JP2016064972A - Carbon nanofiber production process and carbon nanofiber - Google Patents
Carbon nanofiber production process and carbon nanofiber Download PDFInfo
- Publication number
- JP2016064972A JP2016064972A JP2015128444A JP2015128444A JP2016064972A JP 2016064972 A JP2016064972 A JP 2016064972A JP 2015128444 A JP2015128444 A JP 2015128444A JP 2015128444 A JP2015128444 A JP 2015128444A JP 2016064972 A JP2016064972 A JP 2016064972A
- Authority
- JP
- Japan
- Prior art keywords
- cnf
- catalyst
- carbon
- cobalt
- oxide
- 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
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 148
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 128
- 239000010941 cobalt Substances 0.000 claims abstract description 57
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 54
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 17
- 238000001069 Raman spectroscopy Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 description 70
- 238000003786 synthesis reaction Methods 0.000 description 69
- 238000011068 loading method Methods 0.000 description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 26
- 238000005259 measurement Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 238000009826 distribution Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002048 multi walled nanotube Substances 0.000 description 5
- 239000010412 oxide-supported catalyst Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- -1 oxides Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical group [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- KEHCHOCBAJSEKS-UHFFFAOYSA-N iron(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Fe+2] KEHCHOCBAJSEKS-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KJLFZWJDCDJCFB-UHFFFAOYSA-N nickel(ii) titanate Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ni+2] KJLFZWJDCDJCFB-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Abstract
Description
本発明は、活性種としてコバルトを主成分とする金属を、チタンを含有する比表面積が２０〜１４０ｍ２／ｇの酸化物または複合酸化物からなる担体に担持した触媒を用いた、一酸化炭素を炭素源とするカーボンナノファイバーの製造方法、並びにこの製造方法により得られるカーボンナノファイバーに関する。 The present invention relates to carbon monoxide using a catalyst in which a metal having cobalt as a main component as an active species is supported on a support containing an oxide or composite oxide containing titanium and having a specific surface area of 20 to 140 m 2 / g. The present invention relates to a method for producing carbon nanofibers using as a carbon source, and carbon nanofibers obtained by this production method.
樹脂に導電性付与するためのフィラーとして、あるいは各種電池、特にリチウムイオン電池の電極の導電性付与材として、導電性炭素材であるアセチレンブラックやカーボンナノファイバー（以下ＣＮＦと記載）、およびこれらの混合物が用いられる。特にＣＮＦを用いるあるいは添加する場合、比較的低い導電性炭素材含量で高い導電率が得られる特徴があり、期待が集まっている。ここでＣＮＦは一般的に５〜１００ｎｍの外径、ファイバー長の外径に対する比を示すアスペクト比は１０以上という繊維状の形状を有する。 As a filler for imparting conductivity to a resin, or as a conductivity imparting material for electrodes of various batteries, particularly lithium ion batteries, acetylene black or carbon nanofiber (hereinafter referred to as CNF), which is a conductive carbon material, and these A mixture is used. In particular, when CNF is used or added, there is a feature that high conductivity can be obtained with a relatively low content of conductive carbon material, and expectations are gathered. Here, CNF generally has a fibrous shape having an outer diameter of 5 to 100 nm and an aspect ratio indicating a ratio of the fiber length to the outer diameter of 10 or more.
従来、ＣＮＦの製造には、電極放電法、触媒気相成長法、レーザ法等が用いられている。このうち、触媒気相成長法では、工業的にＣＮＦを成長させる遷移金属粒子を触媒とし、炭素源である原料ガス、たとえばアセチレンやベンゼンと接触させることにより、一般的には９００℃以上の高温で触媒粒子よりＣＮＦを成長させる。なかでも、コバルト等の遷移金属成分を触媒とし、原料として一酸化炭素を主体とするガスからＣＮＦを製造する方法が、高純度、高品位のＣＮＦを、比較的低温で得る方法として着目されている（特許文献１〜５）。 Conventionally, an electrode discharge method, a catalytic vapor phase growth method, a laser method, or the like is used for manufacturing CNF. Among them, in the catalytic vapor phase growth method, transition metal particles for industrially growing CNF are used as a catalyst, and are generally brought into contact with a source gas that is a carbon source, for example, acetylene or benzene. Then, CNF is grown from the catalyst particles. Among them, a method of producing CNF from a gas mainly composed of carbon monoxide as a raw material using a transition metal component such as cobalt as a catalyst has attracted attention as a method for obtaining high purity and high quality CNF at a relatively low temperature. (Patent Documents 1 to 5).
