixing a predetermined amount of aqueous solutions such as nickel nitrate and acetnickel with iron nitrate and acet iron to maintain an alloy close to a solid solution and a solid solution. Addition is carried so that a solution of a compound of nickel and iron is adsorbed to a certain amount on the activated carbon fibers. At this time, the amount of activated carbon fiber is 0.1 to 60% by weight, more preferably 1 to 30% by weight of an alloy of nickel and iron or a single metal of nickel when the compound of nickel and iron is calculated only from the metal of nickel and iron. % Is preferred. Activated carbon fiber loaded with the prepared metal compound has an oxygen content of 5 vol% to 40 vol%, more preferably 10 vol% to 30 vol% and 150 ° C using a gas containing nitrogen, argon or helium. More than 550 degrees Celsius or less is more preferred, the oxidation and gasification process of the oxides of nickel and iron to the pore and surface of the activated carbon fibers by the oxidation gasification treatment so that the residual amount of activated carbon fibers at a temperature of 250 degrees Celsius or more and less than 450 degrees Celsius Oxidize to ensure uniform dispersion. The prepared metal oxide-supported activated carbon fibers have a form in which most metal oxides are uniformly dispersed in the pores and surfaces of the activated carbon fibers by oxidizing gasification. To reduce this metal oxide to metal at 400 degrees Celsius using a mixture of gases such as nitrogen, argon, helium, etc. containing 5% to 40% by volume of hydrogen, more preferably 8% to 25% by volume. More preferably 800 degrees Celsius, preferably from 450 to 700 degrees Celsius, from 1 hour to 48 hours, more preferably from 1 hour 30 minutes to 24 hours once to three times, more preferably once to twice A catalyst-supported activated carbon fiber in which alloys of and iron or metal particles of nickel are uniformly dispersed in pores and surfaces is prepared. When the catalyst-supported activated carbon fibers were not subjected to oxidizing gasification, the specific surface area measured by the nitrogen BIT method was 50 m2 / g or less. However, after the oxidizing gasification treatment, the measured values vary depending on the temperature and time, but 100-2000 m2 / The specific surface area of g is shown.
제조한 금속 촉매 담지 활성탄소섬유를 일정량 알루미나 혹은 석영제의 보트 혹은 플레이트 상에 고르게 분산 장착시킨 후, 에칠렌, 아세칠렌, 프로판 등의 탄소수가 2개에서 5개, 보다 바람직하기는 탄소수가 2개에서 4개 함유된 포화 또는 불포화탄화수소와 수소의 혼합가스를 촉매 1밀리 그램 당 0.5 - 30 sccm (분당 도입되는 cc량), 보다 바람직하기는 1 - 10 sccm을 도입하면서 일정시간 열처리를 행하여 극세 섬유상 나노탄소가 표면에 성장한 고표면적 탄소재를 제조한다. 이 때 혼합가스에서 수소의 분압은 0 - 80 체적 %가 바람직하며, 열처리 온도는 섭씨 300도에서 섭씨 800도, 보다 바람직하기는 섭씨 350도에서 섭씨 700도이다. 열처리 시간은 2분에서 12시간 보다, 바람직하기는 20분에서 4시간이 적합하다. 본 발명에서 실시예에서 표시한 바와 같이 촉매 1밀리 그램당 수소분압 25%의 에칠렌 가스를 3.3sccm 도입하여 1시간 열처리를 할 경우, 제조 조건에 따라 다르나, 촉매 중량에 대해 섬유상 나노탄소를 8 배에서 170배의 고수율로 제조하는 것이 가능하였으며, 3시간 반응에서 200배 이상의 수율로 섬유상 나노탄소가 표면에 성장한 고표면적 탄소재를 제조하는 것도 가능하였다.After the metal catalyst-supported activated carbon fibers prepared are dispersed and mounted evenly on a boat or plate made of alumina or quartz, two to five carbon atoms such as ethylene, acetylene and propane, more preferably two carbon atoms The mixed gas of four saturated or unsaturated hydrocarbons and hydrogen contained at 0.5 to 30 sccm per milligram of catalyst (cc amount introduced per minute), more preferably 1 to 10 sccm was subjected to heat treatment for a predetermined period of time to obtain an ultrafine fibrous A high surface area carbon material in which nanocarbon is grown on its surface is produced. At this time, the partial pressure of hydrogen in the mixed gas is preferably 0 to 80% by volume, and the heat treatment temperature is 300 degrees Celsius to 800 degrees Celsius, and more preferably 350 degrees Celsius to 700 degrees Celsius. The heat treatment time is suitable from 2 minutes to 12 hours, preferably 20 minutes to 4 hours. In the present invention, when the heat treatment for 1 hour by introducing 3.3sccm of hydrogen partial pressure 25% ethylene gas per milligram of the catalyst as shown in the embodiment, it depends on the manufacturing conditions, but 8 times the fibrous nanocarbon to the weight of the catalyst It was possible to produce a high yield of 170 times at, and it was also possible to produce a high surface area carbon material in which fibrous nanocarbons were grown on the surface in a yield of 200 times or more in a 3 hour reaction.
