JP2001080912A - Production of carbon nanotube - Google Patents
Production of carbon nanotubeInfo
- Publication number
- JP2001080912A JP2001080912A JP25745799A JP25745799A JP2001080912A JP 2001080912 A JP2001080912 A JP 2001080912A JP 25745799 A JP25745799 A JP 25745799A JP 25745799 A JP25745799 A JP 25745799A JP 2001080912 A JP2001080912 A JP 2001080912A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- catalyst
- carbon nanotubes
- carbon
- containing material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 76
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 110
- 239000000758 substrate Substances 0.000 claims abstract description 107
- 239000000463 material Substances 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 29
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000004530 micro-emulsion Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000011882 ultra-fine particle Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UMGXUWVIJIQANV-UHFFFAOYSA-M didecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC UMGXUWVIJIQANV-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 organic acid salt Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000692885 Nymphalis antiopa Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、カーボンナノチュ
ーブを工業的に有利に製造する方法に関するものであ
る。The present invention relates to a method for industrially advantageously producing carbon nanotubes.
【０００２】[0002]
【従来の技術】カーボンナノチューブは、直径が１〜１
０ｎｍで数１０ｎｍ〜数μｍ程度の長さを有する最も微
細な中空状炭素繊維である。このようなカーボンナノチ
ューブは、大画面平面ディスプレイに用いられるフィー
ルドエミッション用電子源や、自動車用の大容量燃料電
池のための水素吸蔵材料として有用な物質であることか
ら、その工業的製造方法の開発が強く望まれている。カ
ーボンナノチューブを製造する方法として、触媒基材の
存在下で含炭素原料を熱分解させて、その基材上にカー
ボンナノチューブを生成させる方法が知られている。こ
の方法で用いる触媒基材の製法としては、基材表面に微
細な細孔を作り、そこに触媒金属を埋め込む方法や、金
属板のエッチングにより微小な金属粒子を作製する方法
等が用いられている。しかしながら、前記の方法におい
ては、その触媒基板の作製に大きな困難を要する上、そ
の操作を連続化することがむつかしく、実際上、バッチ
方式で実施されている。2. Description of the Related Art Carbon nanotubes have a diameter of 1-1.
It is the finest hollow carbon fiber having a length of about 10 nm to several μm at 0 nm. Since such a carbon nanotube is a useful substance as an electron source for field emission used for a large-screen flat display and a hydrogen storage material for a large-capacity fuel cell for an automobile, the development of an industrial production method thereof has been developed. Is strongly desired. As a method for producing carbon nanotubes, there has been known a method in which a carbon-containing raw material is thermally decomposed in the presence of a catalyst substrate to form carbon nanotubes on the substrate. As a method for producing the catalyst base material used in this method, a method of creating fine pores on the surface of the base material and embedding a catalyst metal therein, or a method of producing fine metal particles by etching a metal plate, and the like are used. I have. However, in the above-mentioned method, the preparation of the catalyst substrate requires great difficulty, and it is difficult to make the operation continuous.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、カーボンナ
ノチューブを工業的に有利に製造する方法を提供するこ
とをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for industrially advantageously producing carbon nanotubes.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、含炭素材料を触媒基
材の存在下で熱分解してカーボンナノチューブを製造す
る方法において、（ｉ）触媒基材の存在下で含炭素材料
を熱分解させて該基材上にカーボンナノチューブを生成
させる工程、（ii）該生成したカーボンナノチューブを
該基材から分離する工程、(iii）該カーボンナノチュー
ブを分離した後の基材上に触媒超微粒子を含む触媒液を
塗布乾燥して、触媒基材を再生する工程、（iv）該再生
基材の存在下で含炭素材料を熱分解させて該基材上にカ
ーボンナノチューブを生成させる工程、からなる一連の
工程を繰返し行うことを特徴とするカーボンナノチュー
ブの製造方法が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, in a method for producing carbon nanotubes by thermally decomposing a carbon-containing material in the presence of a catalyst substrate, (i) thermally decomposing the carbon-containing material in the presence of a catalyst substrate, A step of generating carbon nanotubes on a substrate, (ii) a step of separating the generated carbon nanotubes from the substrate, and (iii) a catalyst solution containing ultrafine catalyst particles on the substrate after the carbon nanotubes are separated. Coating and drying to regenerate the catalyst substrate, and (iv) a step of thermally decomposing the carbon-containing material in the presence of the regenerated substrate to form carbon nanotubes on the substrate. Is repeatedly performed, and a method for producing carbon nanotubes is provided.
【０００５】[0005]
【発明の実施の形態】本発明で用いる触媒基材は、基材
上に触媒液を塗布し、乾燥することによって作製され
る。この場合、触媒液は、含炭素材料を熱分解してカー
ボンナノチューブを合成する際の触媒となる触媒金属超
微粒子を溶媒中に分散させたマイクロエマルジョンから
なる。この触媒液において、その触媒金属としては、通
常、遷移金属が用いられる。この触媒金属としては、特
にＶからVIII族の金属、例えば、ニッケル、コバルト、
モリブデン、鉄、銅、バナジウム、パラジウム等が挙げ
られる。本発明で用いる触媒は金属であることができる
他、金属の化合物、例えば金属ホウ化物、金属酸化物等
であることができ、カーボンナノチューブの合成に触媒
作用を有するものであればどのようなものでもよい。そ
の触媒は溶媒中に超微粒子状で分散し、その平均粒径
は、通常、１〜２０ｎｍ程度である。その触媒超微粒子
の液中濃度は０．１〜１０重量％、好ましくは１〜５重
量％である。その溶媒としては、水及び各種の有機溶媒
が用いられる。有機溶媒には、アルコール、ケトン、エ
ステル、炭化水素等が包含される。その具体例として
は、例えば、メタノール、プロピルアルコール、アミル
アルコール、ヘキサノール、シクロヘキサノール、ヘプ
タノール、オクチルアルコール、シクロヘキサン、メチ
ルエチルケトン、ジエチルケトン、シクロヘプタン、ｎ
−ヘキサン、ｎ−ヘプタン、イソオクタン、ｎ−デカ
ン、ベンゼン、トルエン、キシレン等が挙げられる。本
発明では、その沸点が５０〜２００℃の範囲にある有機
溶媒の使用が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The catalyst substrate used in the present invention is prepared by applying a catalyst solution on the substrate and drying. In this case, the catalyst liquid is composed of a microemulsion in which ultrafine catalytic metal particles serving as a catalyst for synthesizing carbon nanotubes by thermally decomposing a carbon-containing material are dispersed in a solvent. In this catalyst liquid, a transition metal is usually used as the catalyst metal. The catalyst metals include, in particular, metals of groups V to VIII, such as nickel, cobalt,
Molybdenum, iron, copper, vanadium, palladium and the like can be mentioned. In addition to being a metal, the catalyst used in the present invention can be a compound of a metal, for example, a metal boride, a metal oxide, or the like, as long as it has a catalytic action on the synthesis of carbon nanotubes. May be. The catalyst is dispersed in a solvent in the form of ultrafine particles, and the average particle size is usually about 1 to 20 nm. The concentration of the ultrafine catalyst particles in the liquid is 0.1 to 10% by weight, preferably 1 to 5% by weight. Water and various organic solvents are used as the solvent. Organic solvents include alcohols, ketones, esters, hydrocarbons, and the like. Specific examples thereof include, for example, methanol, propyl alcohol, amyl alcohol, hexanol, cyclohexanol, heptanol, octyl alcohol, cyclohexane, methyl ethyl ketone, diethyl ketone, cycloheptane, n
-Hexane, n-heptane, isooctane, n-decane, benzene, toluene, xylene and the like. In the present invention, it is preferable to use an organic solvent having a boiling point in the range of 50 to 200 ° C.