しかし、これらの方法により得られたＣＮＦを樹脂の導電材または導電助剤として使用する場合、導電性は十分ではなく、さらなる高導電性（低体積抵抗率）のＣＮＦが求められている。また、これらの方法により得られたＣＮＦを樹脂に添加した場合、ＣＮＦの合成過程で生じたＣＮＦの絡まり合いにより樹脂中に十分に分散できず、さらなる高分散性のＣＮＦが求められている。 However, when CNF obtained by these methods is used as a resin conductive material or a conductive additive, the conductivity is not sufficient, and CNF having higher conductivity (low volume resistivity) is required. In addition, when CNF obtained by these methods is added to a resin, it cannot be sufficiently dispersed in the resin due to entanglement of CNF generated in the synthesis process of CNF, and further highly dispersible CNF is demanded.
本発明は、上記問題と実情に鑑み、活性種としてコバルトを主成分とする金属を、チタンを含有する比表面積２０〜１４０ｍ２／ｇの酸化物または複合酸化物に担持させた触媒を用いた、一酸化炭素を炭素源とするＣＮＦの製造方法、およびこの製造方法により得られる高い結晶性、高い導電性、高い分散性を有するＣＮＦを提供することを目的とする。 In view of the above problems and circumstances, the present invention uses a catalyst in which a metal mainly composed of cobalt as an active species is supported on an oxide or composite oxide containing titanium and having a specific surface area of 20 to 140 m 2 / g. An object of the present invention is to provide a method for producing CNF using carbon monoxide as a carbon source, and CNF having high crystallinity, high conductivity, and high dispersibility obtained by this production method.
すなわち、上記課題を解決する本発明は、下記より構成される。 That is, this invention which solves the said subject is comprised from the following.
（１）コバルトを主成分とする活性種を、チタンを含有する比表面積が２０〜１４０ｍ２／ｇの酸化物または複合酸化物からなる担体に担持した触媒を用いた、一酸化炭素を炭素源とするカーボンナノファイバーの製造方法。
（２）前記コバルトを主成分とする活性種が、前記チタンを含有する酸化物または複合酸化物からなる担体に０．１〜５０質量％担持した、（１）に記載のカーボンナノファイバーの製造方法。
（３）前記チタンの結晶構造がルチル構造からなる酸化物、またはルチル構造とアナタース構造の両方を含む酸化物から選択される、（１）または（２）に記載のカーボンナノファイバーの製造方法。
（４）反応温度が６００〜８００℃であり、全圧が０．０５〜０．９８ＭＰａであり、一酸化炭素分圧が全圧に対し３０〜９５％であり、水素分圧が一酸化炭素分圧に対し１〜５０％の原料ガスを用いた条件下にて製造する、（１）〜（３）のいずれか一つに記載のカーボンナノファーバーの製造方法。
（５）反応温度が６５０〜８００℃である、（４）に記載のカーボンナノファーバーの製造方法。
（６）（５）に記載の製造方法で得られる、９．８ＭＰａの荷重下で測定した体積抵抗率が０．０３Ω・ｃｍ以下、ラマン分光測定で得られるＤ／Ｇ値が１．０以下、トルエン中の１０μｍ以下の分散粒子が９０体積％以上、の条件を全て満たすカーボンナノファイバー。
（７）９．８ＭＰａの荷重下で測定した体積抵抗率が０．０３Ω・ｃｍ以下、ラマン分光測定で得られるＤ／Ｇ値が１．０以下、トルエン中の１０μｍ以下の分散粒子が９０体積％以上、の条件を全て満たすカーボンナノファイバー。
(1) Carbon monoxide as a carbon source using a catalyst in which an active species containing cobalt as a main component is supported on a support made of an oxide or composite oxide containing titanium and having a specific surface area of 20 to 140 m 2 / g A method for producing carbon nanofibers.
(2) The production of carbon nanofibers according to (1), wherein the active species containing cobalt as a main component is supported in an amount of 0.1 to 50% by mass on a support made of an oxide or composite oxide containing titanium. Method.
(3) The method for producing carbon nanofibers according to (1) or (2), wherein the titanium crystal structure is selected from an oxide having a rutile structure or an oxide containing both a rutile structure and an anatase structure.