본 발명의 활성탄소섬유 상에 성장한 극세 섬유상 나노탄소는, 기존의 섬유상 나노탄소와는 달리 5 - 150 나노미터의 섬유경을 지니고 있으며 섬유경은 제조온도에 의해 크게 변화하였다. 즉, 550도 이상의 고온에서 제조할 경우 활성탄소섬유 상에 성장한 극세 섬유상 나노탄소는 80 - 150 나노미터의 비교적 굵은 섬유경을 지니고 있었으나, 550도 이하 특히 520도 이하의 온도에서 성장한 극세 섬유상 나노탄소 5 - 40 나노미터의 균일한 굵기의 극세 섬유상 나노탄소가 성장한 것을 알 수 있었다. 또한 활성탄소섬유의 표면에 성장한 극세 섬유상 나노탄소는 비교적 잘 발달한 흑연구조를 지니고 있으므로, 불투명성 도전복합재, 불투명성 전자파 차폐재 등의 필러로서 적절한 물질로 사용가능하며, 전기이중층 캐파시터의 전극재료, 연료전지 및 유기반응용의 촉매담체, 나트리움-황, 공기 전지의 전극재, 수질정화 등의 전기탈염전극의 전극재 등에의 응용이 기대된다. 또한 수소 및 메탄의 저장재, 수소와 중수소의 분리제 등으로 사용가능하며, 고표면적을 이용한 DeSOx 및 DeNOx용의 재료로서도 사용이 기대된다.The ultrafine fibrous nanocarbon grown on the activated carbon fiber of the present invention has a fiber diameter of 5 to 150 nanometers, unlike the conventional fibrous nanocarbon, and the fiber diameter is greatly changed by the manufacturing temperature. That is, when manufactured at a high temperature of more than 550 degrees, the ultrafine fibrous nanocarbons grown on the activated carbon fibers had a relatively thick fiber diameter of 80-150 nanometers, but the ultrafine fibrous nanocarbons grown at a temperature of 550 degrees or less, particularly 520 degrees or less. It was found that ultrafine fibrous nanocarbon of uniform thickness of 5-40 nanometers was grown. In addition, since the ultrafine fibrous nanocarbon grown on the surface of activated carbon fiber has a relatively well developed graphite structure, it can be used as a suitable material for fillers such as an opaque conductive composite material and an opaque electromagnetic shielding material, and can be used as an electrode material and fuel of an electric double layer capacitor. Application to catalyst carriers for batteries and organic reactions, natrium-sulfur, electrode materials for air batteries, electrode materials for electrodesalting electrodes such as water purification and the like is expected. In addition, it can be used as a storage material for hydrogen and methane, and a separator for hydrogen and deuterium, and is also expected to be used as a material for DeSOx and DeNOx using a high surface area.
기질인 활성탄소섬유의 세공 내부 또는 표면에 극세나노탄소섬유를 성장시키기 위해 담지하는 촉매는, 철, 니켈, 코발트 등의 천이금속이 단독 내지는 망간, 니켈, 크롬, 몰리브덴, 텅스텐 등의 2차금속(Secondary metal)과의 합금등의 형태로 사용 가능하다.The catalyst supported for growing the ultrafine nanocarbon fibers in or on the surface of the pores of the activated carbon fibers, which are substrates, includes a transition metal such as iron, nickel, and cobalt alone or secondary metals such as manganese, nickel, chromium, molybdenum, and tungsten. It can be used in the form of alloy with (Secondary metal).
니켈을 1차 금속(Common metal) 촉매 단독으로 담지하여 사용할 경우는, 상기한 탄소수 1개 이상의 포화 및 불포화탄화 수소를 반응가스로 사용하며, 철을 1차 금속 촉매로 사용할 경우는 메탄, 일산화탄소, 에칠렌,아세칠렌을 반응가스로, 코발트를 1차 금속 촉매로 사용할 경우는 일산화탄소 및 탄화수소 전체를 반응가스로 사용하는 것이 가능하다.When nickel is used as a primary metal catalyst alone, saturated and unsaturated hydrocarbons having one or more of the above carbon atoms are used as the reaction gas, and when iron is used as the primary metal catalyst, methane, carbon monoxide, When ethylene and acetylene are used as the reaction gas and cobalt is used as the primary metal catalyst, it is possible to use carbon monoxide and the entire hydrocarbon as the reaction gas.
본 발명에서 특징적인 기술은, 기질로 사용한 활성탄소섬유에 1차금속 촉매 내지는 1차 및 2차의 합금촉매의 질화물 등의 화합물을 담지한 후, 이를 일정한 온도에서 산화 가스화 처리하므로써 금속을 산화물로 전이시킴과 동시에 가스화에 의해 기질의 활성탄소섬유의 세공의 체적을 증가시킴으로써 금속의 산화물을 담지한 상태에서 기존의 활성탄소섬유의 비표면적 1014 m2/g보다 월등히 증가한 1620m2/g의 비표면적을 나타냄과 동시에 세공 내부의 금속산화물이 환원과정 및 금속으로 환원한 이후에도 반응가스와 접촉이 원활히 이루어질 수 있도록 평균세공의 크기를 그림5에 나타낸 바와 같이 약8nm의 마이크로세공으로부터 10.5 nm의 마이크로 세공으로 확대하는 것이다.A characteristic technique of the present invention is to support a compound such as a nitride of a primary metal catalyst or a primary and secondary alloy catalyst on an activated carbon fiber used as a substrate, and then convert the metal into an oxide by oxidizing and gasifying at a constant temperature. By increasing the volume of the pores of activated carbon fibers of the substrate by transition and gasification, the specific surface area of 1620m2 / g is significantly increased from 1014 m2 / g of specific activated carbon fibers in the state of supporting metal oxide. At the same time, the average pore size is expanded from about 8 nm micropore to 10.5 nm micropore so that the metal oxide inside the pore can be easily contacted with the reaction gas even after the reduction process and the reduction to the metal. will be.
상기와 같이, 금속촉매의 전구체를 활성탄소섬유에 분산 흡착 시킨 후, 이를 일정한 온도의 산화가스화 처리를 하지 않는 경우 섭씨 550도 이하의 저온에서의 반응가스의 금속과의 확산접촉의 확율이 낮아 극세 나노섬유가 거의 성장하지 않으며, 600도 이상의 반응에서 극세탄소섬유를 표면에 성장 시켜도 생성되어진 탄소재가 45 m2/g의 낮은 비표면적을 나타내는 것이 특징이다.As described above, when the precursor of the metal catalyst is dispersed and adsorbed on the activated carbon fiber, and the oxidation gasification treatment is not performed at a constant temperature, the probability of diffusion contact with the metal of the reaction gas at a low temperature of 550 degrees Celsius or less is extremely low. The nanofibers hardly grow, and the carbon material produced shows a low specific surface area of 45 m2 / g even when the ultrafine carbon fibers are grown on the surface at a reaction temperature of 600 degrees or higher.