【０００６】前記触媒液の調製方法としては、触媒超微
粒子を溶媒中に均一に分散し得る方法であればよく、任
意の方法を用いることができる。その好ましい調製方法
においては、先ず、有機溶媒に界面活性剤を加えて溶解
させる。次に、この界面活性剤を含む有機溶媒に対し
て、その有機溶媒に可溶性の触媒金属化合物を添加し、
溶解させる。次いで、この有機溶媒中の触媒金属化合物
を還元し、超微粒子状の不溶性触媒金属を生成させるこ
とにより、触媒金属超微粒子を含むマイクロエマルジョ
ンが得られる。前記界面活性剤としては、イオン性界面
活性剤、好ましくはカチオン性界面活性剤やアニオン性
界面活性剤が用いられる。この場合、カチオン性界面活
性剤としては、炭素数８〜２２、好ましくは１２〜１８
の長鎖アルキル基やアルケニル基を有する第４級アンモ
ニウム塩を用いることができる。その具体例としては、
ジデシルジメチルアンモニウムブロマイド、ジデシルジ
メチルアンモニウムクロライド、ジドデシルジメチルア
ンモニウムブロマイド（又はクロライド）、セチルトリ
メチルアンモニウムブロマイド（又はクロライド）、ド
デシルトリメチルアンモニウムブロマイド（又はクロラ
イド）等を挙げることができる。アニオン性界面活性剤
の具体例としては、ジオクチルスルホサッシネートナト
リウム塩が挙げられる。界面活性剤の使用割合は、溶液
中、１〜２０重量％、好ましくは７〜１５重量％であ
る。前記可溶性触媒金属化合物としては、触媒金属のハ
ロゲン化物（塩化物、臭化物等）、有機酸塩（酢酸塩
等）、有機錯塩（アセチルアセテート塩等）、硝酸塩等
が挙げられる。As a method for preparing the catalyst liquid, any method can be used as long as it can uniformly disperse the catalyst ultrafine particles in a solvent, and any method can be used. In the preferred preparation method, first, a surfactant is added to an organic solvent and dissolved. Next, a catalyst metal compound soluble in the organic solvent is added to the organic solvent containing the surfactant,
Allow to dissolve. Next, the catalyst metal compound in the organic solvent is reduced to generate ultrafine insoluble catalyst metal, whereby a microemulsion containing ultrafine catalyst metal particles is obtained. As the surfactant, an ionic surfactant, preferably a cationic surfactant or an anionic surfactant is used. In this case, the cationic surfactant has 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
Quaternary ammonium salts having a long-chain alkyl group or alkenyl group can be used. As a specific example,
Didecyldimethylammonium bromide, didecyldimethylammonium chloride, didodecyldimethylammonium bromide (or chloride), cetyltrimethylammonium bromide (or chloride), dodecyltrimethylammonium bromide (or chloride), and the like can be given. Specific examples of the anionic surfactant include dioctyl sulfosuccinate sodium salt. The usage ratio of the surfactant is 1 to 20% by weight, preferably 7 to 15% by weight in the solution. Examples of the soluble catalyst metal compound include a halide (chloride, bromide, etc.), an organic acid salt (acetate, etc.), an organic complex salt (acetyl acetate salt, etc.), a nitrate, etc. of the catalyst metal.
【０００７】溶液中の触媒金属化合物の還元法として
は、水素ガスを用いる還元法の他、ヒドラジンや水素化
ホウ素ナトリウム等の化学的還元剤を用いる方法が挙げ
られるが、化学的還元剤の使用が好ましい。この化学的
還元剤を用いる還元方法は、常温において、理論量の１
モル倍以上、好ましくは２〜１０モル倍の化学的還元剤
を溶液に攪拌下で添加することによって実施される。こ
の場合、その化学的還元剤は、水溶液や有機溶媒溶液の
形態で添加することができる。As a method for reducing a catalytic metal compound in a solution, a method using a chemical reducing agent such as hydrazine or sodium borohydride may be used in addition to a method using hydrogen gas. Is preferred. This reduction method using a chemical reducing agent is performed at room temperature at a theoretical amount of 1%.
It is carried out by adding a chemical reducing agent at a molar ratio of at least 2 times, preferably 2 to 10 times, to the solution with stirring. In this case, the chemical reducing agent can be added in the form of an aqueous solution or an organic solvent solution.