(4) The reaction temperature is 600 to 800 ° C., the total pressure is 0.05 to 0.98 MPa, the carbon monoxide partial pressure is 30 to 95% of the total pressure, and the hydrogen partial pressure is carbon monoxide. The method for producing a carbon nanofiber according to any one of (1) to (3), wherein the production is performed under a condition using 1 to 50% of a source gas with respect to a partial pressure.
(5) The method for producing a carbon nanofiber according to (4), wherein the reaction temperature is 650 to 800 ° C.
(6) The volume resistivity obtained by the production method described in (5), measured under a load of 9.8 MPa, is 0.03 Ω · cm or less, and the D / G value obtained by Raman spectroscopy is 1.0 or less. Carbon nanofibers that satisfy all the conditions that dispersed particles of 10 μm or less in toluene are 90% by volume or more.
(7) The volume resistivity measured under a load of 9.8 MPa is 0.03 Ω · cm or less, the D / G value obtained by Raman spectroscopic measurement is 1.0 or less, and the dispersed particles of 10 μm or less in toluene are 90 volumes. % Of carbon nanofibers that satisfy all of the above conditions.
一酸化炭素を炭素源としＣＮＦを製造する際、特定組成のコバルト／チタン系担持触媒を用いることで、高い結晶性、高い導電性、高い分散性のＣＮＦを製造することが出来ることを見出した。また、本発明によるＣＮＦは、分散性の改善により導電性ネットワークが向上するため、樹脂等に導電フィラーとして用いた場合、導電性が良好となる。 When producing CNF using carbon monoxide as a carbon source, it was found that CNF having high crystallinity, high conductivity, and high dispersibility can be produced by using a cobalt / titanium-based supported catalyst having a specific composition. . In addition, since the conductive network of the CNF according to the present invention improves the dispersibility, the conductivity becomes good when used as a conductive filler in a resin or the like.
本明細書におけるカーボンナノファイバー（ＣＮＦ）の定義は、平均外径５〜１００ｎｍ、ファイバー長の外径に対する比を示すアスペクト比が１０以上であり、多層カーボンナノチューブ（ＭＷＣＮＴ）をも包含する概念であり、より好ましくは、多層カーボンナノチューブを主成分とするものである。本明細書におけるカーボンナノファイバー（ＣＮＦ）の定義には単層カーボンナノチューブ（ＳＷＣＮＴ）は含まれない。単層カーボンナノチューブは高導電性を示す特徴が有るが、カイラリティによる異性体が存在し、またバンドル構造をとる等、実用上の課題が有り、本願の目的とするものではない。本明細書のカーボンナノファイバー（ＣＮＦ）としては、多層カーボンナノチューブが最も好ましい。 The definition of the carbon nanofiber (CNF) in the present specification is a concept including an average outer diameter of 5 to 100 nm, an aspect ratio indicating a ratio of the fiber length to the outer diameter of 10 or more, and also includes a multi-walled carbon nanotube (MWCNT). More preferably, the main component is a multi-walled carbon nanotube. The definition of carbon nanofiber (CNF) in this specification does not include single-walled carbon nanotubes (SWCNT). Single-walled carbon nanotubes have the characteristics of high conductivity, but there are practical problems such as the presence of isomers due to chirality and the formation of a bundle structure, and this is not the purpose of this application. As the carbon nanofiber (CNF) in the present specification, a multi-walled carbon nanotube is most preferable.
本明細書における合成活性とは、単位活性種質量あたり、単位時間あたり得られたＣＮＦの質量である。また本明細書における収量とは単位活性種質量あたり得られたＣＮＦの質量である。ここでいう活性種とはコバルトを主成分とする金属である。 The synthetic activity in this specification is the mass of CNF obtained per unit time per unit active species mass. Moreover, the yield in this specification is the mass of CNF obtained per unit active species mass. The active species here is a metal containing cobalt as a main component.
さらに担体とは、該活性種を担持するための、酸化物または複合酸化物を意味する。 Further, the carrier means an oxide or a composite oxide for supporting the active species.