표 1에는 실시예 1 및 비교예 1의 기질 활성탄소섬유, 가스화 및 가스화하지 않은 금속전구체 담지 기질 활성 탄소섬유, 극세 섬유상 나노탄소를 성장시킨 후의 비표면적을 질소 비이티법으로 측정하여 나타내었다.In Table 1, the specific surface area after growth of the substrate activated carbon fibers of Example 1 and Comparative Example 1, the substrate precursor carbon fibers supported without gasification and gasification, and the ultrafine fibrous nanocarbon were measured and measured by the nitrogen-Biti method.
이하, 본 발명을 실시예에 의하여 구체적으로 예시하지만 본 발명은 하기의 실시예에 의하여 반드시 제한되지는 않는다. 실시예 및 비교예에서 부 및 %는 특별히 지정하지 않는 경우 모두 중량부 및 중량%를 의미한다.Hereinafter, the present invention is specifically illustrated by Examples, but the present invention is not necessarily limited to the following Examples. In Examples and Comparative Examples, parts and% mean parts by weight and% by weight unless otherwise specified.
실시예 1Example 1
고표면적 탄소재를 제조하기 위하여 다음의 실험을 행하였다.In order to produce a high surface area carbonaceous material, the following experiment was conducted.
오오사카 가스사제 피치계 활성탄소섬유 OG15A(비표면적 1014m2/g)을 2토르이하의 압력으로 탈기하면서85도에서8시간 건조하여 기질의 활성탄소섬유로 사용하였다. 건조한 활성탄소섬유에 철과 니켈(철/니켈 중량비 2/8)의 합금촉매를 활성탄소섬유의 표면에 극세 섬유상 나노탄소 제조용 촉매로 담지하기 위해 일본 와코사제 질산철 (試1級. Iron(III) nitrate nonahydrate Fe(NO3)3·9H2O = 404.00 (99%, Wako), mp 35∼40℃, d 1.684, sol in water, ethanol, acetone)과 일본 와코사제 질산니켈(Nickel (II) nitrate hexahydrate Ni(NO3)2·6H2O = 290.79 (98%, Wako), mp 56.7℃, d 2.05, bp 137, sol in 0.4 part water, in alcohol, Ni content 20.19% (Nickel Ni = 58.71)의 일정량을 증류수에 첨가하여 용해시켜 10 중량 %의 용액을 제조한 후, 상기의 오오사카카스사제 활성탄소섬유 10g을 첨가하여 12시간 교반하여 혼련하였다. 상기의 방법으로 제조한 활성탄소섬유의 질산철 및 질산니켈의 혼합슬러지를 회전식 진공건조기(Rotary Evaporator)를 사용하여 섭씨80도에서 40토르 (Torr)의 조건으로 수분을 건조하여 질산철과 질산니켈이 세공 및 표면에 분산 담지된 활성탄소섬유를 제조하였다. 제조한 질산철과 질산니켈이 분산된 활성탄소섬유를 석영제의 보트 (길이x폭x깊이=10x2.5x1.5 / mm (외부값) ) 에 장착한 후 4.5cm의 내경을 지닌 석영관으로 이루어진 수평로의 중간에 두고 공기를 50sccm흘리면서 섭씨350도에서 0.5시간 산화처리하여 활성탄소섬유의 일부를 가스화하였다. 가스화하여 4중량% 정도 중량감소한 금속 산화물 담지 활성탄소섬유를 로내에 그대로 둔 채 30분간 헬륨 분위기를 유지한 후 수소와 헬륨의 혼합가스 110sccm을 사용하여 (水素분압 :20%) 520도에서 1시간 환원처리를 행하여 철과 니켈의 합금이 세공 및 표면에 고르게 분산 담지된 활성탄소섬유를 제조하였다. 제조한 금속산화물 담지 활성탄소섬유는 상온에서 보관하기 위하여 헬륨 분위기에서 상온으로 냉각시킨 후 2 %의 산소를 혼합한 헬륨혼합가스 100sccm을 흘리면서 30분간 수동화 (표면산화) 처리하였다.Pitch-based activated carbon fiber OG15A (specific surface area 1014m 2 / g) manufactured by Osaka Gas Co., Ltd. was dried at 85 ° C. for 8 hours while degassing at a pressure of 2 Torr or less, and used as the activated carbon fiber of the substrate. Iron nitrate manufactured by Wako Japan (일본) to support an alloy catalyst of iron and nickel (iron / nickel weight ratio 2/8) on dry activated carbon fibers as a catalyst for producing ultrafine fibrous nanocarbon on the surface of activated carbon fibers. 1 級. Iron (III) nitrate nonahydrate Fe (NO 3 ) 3 9H 2 O = 404.00 (99%, Wako), mp 35-40 ° C., d 1.684, sol in water, ethanol, acetone and nickel nitrate (Nickel, Japan) (II) nitrate hexahydrate Ni (NO 3 ) 2 6H 2 O = 290.79 (98%, Wako), mp 56.7 ° C, d 2.05, bp 137, sol in 0.4 part water, in alcohol, Ni content 20.19% (Nickel Ni = 58.71) was added to the distilled water to dissolve to prepare a 10% by weight solution, and then 10 g of the activated carbon fiber made by Osaka Kasa Co., Ltd. was added and stirred for 12 hours to knead and kneaded. Ferrous nitrate and nickel nitrate were dried by using a rotary evaporator at a temperature of 80 ° C to 40 Torr, and iron nitrate and nickel nitrate were dispersed and supported on pores and surfaces. Carbon fibers were prepared by using activated carbon fibers containing iron nitrate and nickel nitrate dispersed in a quartz boat (length x width x depth). = 10x2.5x1.5 / mm (external value) and place it in the middle of a horizontal line made of quartz tube with an inner diameter of 4.5cm and oxidize it at 350 degrees Celsius for 0.5 hours while flowing 50sccm of air to Partial gasification was performed by maintaining a helium atmosphere for 30 minutes while leaving activated carbon fibers in the furnace, which had a metal oxide weight loss of about 4% by weight, by using a mixture gas of hydrogen and helium (water pressure partial pressure: 20%). After 1 hour reduction treatment at 520 ° C., an activated carbon fiber in which an alloy of iron and nickel was uniformly dispersed and supported on the pores and the surface was prepared.The prepared metal oxide-supported activated carbon fiber was cooled to room temperature in a helium atmosphere for storage at room temperature. After pass through 100% of helium mixed gas mixed with oxygen of 2%, passivation (surface oxidation) was performed for 30 minutes.