【０００８】前記のようにして得られる触媒超微粒子を
含むマイクロエマルジョンは、そのまま触媒液として使
用することができるが、このものはカーボンナノチュー
ブの合成に好ましくない界面活性剤を含むことから、そ
の界面活性剤を除去して用いるのが好ましい。マイクロ
エマルジョンからの界面活性剤の除去は、そのマイクロ
エマルジョンを遠心処理して、触媒相と溶媒相とに分離
し、その溶媒相を除去した後、その触媒相を溶媒中に再
び分散させてマイクロエマルジョンとする。このような
操作を複数回、通常、２〜８回、好ましくは３〜５回繰
返すことにより、界面活性剤濃度が１重量％以下、好ま
しくは０．１重量％以下の触媒液を得る。その他の方法
として、ウルトラフィルターを用いた透析法により、超
微粒子を抽出濃縮することも可能である。[0008] The microemulsion containing ultrafine catalyst particles obtained as described above can be used as a catalyst solution as it is. However, the microemulsion contains a surfactant which is not preferable for the synthesis of carbon nanotubes. It is preferable to remove the activator before use. Removal of the surfactant from the microemulsion is performed by centrifuging the microemulsion to separate it into a catalyst phase and a solvent phase, removing the solvent phase, and then dispersing the catalyst phase in the solvent again. Emulsion. By repeating such an operation a plurality of times, usually 2 to 8 times, preferably 3 to 5 times, a catalyst solution having a surfactant concentration of 1% by weight or less, preferably 0.1% by weight or less is obtained. As another method, ultrafine particles can be extracted and concentrated by a dialysis method using an ultrafilter.
【０００９】本発明による他の好ましい触媒液の調製方
法においては、水溶性の触媒金属化合物をあらかじめ水
溶液とし、この水溶液を界面活性剤の存在下で有機溶媒
中に超微粒子状で分散させ、得られたマイクロエマルジ
ョンを前記と同様にして後処理することにより実施され
る。水溶液中の触媒金属化合物の濃度は、０．０５モル
／リットル以下、好ましくは０．０２モル／リットル以
下であり、その下限値は特に制約されないが、通常、
０．０００１モル／リットル程度である。In another preferred method for preparing a catalyst solution according to the present invention, a water-soluble catalytic metal compound is previously prepared as an aqueous solution, and this aqueous solution is dispersed in the form of ultrafine particles in an organic solvent in the presence of a surfactant. The microemulsion thus obtained is post-treated in the same manner as described above. The concentration of the catalytic metal compound in the aqueous solution is 0.05 mol / L or less, preferably 0.02 mol / L or less, and the lower limit is not particularly limited.
It is about 0.0001 mol / liter.
【００１０】前記においては、液中に溶解する触媒金属
化合物を還元し、金属状態に還元する方法を示したが、
この還元法による金属への還元に代えて、金属水酸化物
や、金属酸化物、金属硫化物等の不溶性金属化合物の沈
殿を生成させる通常の沈殿法も採用することができる。In the above, a method has been described in which a catalytic metal compound dissolved in a liquid is reduced to a metallic state.
Instead of the reduction to the metal by the reduction method, an ordinary precipitation method for generating a precipitate of an insoluble metal compound such as a metal hydroxide, a metal oxide, and a metal sulfide can also be employed.
【００１１】本発明の触媒液を用いて触媒基材を作製す
るには、基材上に触媒液を塗布し、乾燥する。基材とし
ては、従来公知の各種のものを用いることができる。こ
の基材としては、シリコーンや、セラミックス、ステン
レス等の耐熱性の材料であればよく、特に制約されない
が、疎水性表面を有するものが好ましい。本発明では、
このような材料を少なくともその表面に有するものが用
いられる。その形状は、シート状、板体状、柱状、筒状
等であることができる。本発明では、平板状の大面積基
材を有利に用いることができる。この大面積基材は、平
面ディスプレイに用いられるフィールドエミッション用
電子源を作製する際の触媒基材として有利に用いられ
る。基材上に触媒液を塗布する方法としては、従来公知
の各種の方法を用いることができる。このような方法と
しては、ハケ塗り法、ロール塗布法、スプレー塗布法、
スピンコート法、表面改質した基材への含浸法等が包含
される。本発明では、スクリーン印刷等の印刷法や、微
小ノズルから液体を噴出させるインクジェット法等を好
ましく採用することができる。触媒液を基材上に塗布す
る場合、その触媒液は、基材に対して、その全面に均一
に塗布することができる他、線状、帯状、格子状、ドッ
ト状、その他の任意のパターン状に塗布することができ
る。触媒液の塗布された基材は、これを乾燥することに
より、表面に触媒超微粒子の付着した触媒基材を得るこ
とができる。基材上の触媒粒子は、カーボンナノチュー
ブの生成を促進させる状態であればよく、金属状態の
他、金属硫化物や金属ホウ化物、金属酸化物、金属水酸
化物等の状態であることができる。金属硫化物の場合に
は、その基材上の金属状態の超微粒子に対して、硫化水
素等の硫化剤を反応させることによって得ることができ
る。基材上の触媒超微粒子の付着量は、１００ｃｍ2当
り１０-10〜１０-1モルの割合である。To prepare a catalyst substrate using the catalyst solution of the present invention, the catalyst solution is applied on the substrate and dried. As the substrate, various conventionally known substrates can be used. The substrate is not particularly limited as long as it is a heat-resistant material such as silicone, ceramics, and stainless steel, but is preferably a material having a hydrophobic surface. In the present invention,
A material having such a material at least on its surface is used. The shape can be a sheet, a plate, a column, a tube, or the like. In the present invention, a flat large-area substrate can be advantageously used. This large-area substrate is advantageously used as a catalyst substrate when producing an electron source for field emission used for a flat panel display. As a method for applying the catalyst liquid on the substrate, various conventionally known methods can be used. Such methods include brush coating, roll coating, spray coating,
A spin coating method, a method of impregnating a surface-modified substrate, and the like are included. In the present invention, a printing method such as screen printing, an ink jet method in which a liquid is ejected from a minute nozzle, or the like can be preferably employed. When the catalyst liquid is applied on the base material, the catalyst liquid can be uniformly applied to the entire surface of the base material, and may be in a linear, band, grid, dot, or any other pattern. It can be applied in a shape. By drying the substrate coated with the catalyst liquid, a catalyst substrate having ultrafine catalyst particles adhered to the surface can be obtained. The catalyst particles on the substrate may be in a state that promotes the generation of carbon nanotubes, and may be in a metal state, a metal sulfide, a metal boride, a metal oxide, a metal hydroxide, or the like. . In the case of a metal sulfide, it can be obtained by reacting a sulfurizing agent such as hydrogen sulfide with the ultrafine metal particles on the base material. The attached amount of the ultrafine catalyst particles on the substrate is in a ratio of 10 -10 to 10 -1 mol per 100 cm 2 .