＜活性種＞
本発明は、コバルトを主成分とする活性種を、チタンを含有する酸化物または複合酸化物に担持させたＣＮＦ製造用の固体触媒（以下コバルト／チタン系担持触媒と記載）を用いた、一酸化炭素を炭素源とするＣＮＦの製造である。本発明のコバルト／チタン系担持触媒はＣＮＦ製造の実質的な活性種としてコバルト成分を有する。コバルトとは、金属コバルトのみならず、酸化物、水酸化物、含水酸化物、硝酸塩、酢酸塩、シュウ酸塩および炭酸塩等の化合物を含むこともできる。
<Active species>
The present invention uses a solid catalyst for CNF production (hereinafter referred to as a cobalt / titanium-based supported catalyst) in which an active species containing cobalt as a main component is supported on an oxide or composite oxide containing titanium. This is the production of CNF using carbon oxide as a carbon source. The cobalt / titanium-based supported catalyst of the present invention has a cobalt component as a substantially active species for producing CNF. Cobalt can include not only metallic cobalt but also compounds such as oxides, hydroxides, hydrated oxides, nitrates, acetates, oxalates and carbonates.
触媒の活性種として含まれる第４〜１２族元素の成分中、少なくとも６０モル％以上、好ましくは８０モル％以上、最も好ましくは９０モル％以上がコバルト成分である。 Among the components of Group 4 to 12 elements contained as the active species of the catalyst, at least 60 mol% or more, preferably 80 mol% or more, and most preferably 90 mol% or more is the cobalt component.
他に含まれても良い第４〜１２族元素成分としては鉄、ニッケルの鉄族やマンガン、モリブデンが例示でき、これ以外に第１〜３族、または１４族の成分が含まれてもよい。コバルトとは、金属コバルトのみならず、酸化物、水酸化物、含水酸化物、硝酸塩、酢酸塩、シュウ酸塩および炭酸塩等の化合物を含む概念であり、これに限定されない。 Examples of other Group 4-12 element components that may be included include iron, nickel iron group, manganese, and molybdenum. In addition, Group 1 to Group 3 or Group 14 components may be included. . Cobalt is a concept including not only metallic cobalt but also compounds such as oxides, hydroxides, hydrated oxides, nitrates, acetates, oxalates and carbonates, but is not limited thereto.
＜担体＞
担体としては、チタンを含有する比表面積が２０〜１４０ｍ２／ｇの酸化物または複合酸化物が使用される。比表面積は２５〜１００ｍ２／ｇであることが好ましく、４０〜７０ｍ２／ｇであることがより好ましい。比表面積を２０ｍ２／ｇ以上とすることで、合成活性が向上する。
<Carrier>
As the support, an oxide or composite oxide containing titanium and having a specific surface area of 20 to 140 m 2 / g is used. Preferably the specific surface area is 25~100m 2 / g, more preferably 40~70m 2 / g. By making the specific surface area 20 m 2 / g or more, the synthetic activity is improved.
担体がチタンを含有する酸化物の場合、酸化チタン単独、または他の酸化物との混合物でもよい。酸化チタンは高い合成活性が得られる点で、結晶構造がルチル構造、またはルチル構造とアナタース構造の混合物が好ましい。 When the support is an oxide containing titanium, titanium oxide alone or a mixture with other oxides may be used. Titanium oxide is preferably a rutile structure or a mixture of a rutile structure and an anatase structure in that high synthetic activity is obtained.
チタンを含有する複合酸化物としては、チタン酸カリウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸鉛、チタン酸アルミニウムおよびチタン酸リチウム等が挙げられる。これらの中では、高い合成活性が得られる点でチタン酸バリウムが好ましい。チタンを含有する複合酸化物は、単独でも、または他の酸化物との混合物でもよい。 Examples of the composite oxide containing titanium include potassium titanate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, lead titanate, aluminum titanate and lithium titanate. Among these, barium titanate is preferable in that high synthetic activity can be obtained. The composite oxide containing titanium may be used alone or as a mixture with other oxides.
担体中のチタンを含有する酸化物または複合酸化物は、少なくとも５０質量％以上が好ましく、より好ましくは９０質量％以上であり、最も好ましくは９８質量％以上である。チタンを含有する酸化物または複合酸化物を５０質量％以上とすることで、導電性、結晶性等を向上することができる。 The oxide or composite oxide containing titanium in the carrier is preferably at least 50% by mass or more, more preferably 90% by mass or more, and most preferably 98% by mass or more. By setting the oxide or composite oxide containing titanium to 50% by mass or more, conductivity, crystallinity, and the like can be improved.