상기 제조한 금속산화물 담지 활성탄소섬유 109mg(금속산화물량 9 mg)을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 금속산화물 담지 활성탄소섬유의 가스화시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 섭씨520도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 520도에서 1시간 반응를 행하여 소정량의 (525 mg)의 고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 약424mg으로서 금속촉매의 중량대비 85배의 극세 섬유상 나노탄소가 성장한 것을 확인하였다.109 mg of the metal oxide-supported activated carbon fiber (9 mg of metal oxide) prepared above was mounted in the middle of a quartz tube having an inner diameter of 4.5 cm, and then hydrogen was obtained by using a horizontal furnace used for gasification of the metal oxide-supported activated carbon fiber. The reduction treatment was performed at 520 degrees Celsius for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of and helium. The reaction was carried out at 520 ° C for 1 hour while flowing 200 sccm (25 vol% of hydrogen partial pressure) of mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount (525 mg) of high surface area carbonaceous material. It was confirmed that the growth amount of the ultrafine carbon fiber except the activated carbon fiber of the substrate was about 424 mg, and the microfine fibrous nanocarbon of 85 times the weight of the metal catalyst was grown.
제조한 고표면적 탄소재를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 표 2에 정리하였다.Table 2 shows the isothermal curves of the prepared high surface area carbonaceous material by nitrogen BIT method and calculated by the Dubinin equation.
제조한 고표면적 탄소재의 섬유형태를 알기 위하여, 고분해주사형 전자현미경(Jeol,JSM 64O3F)의 관찰을 행하여 촬영한 사진을 그림 1 및 그림 2에 나타내었다. 제조한 고표면적 탄소재는 기질로 사용한 활성탄소섬유의 세공 또는 표면에 극세 섬유상 나노탄소가 무수히 성장하여 표면에 고르게 존재하는 것을 확인할 수 있었다.In order to know the fiber morphology of the prepared high surface area carbonaceous material, photographs taken by observation of a high resolution scanning electron microscope (Jeol, JS 64O3F) are shown in Fig. 1 and Fig. 2. The prepared high surface area carbon material was able to confirm that microfine fibrous nanocarbon grows in the pores or surface of the activated carbon fiber used as a substrate and is evenly present on the surface.
기질의 활성탄소섬유의 세공 내지는 표면에 성장한 극세 나노섬유의 섬유경은 약 25 nm의 균일한 분포를 하고 있음을 알 수 있었다.It was found that the fiber diameter of the ultrafine nanofibers grown on the pores or surfaces of the activated carbon fibers of the substrate had a uniform distribution of about 25 nm.
상기의 제조법으로 간단한 촉매 담지법에 의해 기질인 활성탄소섬유의 표면에 섬유상 극세나노탄소가 고르게 성장한 고표면적 탄소재의 제조가 가능하였다.With the above production method, it was possible to produce a high surface area carbon material in which fibrous ultra-nanocarbon was evenly grown on the surface of activated carbon fiber as a substrate by a simple catalyst supporting method.
실시예 2Example 2
상기 실시예 1에서 제조한 철/니켈 (중량비 2/8)의 합금촉매를 담지한 활성탄소섬유의 기질을 이용하여 활성탄소섬유의 세공 내지는 표면에 섬유상 나노탄소 제조용 촉매30mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 520도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 섭씨520도에서 20분 반응를 행하여 소정량의 (340 mg)의고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 약239mg으로서 금속촉매의 중량대비 48배의 극세 섬유상 나노탄소가 성장한 것을 확인하였다. 제조한 섬유상 나노탄소를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 역시 표 2에 정리하였다.Using a substrate of an activated carbon fiber carrying an alloy catalyst of iron / nickel (weight ratio 2/8) prepared in Example 1, 30 mg of the catalyst for producing fibrous nanocarbon in the pore or surface of the activated carbon fiber was 4.5 cm in inner diameter. After attaching to the middle part of the quartz tube, the reduction process was carried out at 520 ° C for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of hydrogen and helium using a horizontal furnace used for preparing the catalyst. A predetermined amount (340 mg) of high surface area carbonaceous material was produced by reacting 20 minutes at 520 degrees Celsius while flowing 200 sccm (25 vol% of hydrogen partial pressure) of ethylene and hydrogen on the reduced catalyst. It was confirmed that the growth amount of the ultrafine carbon fiber except the activated carbon fiber of the substrate was about 239 mg, and the ultrafine fibrous nanocarbon of 48 times the weight of the metal catalyst was grown. After obtaining the isothermal curves of the fibrous nanocarbons prepared by the N2 BET method, the specific surface areas calculated by the Dubinin formula are also summarized in Table 2.