【００１２】本発明によるカーボンナノチューブの製造
方法は、触媒基材の存在下で含炭素材料を熱分解し、そ
の基材上にカーボンナノチューブを生成させるカーボン
ナノチューブ生成工程と、その基材上に生成したカーボ
ンナノチューブを基材から分離するカーボンナノチュー
ブ分離工程を包含する。カーボンナノチューブ生成工程
は、その触媒基材に含炭素材料の気体を接触させた状態
おいてその含炭素材料の気体を高温に加熱し、熱分解さ
せることにより実施される。この場合の含炭素材料の加
熱方法には、マイクロ波加熱、電気ヒータによる加熱、
レーザによる加熱等の各種の加熱方法が包含されるが、
加熱帯域を特定化し得る点で、マイクロ波加熱の使用が
好ましい。[0012] The method for producing carbon nanotubes according to the present invention comprises a step of generating carbon nanotubes by thermally decomposing a carbon-containing material in the presence of a catalyst substrate and forming carbon nanotubes on the substrate. Separating the carbon nanotubes from the base material. The carbon nanotube generation step is performed by heating the gas of the carbon-containing material to a high temperature and thermally decomposing the gas in a state where the gas of the carbon-containing material is in contact with the catalyst base material. The heating method of the carbon-containing material in this case includes microwave heating, heating with an electric heater,
Various heating methods such as heating by laser are included,
Use of microwave heating is preferred in that the heating zone can be specified.
【００１３】触媒基材からのカーボンナノチューブの分
離は、その基材面にスクレーパの刃先を接触させ、その
基材からカーボンナノチューブを掻落して分離すること
ができる。前記したように、本発明で用いる基材は移動
していることから、そのスクレーパの刃先を基材面に接
触させると、その基材面に生成したカーボンナノチュー
ブは、そのスクレーパの刃先により掻落される。スクレ
ーパとしては、基板面に生成したカーボンナノチューブ
をその基材から分離し得るものであればよく、特に制約
されるものではないが、通常は、鋭利な刃先を有するブ
レードを用いることができる。The separation of the carbon nanotubes from the catalyst base material can be performed by bringing the blade of a scraper into contact with the base material surface and scraping the carbon nanotubes from the base material. As described above, since the substrate used in the present invention is moving, when the blade edge of the scraper is brought into contact with the substrate surface, the carbon nanotubes generated on the substrate surface are scraped off by the blade edge of the scraper. You. The scraper is not particularly limited as long as it can separate the carbon nanotubes generated on the substrate surface from the base material, and is not particularly limited. Usually, a blade having a sharp cutting edge can be used.
【００１４】本発明の方法は、カーボンナノチューブを
分離した後の基材上に触媒液を塗布乾燥させて、触媒基
材を再生する触媒基材再生工程を包含する。この触媒基
材の再生は、前記した触媒基材の作製工程と同様にして
実施することができる。このように再生された触媒基材
は、その表面が活性化されたもので、含炭素材料の気体
をその表面に接触させた状態で熱分解させることによ
り、その基材面にカーボンナノチューブを生成すること
ができる。The method of the present invention includes a catalyst substrate regenerating step of regenerating the catalyst substrate by applying and drying a catalyst solution on the substrate after separating the carbon nanotubes. The regeneration of the catalyst substrate can be performed in the same manner as in the above-described step of producing the catalyst substrate. The surface of the regenerated catalyst substrate is activated, and carbon nanotubes are generated on the substrate surface by thermally decomposing the gas containing the carbon-containing material in contact with the surface. can do.
【００１５】本発明の方法は、前記したカーボンナノチ
ューブの生成工程、カーボンナノチューブの分離工程及
び触媒基板の再生工程からなる一連の工程を繰返し行う
ことによって実施される。この場合、それらの一連の工
程は、触媒基材として回転移動又は往復移動するものを
用い、同じ密閉性容器内において繰返し行うのが好まし
い。[0015] The method of the present invention is carried out by repeating a series of steps including the step of producing carbon nanotubes, the step of separating carbon nanotubes, and the step of regenerating a catalyst substrate. In this case, it is preferable that a series of these steps be repeatedly performed in the same hermetically sealed container using a catalyst substrate that rotates or reciprocates.
【００１６】図１に本発明の実施に際して用いられるフ
ロー説明図を示す。図１において、１１は密閉容器、１
２はガス導入管、１３はガス排出管を示す。Ａは、触媒
基材と、加熱装置と、スクレーパとからなる密閉容器内
に配置される設備を示す。容器内設備Ａは、前記した一
連の工程を連続的又は間欠的に繰返し実施し得るもので
あればよく、その具体的構造例を図２〜図４に示す。こ
れらの図において、１は触媒基材、２は触媒液塗布器、
３は触媒液塗布面（活性化表面）、４はマイクロ波発振
器、５は導波管、６はカーボンナノチューブ、７はスク
レーパ、８は回転軸を各示す。FIG. 1 is an explanatory diagram of a flow used in carrying out the present invention. In FIG. 1, reference numeral 11 denotes a closed container, 1
Reference numeral 2 denotes a gas introduction pipe, and 13 denotes a gas discharge pipe. A shows equipment arranged in a closed container including a catalyst base material, a heating device, and a scraper. The in-vessel equipment A is only required to be able to repeat the above-described series of steps continuously or intermittently, and specific examples of its structure are shown in FIGS. In these figures, 1 is a catalyst substrate, 2 is a catalyst liquid applicator,
Reference numeral 3 denotes a catalyst liquid application surface (activation surface), 4 denotes a microwave oscillator, 5 denotes a waveguide, 6 denotes a carbon nanotube, 7 denotes a scraper, and 8 denotes a rotation axis.