コバルト担持率は多いほどＣＮＦの収量が上がるが、多すぎるとコバルトの粒子径が大きくなり、生成するＣＮＦが太くなるため、活性種あたりの合成活性が低下する。一方、コバルト担持率が少ないと、担持されるコバルトの粒子径が小さくなり、細いカーボンナノチューブが得られるが、触媒あたりの合成活性が低くなる傾向がある。最適なコバルト担持率は、担体の細孔容量や外表面積、担持方法によって異なるが、０．１〜５０質量％が好ましく、１〜４０質量％がより好ましく、５〜３０質量％が最も好ましい。担持率を０．１〜５０質量％とすることで、触媒あたりの合成活性が向上し、コストが有利となる。 The higher the cobalt loading, the higher the yield of CNF. However, if the cobalt loading is too large, the particle size of cobalt increases and the generated CNF becomes thicker, so the synthetic activity per active species decreases. On the other hand, when the cobalt loading ratio is small, the particle diameter of the supported cobalt becomes small and thin carbon nanotubes are obtained, but the synthetic activity per catalyst tends to be low. The optimum cobalt loading varies depending on the pore volume, outer surface area, and loading method of the carrier, but is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and most preferably 5 to 30% by mass. By setting the loading ratio to 0.1 to 50% by mass, the synthesis activity per catalyst is improved and the cost is advantageous.
なお、担持率は以下の式に基づいて計算した。
担持率＝活性種（金属分として）の質量／担体の質量×１００（％）
The loading rate was calculated based on the following formula.
Loading rate = mass of active species (as metal component) / mass of support × 100 (%)
活性種を担体に担持する場合、担持方法は特に限定されない。例えば、コバルトの塩を溶解させた非水溶液中（例えばエタノール溶液）又は水溶液中に、チタンを含有する酸化物または複合酸化物を含浸し、充分に分散混合した後、水分を除去し、空気中で焼成することにより、活性種を担体へ担持させることができる。また、単純にコバルトの塩を溶解させた非水（例えばエタノール）又は水溶液中に、チタンを含有する酸化物または複合酸化物を含浸し、充分に分散混合した後、水分除去乾燥させただけでも良い。あるいはコバルトの塩を溶解させた非水中又は水溶液中に、チタンを含有する酸化物または複合酸化物を含浸し、充分に分散混合した後、アルカリにて中和した後に水分を除去し、乾燥させ、焼成してもよい。 When the active species is supported on the carrier, the supporting method is not particularly limited. For example, impregnating a titanium-containing oxide or composite oxide in a non-aqueous solution (for example, ethanol solution) or an aqueous solution in which a cobalt salt is dissolved, thoroughly dispersing and mixing, removing moisture, and in the air The active species can be supported on the carrier by baking with s. Also, simply impregnating a titanium-containing oxide or composite oxide in a non-aqueous solution (for example, ethanol) or an aqueous solution in which a cobalt salt is dissolved, thoroughly dispersing and mixing, and then removing and drying the water. good. Or after impregnating titanium-containing oxide or composite oxide in non-water or aqueous solution in which cobalt salt is dissolved, thoroughly disperse and mix, neutralize with alkali, remove moisture, and dry. You may bake.
＜ＣＮＦ製造条件＞
本発明では、一酸化炭素をＣＮＦの炭素源とするが、原料ガスとして使用する一酸化炭素は、二酸化炭素や水素との混合ガスとして使用してもよく、窒素ガス等の不活性ガスを含んでいてもよい。一酸化炭素の分圧は全圧に対し３０〜９５％であることが好ましい。一酸化炭素分圧が３０％未満であると、活性が低下してしまうし、また得られるＣＮＦの結晶性や導電性が低下してしまう。また一酸化炭素分圧が９５％より高いと、触媒の失活が激しくなり活性、収量が低下してしまう場合がある。
<CNF production conditions>
In the present invention, carbon monoxide is used as a carbon source for CNF, but carbon monoxide used as a raw material gas may be used as a mixed gas with carbon dioxide or hydrogen, and contains an inert gas such as nitrogen gas. You may go out. The partial pressure of carbon monoxide is preferably 30 to 95% with respect to the total pressure. If the carbon monoxide partial pressure is less than 30%, the activity is lowered, and the crystallinity and conductivity of the obtained CNF are also lowered. On the other hand, if the carbon monoxide partial pressure is higher than 95%, the deactivation of the catalyst becomes severe and the activity and yield may be reduced.