제조한 고표면적 탄소재는 기질의 활성탄소섬유의 세공 내부 내지는 표면에 실시예 1에 비해 비교적 굵은 섬유상 나노탄소가 성장한 모습을 나타내었다. 성장한 섬유상 나노탄소의 조직은 탄소육각망면이 섬유축 방향에 30도 정도의 각도로 배열하고 있는 구조 (깃털 구조, Feather structure)로서 섬유축과 평행방향으로 탄소의 육각망면이 배열하고 있는 탄소나노튜브와는 다른 구조를 지니고 있음을 알 수 있었다. 성장한 섬유의 섬유경은 평균 22 nm를 나타내었다.The prepared high surface area carbonaceous material exhibited a relatively thick fibrous nanocarbon growth on the inside or surface of the pores of the activated carbon fiber of the substrate. The structure of the grown fibrous nanocarbon is a structure in which the carbon hexagonal net surface is arranged at an angle of about 30 degrees to the fiber axis direction (feather structure), and the carbon nanotubes in which the hexagonal net surface of carbon is arranged in parallel with the fiber axis It can be seen that it has a different structure from. The fiber diameter of the grown fiber showed an average of 22 nm.
실시예 3Example 3
상기 실시예 1에서 제조한 철/니켈 (중량비 2/8)의 합금촉매를 담지한 활성탄소섬유의 기질을 이용하여 활성탄소섬유의 세공 내지는 표면에 섬유상 나노탄소 제조용 촉매30mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 550도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 섭씨550도에서 1시간 반응를 행하여 소정량의 (580 mg)의고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 약471mg으로서 금속촉매의 중량대비 94배의 극세 섬유상 나노탄소가 성장한 것을 확인하였다. 제조한 섬유상 나노탄소를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 역시 표 2에 정리하였다.Using a substrate of an activated carbon fiber carrying an alloy catalyst of iron / nickel (weight ratio 2/8) prepared in Example 1, 30 mg of the catalyst for producing fibrous nanocarbon in the pore or surface of the activated carbon fiber was 4.5 cm in inner diameter. After attaching to the middle part of the quartz tube, the reduction process was performed at 550 ° C for 2 hours while flowing 100 sccm of hydrogen and helium (20 vol% of partial pressure of hydrogen) using a horizontal furnace used for preparing the catalyst. The reaction was carried out at 550 degrees Celsius for 1 hour while flowing 200 sccm of a mixed gas of ethylene and hydrogen (25 vol% of hydrogen) on the reduced catalyst to prepare a predetermined amount of (580 mg) of a high surface area carbonaceous material. It was confirmed that the growth amount of the ultrafine carbon fiber except the activated carbon fiber of the substrate was about 471 mg, and the ultrafine fibrous nanocarbon of 94 times the weight of the metal catalyst was grown. After obtaining the isothermal curves of the fibrous nanocarbons prepared by the N2 BET method, the specific surface areas calculated by the Dubinin formula are also summarized in Table 2.
제조한 고표면적 탄소재는 기질의 활성탄소섬유의 세공 내부 내지는 표면에 실시예 1에 비해 비교적 굵은 섬유상 나노탄소가 성장한 모습을 나타내었다. 성장한 섬유상 나노탄소의 조직은 탄소육각망면이 섬유축 방향에 30도 정도의 각도로 배열하고 있는 구조 (깃털 구조, Feather structure)로서 섬유축과 평행방향으로 탄소의 육각망면이 배열하고 있는 탄소나노튜브와는 다른 구조를 지니고 있음을 알 수 있었다. 성장한 섬유의 섬유경은 평균 65 nm를 나타내었다.The prepared high surface area carbonaceous material exhibited a relatively thick fibrous nanocarbon growth on the inside or surface of the pores of the activated carbon fiber of the substrate. The structure of the grown fibrous nanocarbon is a structure in which the carbon hexagonal net surface is arranged at an angle of about 30 degrees to the fiber axis direction (feather structure), and the carbon nanotubes in which the hexagonal net surface of carbon is arranged in parallel with the fiber axis It can be seen that it has a different structure from. The fiber diameter of the grown fiber showed an average of 65 nm.
실시예 4Example 4
상기 실시예 1에서 제조한 철/니켈 (중량비 2/8)의 합금촉매를 담지한 기질의 활성탄소섬유 109mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 600도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 섭씨600도에서 1시간 반응를 행하여 소정량의 (720 mg)의 고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 약619mg으로서 금속촉매의 중량대비 124배의 극세 섬유상 나노탄소가 성장한 것을 확인하였다.109 mg of the activated carbon fiber of the substrate supporting the alloy catalyst of iron / nickel (weight ratio 2/8) prepared in Example 1 was mounted in the middle of a quartz tube having an inner diameter of 4.5 cm, and then used for preparing the catalyst. The furnace was subjected to a reduction treatment at 600 ° C. for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of hydrogen and helium. The reaction was carried out at 600 degrees Celsius for 1 hour while flowing 200 sccm (25 vol% of hydrogen partial pressure) of mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount (720 mg) of high surface area carbonaceous material. It was confirmed that the growth amount of the ultrafine carbon fiber except the activated carbon fiber of the substrate was about 619 mg, and the microfine fibrous nanocarbon of 124 times the weight of the metal catalyst was grown.
제조한 섬유상 나노탄소를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 역시 표 2에 정리하였다.After obtaining the isothermal curves of the fibrous nanocarbons prepared by the N2 BET method, the specific surface areas calculated by the Dubinin formula are also summarized in Table 2.
제조한 고표면적 탄소재는 기질의 활성탄소섬유의 세공 내부 내지는 표면에 실시예 1에 비해 비교적 굵은 섬유상 나노탄소가 성장한 모습을 나타내었다. 성장한 섬유상 나노탄소의 조직은 탄소육각망면이 섬유축 방향에 30도 정도의 각도로 배열하고 있는 구조 (깃털 구조, Feather structure)로서 섬유축과 평행방향으로 탄소의 육각망면이 배열하고 있는 탄소나노튜브와는 다른 구조를 지니고 있음을 알 수 있었다. 성장한 섬유의 섬유경은 평균 88 nm를 나타내었다.The prepared high surface area carbonaceous material exhibited a relatively thick fibrous nanocarbon growth on the inside or surface of the pores of the activated carbon fiber of the substrate. The structure of the grown fibrous nanocarbon is a structure in which the carbon hexagonal net surface is arranged at an angle of about 30 degrees to the fiber axis direction (feather structure), and the carbon nanotubes in which the hexagonal net surface of carbon is arranged in parallel with the fiber axis It can be seen that it has a different structure from. The average fiber diameter of the grown fibers was 88 nm.