【００１７】図２に示した設備Ａにおいて、円板状の触
媒基材１は連続的又は間欠的に回転する。この設備Ａを
用いてカーボンナノチューブを製造する際には、その基
材１の表面に触媒液塗布器２から触媒液を塗布乾燥して
基材表面を活性化させる。この活性化表面３を有する触
媒基材は、その回転軸９により矢印方向に回転している
ことから、導波管５の位置に移動し、ここでマイクロ波
の照射を受ける。マイクロ波の照射を受けた基材面は、
高温に加熱され、この基材面に接触する含炭素材料の気
体は熱分解され、その基材面にカーボンナノチューブが
生成される。カーボンナノチューブの生成した基材面
は、その回転によりスクレーパ７の位置に移動し、ここ
でその基材上のカーボンナノチューブはそのスクレーパ
７により掻落される。カーボンナノチューブの掻落され
た後の基材面は、その回転により、触媒液塗布器２の位
置に移動し、ここで触媒液が塗布乾燥される。In the equipment A shown in FIG. 2, the disc-shaped catalyst substrate 1 rotates continuously or intermittently. When carbon nanotubes are produced using this equipment A, the catalyst liquid is applied to the surface of the substrate 1 from the catalyst liquid applicator 2 and dried to activate the substrate surface. Since the catalyst substrate having the activation surface 3 is rotated in the direction of the arrow by the rotation axis 9, the catalyst substrate moves to the position of the waveguide 5, where it is irradiated with microwaves. The substrate surface that has been irradiated with microwaves
Heated to a high temperature, the gas of the carbon-containing material that comes into contact with the substrate surface is thermally decomposed, and carbon nanotubes are generated on the substrate surface. The rotation of the base material surface on which the carbon nanotubes are generated moves to the position of the scraper 7, where the carbon nanotubes on the base material are scraped off by the scraper 7. The substrate surface after the carbon nanotubes are scraped is moved to the position of the catalyst liquid applicator 2 by its rotation, where the catalyst liquid is applied and dried.
【００１８】図３に示した設備Ａにおいて、長方形状の
板体からなる触媒基材１は、矢印方向に連続的又は間欠
的に往復移動する。この設備Ａを用いてカーボンナノチ
ューブを製造する際には、図面において左側方向（又は
下方向）に移動するその基材１の表面に触媒液塗布器２
から触媒液を塗布乾燥して基材表面を活性化させる。こ
の活性化表面３を有する触媒基材は、矢印方向に往復移
動することから、導波管５の位置に移動し、ここでマイ
クロ波の照射を受ける。高マイクロ波の照射を受けた基
材面は、高温は加熱され、この基材面に接触する含炭素
材料の気体は熱分解され、その基材面にカーボンナノチ
ューブが生成される。カーボンナノチューブの生成した
基材面は、その基材の移動によりスクレーパ７の位置に
移動し、ここでその基材上のカーボンナノチューブはそ
のスクレーパ７により掻落される。基材１の右端ａ（又
は上端ａ）がスクレーパ７の位置より左側（又は下方）
まで移動したときに、基材１は右方向（又は上方向）に
移動し、その基材の左端（又は下端）が触媒液塗布器２
の位置より右端（又は上側）にまで移動したときに、基
材１は再び左側（又は下方向）に移動する。基材１が右
側（又は上方向）に移動するときには、そのマイクロ波
発振器４及び触媒液塗布器２は、その操作停止するかあ
るいはその移動を急速に行う。In the equipment A shown in FIG. 3, the catalyst substrate 1 composed of a rectangular plate reciprocates continuously or intermittently in the direction of the arrow. When carbon nanotubes are manufactured using this equipment A, the catalyst liquid applicator 2 is applied to the surface of the substrate 1 which moves leftward (or downward) in the drawing.
To activate the substrate surface by applying and drying a catalyst solution. Since the catalyst substrate having the activation surface 3 reciprocates in the direction of the arrow, it moves to the position of the waveguide 5, where it is irradiated with microwaves. The substrate surface that has been irradiated with the high microwaves is heated at a high temperature, and the gas of the carbon-containing material that comes into contact with the substrate surface is thermally decomposed to generate carbon nanotubes on the substrate surface. The substrate surface on which the carbon nanotubes are generated moves to the position of the scraper 7 due to the movement of the substrate, where the carbon nanotubes on the substrate are scraped off by the scraper 7. The right end a (or the upper end a) of the substrate 1 is on the left side (or below) the position of the scraper 7
When the base material 1 moves to the right (or upward), the left end (or lower end) of the base material is
When the substrate 1 moves to the right end (or upper side) from the position, the substrate 1 moves to the left side (or lower direction) again. When the substrate 1 moves to the right (or upward), the operation of the microwave oscillator 4 and the catalyst liquid applicator 2 is stopped or the movement is rapidly performed.
【００１９】図４に示した設備Ａにおいて、円柱状又は
円筒状の触媒基材１は連続的又は間欠的に回転する。こ
の設備Ａを用いてカーボンナノチューブを製造する際に
は、その基材１の側面に触媒液塗布器２から触媒液を塗
布乾燥して基材表面を活性化させる。この活性化表面３
を有する触媒基材は、その回転軸８により矢印方向に回
転されていることから、導波管５の位置に移動し、ここ
でマイクロ波の照射を受ける。マイクロ波の照射を受け
た基材面は、高温は加熱され、この基材面に接触する含
炭素材料の気体は熱分解され、その基材面にカーボンナ
ノチューブが生成される。カーボンナノチューブの生成
した基材面は、その回転によりスクレーパ７の位置に移
動し、ここでその基材上のカーボンナノチューブはその
スクレーパ７により掻落される。カーボンナノチューブ
の掻落された後の基材面は、その回転により、触媒液塗
布器２の位置に移動し、ここで触媒液が塗布乾燥され
る。In the equipment A shown in FIG. 4, the columnar or cylindrical catalyst substrate 1 rotates continuously or intermittently. When carbon nanotubes are manufactured using this equipment A, the catalyst liquid is applied to the side surface of the substrate 1 from the catalyst liquid applicator 2 and dried to activate the substrate surface. This activated surface 3
Is rotated in the direction of the arrow by the rotation axis 8 thereof, and moves to the position of the waveguide 5 where it is irradiated with microwaves. The substrate surface that has been irradiated with the microwaves is heated at a high temperature, the gas of the carbon-containing material that comes into contact with the substrate surface is thermally decomposed, and carbon nanotubes are generated on the substrate surface. The rotation of the base material surface on which the carbon nanotubes are generated moves to the position of the scraper 7, where the carbon nanotubes on the base material are scraped off by the scraper 7. The substrate surface after the carbon nanotubes are scraped is moved to the position of the catalyst liquid applicator 2 by its rotation, where the catalyst liquid is applied and dried.