실시예 5Example 5
상기 실시예 1에서 제조한 철/니켈 (중량비 2/8)의 합금촉매를 담지한 기질의 활성탄소섬유 109mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 600도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 섭씨650도에서 1시간 반응를 행하여 소정량의 (330 mg)의고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 약229mg으로서 금속촉매의 중량대비 46배의 극세 섬유상 나노탄소가 성장한 것을 확인하였다.109 mg of the activated carbon fiber of the substrate supporting the alloy catalyst of iron / nickel (weight ratio 2/8) prepared in Example 1 was mounted in the middle of a quartz tube having an inner diameter of 4.5 cm, and then used for preparing the catalyst. The furnace was subjected to a reduction treatment at 600 ° C. for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of hydrogen and helium. The reaction was carried out at 650 degrees Celsius for 1 hour while flowing 200 sccm (25 vol% of hydrogen partial pressure) of mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount of (330 mg) of high surface area carbonaceous material. The growth amount of the ultrafine carbon fiber except the activated carbon fiber of the substrate was about 229 mg, and it was confirmed that the ultrafine fibrous nanocarbon grew by 46 times the weight of the metal catalyst.
제조한 섬유상 나노탄소를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 역시 표 2에 정리하였다.After obtaining the isothermal curves of the fibrous nanocarbons prepared by the N2 BET method, the specific surface areas calculated by the Dubinin formula are also summarized in Table 2.
제조한 고표면적 탄소재는 기질의 활성탄소섬유의 세공 내부 내지는 표면에 실시예 1에 비해 비교적 굵은 섬유상 나노탄소가 성장한 모습을 나타내었다. 성장한 섬유의 섬유경은 평균 43 nm를 나타내었다.The prepared high surface area carbonaceous material exhibited a relatively thick fibrous nanocarbon growth on the inside or surface of the pores of the activated carbon fiber of the substrate. The average fiber diameter of the grown fibers was 43 nm.
실시예 6Example 6
상기 실시예 1에서 제조한 철/니켈 (중량비 2/8)의 합금촉매를 담지한 기질의 활성탄소섬유 109mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 600도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 50 체적%)를 흘리면서 섭씨600도에서 1시간 반응를 행하여 소정량의 (660 mg)의고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 약555mg으로서 금속촉매의 중량대비 111배의 극세 섬유상 나노탄소가 성장한 것을 확인하였다.109 mg of the activated carbon fiber of the substrate supporting the alloy catalyst of iron / nickel (weight ratio 2/8) prepared in Example 1 was mounted in the middle of a quartz tube having an inner diameter of 4.5 cm, and then used for preparing the catalyst. The furnace was subjected to a reduction treatment at 600 ° C. for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of hydrogen and helium. The reaction was carried out at 600 ° C. for 1 hour while flowing 200 sccm (50 vol% of hydrogen partial pressure) of mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount of (660 mg) of high surface area carbonaceous material. It was confirmed that the growth amount of the ultrafine carbon fiber except the activated carbon fiber of the substrate was about 555 mg, and the ultrafine fibrous nanocarbon of 111 times the weight of the metal catalyst was grown.
제조한 섬유상 나노탄소를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 역시 표 2에 정리하였다.After obtaining the isothermal curves of the fibrous nanocarbons prepared by the N2 BET method, the specific surface areas calculated by the Dubinin formula are also summarized in Table 2.
제조한 고표면적 탄소재는 기질의 활성탄소섬유의 세공 내부 내지는 표면에 실시예 1에 비해 비교적 굵은 섬유상 나노탄소가 성장한 모습을 나타내었다. 성장한 섬유상 나노탄소의 조직은 탄소육각망면이 섬유축 방향에 30도 정도의 각도로 배열하고 있는 구조 (깃털 구조, Feather structure)로서 섬유축과 평행방향으로 탄소의 육각망면이 배열하고 있는 탄소나노튜브와는 다른 구조를 지니고 있음을 알 수 있었다. 성장한 섬유의 섬유경은 평균 82 nm를 나타내었다.The prepared high surface area carbonaceous material exhibited a relatively thick fibrous nanocarbon growth on the inside or surface of the pores of the activated carbon fiber of the substrate. The structure of the grown fibrous nanocarbon is a structure in which the carbon hexagonal net surface is arranged at an angle of about 30 degrees to the fiber axis direction (feather structure), and the carbon nanotubes in which the hexagonal net surface of carbon is arranged in parallel with the fiber axis It can be seen that it has a different structure from. The fiber diameter of the grown fiber showed an average of 82 nm.
실시예 7Example 7
상기 실시예 1에서 제조한 철/니켈 (중량비 2/8)의 합금촉매를 담지한 기질의 활성탄소섬유 109mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 600도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 섭씨600도에서 0.5시간 반응를 행하여 소정량의 (322 mg)의고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 약221mg으로서 금속촉매의 중량대비 44배의 극세 섬유상 나노탄소가 성장한 것을 확인하였다.109 mg of the activated carbon fiber of the substrate supporting the alloy catalyst of iron / nickel (weight ratio 2/8) prepared in Example 1 was mounted in the middle of a quartz tube having an inner diameter of 4.5 cm, and then used for preparing the catalyst. The furnace was subjected to a reduction treatment at 600 ° C. for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of hydrogen and helium. The reaction was carried out at 600 degrees Celsius for 0.5 hours while flowing 200 sccm (25 vol% of hydrogen partial pressure) of mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount (322 mg) of high surface area carbonaceous material. It was confirmed that the growth amount of the ultrafine carbon fiber except the activated carbon fiber of the substrate was about 221 mg, which was 44 times the ultrafine fibrous nanocarbon growth of the metal catalyst.