【００２０】前記で示した容器内設備Ａは、いずれもそ
の加熱装置としてマイクロ波発振器を用いるものである
が、その加熱装置としては、電気加熱炉を用いることも
可能である。この場合には、その容器内が高温に保持さ
れることから、触媒液塗布器２は、これを断熱材で保護
するとともに、水冷して、触媒液の蒸発による損失を防
止する。Each of the in-vessel equipment A described above uses a microwave oscillator as a heating device, but an electric heating furnace can be used as the heating device. In this case, since the inside of the container is kept at a high temperature, the catalyst liquid applicator 2 protects the container with a heat insulating material and water-cools to prevent loss due to evaporation of the catalyst liquid.
【００２１】本発明で用いる含炭素材料は特に制約され
ず、高温で炭素化されるものであればよい。このような
ものとしては、一酸化炭素の他、メタン、エタン、プロ
パン、ブタン等の飽和炭化水素；エチレン、プロピレ
ン、ブテン、イソブテン等の不飽和炭化水素；アセチレ
ン等のアセチレン系化合物；ベンゼン、トルエン、キシ
レン、ナフタレン等の芳香族炭化水素、これらの混合物
（例えば、ナフサや軽油等）等が包含される。本発明で
は、取扱いの容易さや、価格の点、炭素含有率等の点か
ら、有機炭素材料、特に、沸点が８０〜１４４℃の液状
芳香族炭化水素、例えば、ベンゼル、トルエン、キシレ
ン、それらの混合物の使用が好ましい。The carbon-containing material used in the present invention is not particularly limited as long as it can be carbonized at a high temperature. Examples of such compounds include, in addition to carbon monoxide, saturated hydrocarbons such as methane, ethane, propane, and butane; unsaturated hydrocarbons such as ethylene, propylene, butene, and isobutene; acetylene-based compounds such as acetylene; , Xylene, naphthalene, and other aromatic hydrocarbons, and mixtures thereof (for example, naphtha, light oil, and the like). In the present invention, in terms of ease of handling, price, carbon content, etc., organic carbon materials, particularly liquid aromatic hydrocarbons having a boiling point of 80 to 144 ° C., such as benzene, toluene, xylene, and the like, The use of a mixture is preferred.
【００２２】前記含炭素材料を熱分解する場合、その含
炭素材料の気体中に水素ガスをキャリアーガスとして混
入することができる。また、含炭素材料には、硫化水素
やメルカプタン等のイオウ化合物を適量加えることがで
きる。これにより、基材上に真っ直ぐなカーボンナノチ
ューブを得ることができる。When the carbon-containing material is thermally decomposed, hydrogen gas can be mixed as a carrier gas into the gas of the carbon-containing material. Further, an appropriate amount of a sulfur compound such as hydrogen sulfide or mercaptan can be added to the carbon-containing material. Thereby, straight carbon nanotubes can be obtained on the base material.
【００２３】図１に示した装置を用いてカーボンナノチ
ューブの製造を行うには、気体状の含炭素材料又は液体
状の含炭素材料を気化させて形成した気体を、水素等の
キャリヤーガスや気体状のイオウ化合物もしくはイオウ
化合物を気化して形成した気体とともに、ガス導入管１
２を介して密閉容器１１内に導入する。容器１１内に
は、設備Ａが配設されており、この容器内において、前
記した一連の工程が繰返し実施される。容器１１内の温
度は、含炭素材料を熱分解する方式により異なるが、マ
イクロ波による加熱装置を用いる場合、その加熱帯域
は、そのマイクロ波発振器に連通する導波管により特定
化されるので、その加熱帯域のみが高温加熱される。従
って、密閉容器内の空間温度はそれ程高温度にならず、
通常５００℃以下である。一方、電気加熱炉等で密閉容
器を加熱する場合には、その容器内温度は、その含炭素
材料の熱分解温度（たとえば、４００〜１５００℃、好
ましくは８００〜１２００℃）に保持される。前記設備
Ａで得られるカーボンナノチューブは、その容器間底部
に収容され、一方、容器内のガスは、真空排気系に連通
するガス排出管１３を介して排出される。In order to produce carbon nanotubes using the apparatus shown in FIG. 1, a gas formed by vaporizing a gaseous carbon-containing material or a liquid carbon-containing material is converted into a carrier gas such as hydrogen or a gas. Together with a sulfur compound in a gaseous state or a gas formed by vaporizing a sulfur compound,
2 into the closed container 11. The equipment A is provided in the container 11, and the series of steps described above is repeatedly performed in the container. The temperature in the container 11 varies depending on the method of thermally decomposing the carbon-containing material. However, when a heating device using a microwave is used, the heating zone is specified by a waveguide communicating with the microwave oscillator. Only that heating zone is heated to a high temperature. Therefore, the space temperature in the closed container does not become so high,
It is usually 500 ° C. or less. On the other hand, when the closed container is heated by an electric heating furnace or the like, the temperature in the container is maintained at the thermal decomposition temperature of the carbon-containing material (for example, 400 to 1500 ° C, preferably 800 to 1200 ° C). The carbon nanotubes obtained in the facility A are accommodated in the bottom between the containers, while the gas in the container is exhausted through a gas exhaust pipe 13 communicating with a vacuum exhaust system.
【００２４】[0024]
【発明の効果】本発明によれば、カーボンナノチューブ
を連続的かつ安価に製造することができるので、その産
業的意義は多大である。According to the present invention, carbon nanotubes can be continuously and inexpensively produced, so that their industrial significance is great.
【００２５】[0025]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００２６】実施例１ （１）触媒液の調製 トルエン９ｇ中にカチオン性界面活性剤であるジデシル
ジメチルアンモニウムブロマイド（ＤＤＡＢ）を１ｇ溶
かし１時間攪拌する。次に塩化コバルト六水和物１２ｍ
ｇを溶液中に導入し、さらに１時間攪拌する。この溶液
は透明な水色を示す。その後、０．００５Ｍの水素化ホ
ウ素ナトリウム水溶液を１５μｌ滴下して塩化コバルト
を還元する。滴下後、溶液は黒く懸濁し銀白色の沈殿物
を生じる。次に、この沈殿物を含む溶液を１２０００ｒ
ｐｍで１０分間遠心分離機にかけ、上澄みを除去した
後、トルエンを追加して再分散し、遠心処理する工程を
を４回繰り返すことにより、余分な界面活性剤を除去
し、コバルト粒子を精製する。このようにして得られた
触媒液において、そのコバルト粒子の平均粒径は、約４
ｎｍであった。また、その界面活性剤濃度は、１重量％
以下であった。Example 1 (1) Preparation of Catalyst Solution In 9 g of toluene, 1 g of didecyldimethylammonium bromide (DDAB) as a cationic surfactant was dissolved and stirred for 1 hour. Next, cobalt chloride hexahydrate 12m
g are introduced into the solution and stirred for a further hour. This solution shows a clear light blue color. Thereafter, 15 μl of a 0.005 M aqueous sodium borohydride solution is added dropwise to reduce cobalt chloride. After the addition, the solution is suspended in black and forms a silver-white precipitate. Next, the solution containing the precipitate was added to 12,000 r.
After centrifuging at 10 pm for 10 minutes to remove the supernatant, re-dispersing by adding toluene, and repeating the process of centrifugation four times to remove excess surfactant and purify the cobalt particles. . In the catalyst solution thus obtained, the average particle size of the cobalt particles is about 4
nm. The surfactant concentration is 1% by weight.
It was below.
【００２７】（２）触媒基材の作製 前記（１）で得た触媒液を、５ｍｍ四方のシリコン基材
上に滴下して、均一な触媒液膜を形成した後、これを室
温℃で乾燥してその基材面にコバルト粒子を付着させ
た。これにより、表面にコバルト粒子が均一に付着した
触媒基材を得ることができた。次に、この触媒基材のコ
バルト粒子に対して、硫化水素/水素混合ガス（硫化水
素濃度：１０モル％）を４００℃で２時間流通接触させ
て、硫化水素の還元とコバルト粒子の硫化を同時に行っ
て、硫化コバルト粒子が表面に付着した触媒基材を得
た。(2) Preparation of catalyst base material The catalyst solution obtained in the above (1) was dropped on a silicon substrate of 5 mm square to form a uniform catalyst solution film, which was then dried at room temperature. Then, cobalt particles were attached to the substrate surface. As a result, a catalyst substrate having cobalt particles uniformly adhered to the surface was obtained. Next, a hydrogen sulfide / hydrogen mixed gas (hydrogen sulfide concentration: 10 mol%) is brought into flow contact with the cobalt particles of the catalyst substrate at 400 ° C. for 2 hours to reduce hydrogen sulfide and sulfide the cobalt particles. Simultaneously, a catalyst substrate having cobalt sulfide particles adhered to the surface was obtained.
【００２８】（３）カーボンナノチューブの合成 前記（２）で得た触媒基材を密閉容器に入れ、アセチレ
ン／Ｎ2混合ガス（アセチレン濃度：１モル％）を流通
させながらその基材表面に、−３５０〜−４００Ｖのバ
イアス電圧をかけながら、マイクロ波導波管を介してマ
イクロ波（周波数：２４５０ＭＨｚ）を照射した。この
マイクロ波照射した。次に、この基材を容器から取出し
た。この基材垂直に配向した真っ直ぐなカーボンナノチ
ューブが生成されていることが確認された。このカーボ
ンナノチューブをブレード刃により基材から掻落して分
離した。次に、このカーボンナノチューブを分離した後
の基材を用い、前記一連の操作を繰返した。この場合に
も、基材上にカーボンナノチューブが生成していること
が確認された。(3) Synthesis of Carbon Nanotubes The catalyst base material obtained in the above (2) is placed in a closed container, and an acetylene / N 2 mixed gas (acetylene concentration: 1 mol%) is passed through the base material surface while flowing the mixture. Microwaves (frequency: 2450 MHz) were irradiated through a microwave waveguide while applying a bias voltage of -350 to -400V. This microwave irradiation was performed. Next, the substrate was taken out of the container. It was confirmed that straight carbon nanotubes oriented perpendicular to the substrate were generated. The carbon nanotubes were scraped off from the substrate by a blade blade and separated. Next, the above series of operations was repeated using the base material after separating the carbon nanotubes. Also in this case, it was confirmed that carbon nanotubes were generated on the substrate.
【００２９】前記カーボンナノチューブの合成において
は、容器内のおける基材の移動、触媒液の塗布及び生成
したカーボンナノチューブの基材からの分離は行わなか
ったが、これらの操作は、実装置においては、適当な装
置の配置により、容易に実施することができるものであ
る。従って、同一容器内において、前記一連の操作を繰
返し行うことにより、カーボンナノチューブを連続的に
製造することができ、工業的に有利なプロセスを得るこ
とができる。In the synthesis of the carbon nanotubes, the movement of the substrate in the vessel, the application of the catalyst solution, and the separation of the generated carbon nanotubes from the substrate were not performed. , Can be easily implemented by arranging appropriate devices. Therefore, by repeatedly performing the above series of operations in the same container, carbon nanotubes can be continuously produced, and an industrially advantageous process can be obtained.
【図１】本発明を実施する場合のフロー説明図である。FIG. 1 is an explanatory diagram of a flow when implementing the present invention.
【図２】本発明の実施例に際して密閉容器内に配置され
る設備の１つの例についての構造説明図である。FIG. 2 is a structural explanatory view of one example of equipment arranged in a closed container in the embodiment of the present invention.
【図３】本発明の実施例に際して密閉容器内に配置され
る設備の他の例についての構造説明図である。FIG. 3 is a structural explanatory view of another example of equipment arranged in a closed container in the embodiment of the present invention.
【図４】本発明の実施例に際して密閉容器内に配置され
る設備のさらに他の例についての構造説明図である。FIG. 4 is a structural explanatory view of still another example of the equipment arranged in the closed container in the embodiment of the present invention.