제조한 섬유상 나노탄소를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 역시 표 2에 정리하였다.After obtaining the isothermal curves of the fibrous nanocarbons prepared by the N2 BET method, the specific surface areas calculated by the Dubinin formula are also summarized in Table 2.
제조한 고표면적 탄소재는 기질의 활성탄소섬유의 세공 내부 내지는 표면에 실시예 1에 비해 비교적 굵은 섬유상 나노탄소가 성장한 모습을 나타내었다. 성장한 섬유의 섬유경은 평균 73 nm를 나타내었다.The prepared high surface area carbonaceous material exhibited a relatively thick fibrous nanocarbon growth on the inside or surface of the pores of the activated carbon fiber of the substrate. The average fiber diameter of the grown fibers was 73 nm.
비교예1Comparative Example 1
오오사카 가스사제 피치계 활성탄소섬유 0G15A(비표면적 1014m2/g)를 2토르이하의 압력으로 탈기하면서 섭씨85도에서8시간 건조하여 기질의 활성탄소섬유로 사용하였다. 건조한 활성탄소섬유에 철과 니켈(철/니켈 중량비 2/8)의 합금촉매를 활성탄소 섬유의 표면에 극세 섬유상 나노탄소 제조용 촉매를 담지하기 위해 일본 와코사제 질산철 (試□1級. Iron(III) nitrate nonahydrate Fe(NO3)3·9H2O = 404.00 (99%, wako), mp 35∼40℃, d 1.684, sol in water, ethanol, acetone)과 일본 와코사제 질산니켈(Nickel (II) nitrate hexahydrate Ni(NO3)2·6H2O = 290.79 (98%, Wako), mp 56.7℃, d 2.05, bp 137, sol in 0.4 part water, in alcohol, Ni content 20.19% (Nickel Ni = 58.71)의 일정량을 증류수에 첨가하여 용해시켜 10 중량 %의 용액을 제조한 후, 상기의 오오사카카스사제 활성탄소섬유 10g을 첨가하여 12시간 교반하여 혼련하였다. 상기의 방법으로 제조한 활성탄소섬유의 질산철 및 질산니켈의 혼합슬러지를 회전식 진공건조기(Rotary Evaporator)를 사용하여 섭씨80도에서 40토르 (Torr)의 조건으로 수분을 건조하여 질산철과 질산니켈이 세공 및 표면에 분산 담지된 활성탄소섬유를 제조하였다.Pitch-based activated carbon fiber 0G15A (specific surface area 1014m 2 / g) manufactured by Osaka Gas Co., Ltd. was dried at 85 degrees Celsius for 8 hours while degassing at a pressure of 2 Torr or less, and used as the activated carbon fiber of the substrate. Iron nitrate (제 □ 1..Iron) manufactured by Wako, Japan, was used to carry an alloy catalyst of iron and nickel (iron / nickel weight ratio 2/8) on a dry activated carbon fiber to carry a catalyst for producing ultrafine fibrous nanocarbon on the surface of the activated carbon fiber. III) nitrate nonahydrate Fe (NO 3 ) 3 9 H 2 O = 404.00 (99%, wako), mp 35-40 ° C., d 1.684, sol in water, ethanol, acetone and Nickel (II) ) nitrate hexahydrate Ni (NO 3 ) 2 · 6H 2 O = 290.79 (98%, Wako), mp 56.7 ° C, d 2.05, bp 137, sol in 0.4 part water, in alcohol, Ni content 20.19% (Nickel Ni = 58.71 After dissolving by adding a certain amount of) to distilled water to prepare a 10% by weight solution, 10 g of the activated carbon fiber made by Osaka Kasa Co., Ltd. was added and stirred for 12 hours to knead the nitric acid of the activated carbon fiber prepared by the above method. Mixed sludge of iron and nickel nitrate was used in a rotary evaporator at 80 degrees Celsius to 40 Torr. The moisture was dried to produce activated carbon fibers in which iron nitrate and nickel nitrate were dispersed and supported on pores and surfaces.
이렇게 실시예 1과는 달리, 산화 가스화 처리하지 않고 제조한 금속산화물 담지 활성탄소섬유 114mg(금속 전구체량 14 mg)을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 금속산화물 담지 활성탄소섬유의 가스화시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 섭씨520도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 520도에서 2시간 반응를 행하여 소정량의 (98 mg)의 고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 0mg으로서 오히려 금속 전구체를 담지한 기질의 활성탄소섬유의 중량보다 반응 후 중량이 준 것을 알 수 있었다. 이는 활성탄소섬유에 일부 존재하는 산화관능기가 환원 및 반응과정에서 환원되어 제거 된 것과 환원반응 중에 일부 활성탄소섬유가 환원 가스화되어 중량이 줄어 든 것으로 추정되었다.Thus, unlike Example 1, 114 mg of metal oxide-supported activated carbon fibers (14 mg of metal precursor) prepared without oxidizing and gasification were mounted on the middle of a quartz tube having an inner diameter of 4.5 cm, and then the metal oxide-supported activity. The reduction treatment was performed at 520 degrees Celsius for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of hydrogen and helium using a horizontal furnace used for gasification of carbon fibers. The reaction was carried out at 520 ° C for 2 hours while flowing 200 sccm (25 vol% of hydrogen partial pressure) of mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount (98 mg) of high surface area carbonaceous material. The growth amount of the ultrafine carbon fibers excluding the activated carbon fibers of the substrate was 0 mg, and it was found that the weight was higher than the weight of the activated carbon fibers of the substrate supporting the metal precursor. It is estimated that some of the oxidative functional groups present in the activated carbon fibers were reduced and removed during the reduction and reaction process, and some of the activated carbon fibers were reduced gasification during the reduction reaction.