１ 基材 ２ 触媒液塗布器 ３ 触媒液塗布面 ４ マイクロ波発振器 ５ 導波管 ６ カーボンナノチューブ ７ スクレーパ １１ 密閉容器 DESCRIPTION OF SYMBOLS 1 Base material 2 Catalyst liquid applicator 3 Catalyst liquid application surface 4 Microwave oscillator 5 Waveguide 6 Carbon nanotube 7 Scraper 11 Sealed container
【手続補正書】[Procedure amendment]
【提出日】平成１２年７月１７日（２０００．７．１
７）[Submission Date] July 17, 2000 (2007.1)
7)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００４[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、含炭素材料を触媒基
材の存在下で熱分解してカーボンナノチューブを製造す
る方法において、（ｉ）触媒基材の存在下で含炭素材料
を熱分解させて該基材上にカーボンナノチューブを生成
させる工程、（ii）該生成したカーボンナノチューブを
該基材から分離する工程、(iii）該カーボンナノチュー
ブを分離した後の基材上に触媒超微粒子を含む触媒液を
塗布乾燥して、触媒基材を再生する工程、（iv）該再生
基材の存在下で含炭素材料を熱分解させて該基材上にカ
ーボンナノチューブを生成させる工程、からなる一連の
工程を、連続的又は間欠的に回転又は往復移動する触媒
基材を用いて、同じ密閉容器内において繰返し行うこと
を特徴とするカーボンナノチューブの製造方法が提供さ
れる。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, in a method for producing carbon nanotubes by thermally decomposing a carbon-containing material in the presence of a catalyst substrate, (i) thermally decomposing the carbon-containing material in the presence of a catalyst substrate, A step of generating carbon nanotubes on a substrate, (ii) a step of separating the generated carbon nanotubes from the substrate, and (iii) a catalyst solution containing ultrafine catalyst particles on the substrate after the carbon nanotubes are separated. Coating and drying to regenerate the catalyst substrate, and (iv) a step of thermally decomposing the carbon-containing material in the presence of the regenerated substrate to form carbon nanotubes on the substrate. , A catalyst that rotates or reciprocates continuously or intermittently
There is provided a method for producing carbon nanotubes, wherein the method is repeatedly performed in the same closed container using a substrate .
───────────────────────────────────────────────────── フロントページの続き (71)出願人 597045549 湯村 守雄 茨城県つくば市竹園３−411−４ (71)出願人 598129118 内田 邦夫 茨城県つくば市吾妻２−805−1207 (71)出願人 597045561 伊ヶ崎 文和 茨城県つくば市松代５−629−２ (71)出願人 597045550 栗木 安則 茨城県つくば市並木２−142−102 (74)上記６名の代理人 100074505 弁理士 池浦 敏明 (72)発明者 大嶋 哲 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 吾郷 浩樹 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 湯村 守雄 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 内田 邦夫 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 伊ヶ崎 文和 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 栗木 安則 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 Ｆターム(参考） 4G046 CA01 CC01 CC06 CC08 4G069 AA03 AA08 BB02A BB04A BB09B BB18A BC31A BC54A BC59A BC66A BC67A BC67B BC68A BC72A BD01A BD01B BD05B CB81 DA06 EA01Y EA08 FA03 FB17 FB18 FB19 FB20 FC04 ──────────────────────────────────────────────────の Continuing from the front page (71) Applicant 597045549 Morio Yumura 3-411-4 Takezono, Tsukuba, Ibaraki (71) Applicant 598129118 Kunio Uchida 2-805-1207, Azuma, Tsukuba, Ibaraki (71) Applicant 597045561 Igasaki Bunwa Ibaraki Prefecture Tsukuba City Matsushiro 5-629-2 (71) Applicant 597045550 Kuriki Yasunori Ibaraki Prefecture Tsukuba City Namiki 2-142-102 (74) The above six agents 100074505 Patent Attorney Ikeura Toshiaki (72) Inventor Oshima Tetsu Ichigo, Tsukuba City, Ibaraki Prefecture 1-1-1, Higashi, National Institute of Advanced Industrial Science and Technology (72) Inventor Hiroki Ago 1-1-1, Higashi, Tsukuba City, Ibaraki Prefecture, National Institute of Advanced Industrial Science and Technology (72) Inventor, Morio Yumura Morio Yumura Ibaraki 1-1-1 Higashi, Tsukuba, Japan Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Kunio Uchida 1 Higashi, Tsukuba, Ibaraki No. 1 Inside the Institute of Materials Science and Technology, Institute of Industrial Science and Technology (72) Inventor Bunkazu Igasaki 1-1, Higashi, Tsukuba, Ibaraki Prefecture Inside the Institute of Materials Science and Technology, Institute of Industrial Science and Technology (72) Inventor Yasunori Kuriki 1, Higashi, Tsukuba, Ibaraki No. 1 F-term in the National Institute of Advanced Industrial Science and Technology, Material Engineering and Industrial Technology Research Laboratories
Claims (2)
してカーボンナノチューブを製造する方法において、
（ｉ）触媒基材の存在下で含炭素材料を熱分解させて該
基材上にカーボンナノチューブを生成させる工程、（i
i）該生成したカーボンナノチューブを該基材から分離
する工程、(iii）該カーボンナノチューブを分離した後
の基材上に触媒超微粒子を含む触媒液を塗布乾燥して、
触媒基材を再生する工程、（iv）該再生触媒基材の存在
下で含炭素材料を熱分解させて該基材上にカーボンナノ
チューブを生成させる工程、からなる一連の工程を繰返
し行うことを特徴とするカーボンナノチューブの製造方
法。A method for producing carbon nanotubes by thermally decomposing a carbon-containing material in the presence of a catalyst substrate,
(I) a step of thermally decomposing the carbon-containing material in the presence of the catalyst substrate to form carbon nanotubes on the substrate;
i) a step of separating the generated carbon nanotubes from the substrate, (iii) a catalyst liquid containing ultrafine catalyst particles is applied and dried on the substrate after separating the carbon nanotubes,
Repeating a series of steps including a step of regenerating a catalyst base material, and (iv) a step of thermally decomposing a carbon-containing material in the presence of the regenerated catalyst base material to generate carbon nanotubes on the base material. A method for producing a carbon nanotube, which is characterized by:
動する触媒基材を用いて、同じ密閉容器内において行う
請求項１の方法。2. The method according to claim 1, wherein the series of steps is carried out in the same closed vessel using a catalyst substrate that moves continuously or intermittently.
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