비교예 2Comparative Example 2
상기 비교예 1에서 제조한 철/니켈 (중량비 2/8)의 합금촉매를 담지한 기질의 활성탄소섬유 114mg을 4.5cm의 내경을 지닌 석영관의 중간부에 장착한 후, 촉매 제조시 사용한 수평로를 사용하여 수소와 헬륨의 혼합가스 100sccm(수소분압 20체적 %)을 흘리면서 600도에서 2시간 환원처리를 행하였다. 환원한 촉매 상에 에칠렌과 수소의 혼합가스 200sccm (수소분압 25 체적%)를 흘리면서 섭씨600도에서 2시간 반응를 행하여 소정량의 (535 mg)의고표면적 탄소재를 제조하였다. 기질의 활성탄소섬유를 제외한 극세탄소섬유의 성장량은 421mg으로서 금속촉매의 중량대비 84배의 중량의 극세 섬유상 나노탄소가 성장한 것을 확인하였다.114 mg of the activated carbon fiber of the substrate supporting the alloy catalyst of iron / nickel (weight ratio 2/8) prepared in Comparative Example 1 was mounted on the middle part of the quartz tube having an inner diameter of 4.5 cm, and then used for preparing the catalyst. The furnace was subjected to a reduction treatment at 600 ° C. for 2 hours while flowing 100 sccm (20 vol% of hydrogen partial pressure) of a mixed gas of hydrogen and helium. The reaction was carried out at 600 degrees Celsius for 2 hours while flowing 200 sccm (25 vol% of hydrogen partial pressure) of mixed gas of ethylene and hydrogen on the reduced catalyst to prepare a predetermined amount (535 mg) of high surface area carbonaceous material. The growth amount of the ultrafine carbon fibers excluding the active carbon fibers of the substrate was 421 mg, and it was confirmed that the ultrafine fibrous nanocarbons were 84 times the weight of the metal catalyst.
제조한 섬유상 나노탄소를 질소 비이티(N2 BET)법으로 등온곡선을 구한 후 이를 듀비닌(Dubinin)식으로 계산한 비표면적을 역시 표 2에 정리하였다.After obtaining the isothermal curves of the fibrous nanocarbons prepared by the N2 BET method, the specific surface areas calculated by the Dubinin formula are also summarized in Table 2.
제조한 탄소재는 표2에 나타낸 바와 같이 비표면적인 34m2/g으로서 비교적 낮은 비표면적을 나타내었다.The carbon material produced had a relatively low specific surface area as a specific surface area of 34 m 2 / g as shown in Table 2.
표 1. 고표면적 탄소재의 제조 단계별 비표면적의 변화Table 1. Variation of specific surface area by manufacturing of high surface area carbon materials
(단위: ㎡/g)(Unit: ㎡ / g)
표 2. 제조한 고표면적 탄소재의 물성Table 2. Physical properties of manufactured high surface area carbon materials
상의 설명과 같이, 본 발명에 의해 현재까지 제조가 불가하였던 활성탄소섬유의 세공 내지는 표면에 극세 섬유상 나노탄소를 성장시킨 고표면적 탄소재 및 그 제조가 가능하며, 제조한 고표면적 탄소재는 기질의 활성탄소섬유의 표면 및 성장한 섬유상 나노탄소의 고표면적을 이용하여 복합재, 전자파 차폐재 등의 필러, 전기 이중층 캐파시터 및 전기탈염용 전극재로서의 응용이 가능하며, 나아가서 연료전지, 일반 유기화학반응용의 촉매 담체, 수소, 메탄의 저장재 및 분리재, DeNOx, DeSOx, 다이옥신 및 수질 중의 유해 유기물질, 클로로화합물, 수질 및 대기의 혐오성 물질의 흡착제거재로 사용이 적합하다As described above, a high surface area carbon material in which ultrafine fibrous nanocarbons are grown in pores or surfaces of activated carbon fibers, which has not been manufactured by the present invention, can be manufactured, and the prepared high surface area carbon material can be used as a substrate active material. By using the surface of carbon fiber and the high surface area of the grown fibrous nanocarbon, it can be applied as a filler for composite materials, electromagnetic shielding materials, electric double layer capacitor and electrode material for electrodesalting, and furthermore, catalyst for fuel cell and general organic chemical reaction. It is suitable for use as a carrier, separator and storage material of hydrogen, methane, DeNOx, DeSOx, dioxin and adsorption removal material of harmful organic substances, chloro compounds, water and atmosphere aversive substances in water.
도 1은 실시예1에 의해 제조한 고비표면적 탄소재의 고분해 주사형 전자 현미경사진1 is a high resolution scanning electron micrograph of a high specific surface area carbon material prepared in Example 1
도 2은 실시예1에 의해 제조한 고비표면적 탄소재의 표면에 성장한 섬유상 나노탄소재의 고분해능 주사형 전자 현미경 사진Figure 2 is a high resolution scanning electron micrograph of a fibrous nanocarbon material grown on the surface of the high specific surface area carbon material prepared in Example 1
도 3은 실시예2에 의해 제조한 고비표면적 탄소재의 고분해 주사형 전자현미경 사진3 is a high resolution scanning electron micrograph of a high specific surface area carbon material prepared in Example 2;
도 4는 비교예1에 의해 제조한 고비표면적 탄소재의 고분해주사형 전자현미경 사진4 is a high resolution scanning electron micrograph of a high specific surface area carbon material prepared in Comparative Example 1
도 5는 실시예 1에 의해 제조한 고비표면적 탄소재의 기공크기의 분포도의 변화5 is a change in pore size distribution of the high specific surface area carbon material prepared in Example 1
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