水素分圧は一酸化炭素分圧に対し１〜５０％であることが好ましく、５〜４５％がより好ましい。水素分圧が５０％を超えると、触媒活性が低下し、得られるＣＮＦの結晶性や導電性が低下する場合がある。水素分圧が５％未満の場合、早期に触媒の失活が起こり活性や収量が低下する場合がある。 The hydrogen partial pressure is preferably 1 to 50%, more preferably 5 to 45%, relative to the carbon monoxide partial pressure. If the hydrogen partial pressure exceeds 50%, the catalytic activity may decrease, and the crystallinity and conductivity of the resulting CNF may decrease. If the hydrogen partial pressure is less than 5%, the catalyst may be deactivated early and the activity and yield may be reduced.
全圧は絶対圧で０．０５〜０．９８ＭＰａが好ましく、０．１（大気圧）〜０．５ＭＰａがより好ましい。全圧が０．９８ＭＰａを超えると、製造に当たり高圧対応設備費用やユーティリティコストが嵩んでしまう可能性があり、０．０５ＭＰａ未満では活性が低下する場合がある。また０．１ＭＰａ（大気圧）と比較し大きく減圧である場合には、高温の反応器に対し大気（酸素）の混入を防ぐためのシールが難しく、好ましくない場合がある。 The total pressure is preferably 0.05 to 0.98 MPa in absolute pressure, more preferably 0.1 (atmospheric pressure) to 0.5 MPa. If the total pressure exceeds 0.98 MPa, the equipment costs and utility costs for high pressure may increase during production, and if it is less than 0.05 MPa, the activity may decrease. Further, when the pressure is greatly reduced as compared with 0.1 MPa (atmospheric pressure), it is difficult to seal the high-temperature reactor to prevent air (oxygen) from being mixed, which may not be preferable.
本発明においては上記の条件を満たした上で、全ガス流速が１ＮＬ／ｇ−活性種・分以上であることが好ましく、２０〜２００ＮＬ／ｇ−活性種・分以上の条件を満たすことがより好ましい。全ガス流速をこの範囲に設定することで、ＣＮＦを高い合成活性で製造することができる。ここでいう高い合成活性とは、具体的には１５ｇ−ＣＮＦ／ｇ−活性種・ｈ（時間）以上であることを意味する。全ガス流速の上限は特にないが、２００ＮＬ／ｇ−活性種・分を超えると、ガスの流量が多すぎて、余熱のためのユーティティコストが嵩み、好ましくない。 In the present invention, after satisfying the above conditions, the total gas flow rate is preferably 1 NL / g-active species / minute or more, more preferably 20-200 NL / g-active species / minute or more. preferable. By setting the total gas flow rate within this range, CNF can be produced with high synthetic activity. The high synthetic activity here means specifically 15 g-CNF / g-active species · h (hour) or more. The upper limit of the total gas flow rate is not particularly limited, but if it exceeds 200 NL / g-active species / minute, the gas flow rate is too high, and the utility cost for residual heat increases, which is not preferable.
尚、「ＮＬ」とは標準状態（０℃、１気圧）に換算したガス量Ｌ（リットル）を示し、「ＮＬ／ｇ−活性種・分」とは、単位触媒存在下（触媒１ｇあたり）での１分間のガス流量を示す。 “NL” indicates a gas amount L (liter) converted to a standard state (0 ° C., 1 atm), and “NL / g-active species / minute” indicates the presence of a unit catalyst (per 1 g of catalyst). 1 shows the gas flow rate for 1 minute.
本発明の反応温度は、６００〜８００℃が好ましく、６５０〜８００℃であることが最も好ましい。反応温度をこの範囲に設定することで、９．８ＭＰａで測定した体積抵抗率が０．０３Ω・ｃｍ以下である導電性に優れたＣＮＦを高活性で製造することが出来る。また本製造条件を満たすことで、ラマン分光測定で得られるＤ／Ｇ値が１．０以下である結晶性に優れたＣＮＦを高活性で製造することが出来る。 600-800 degreeC is preferable and, as for the reaction temperature of this invention, it is most preferable that it is 650-800 degreeC. By setting the reaction temperature within this range, a highly conductive CNF having a volume resistivity of 0.03 Ω · cm or less measured at 9.8 MPa can be produced with high activity. Moreover, by satisfying this production condition, CNF excellent in crystallinity having a D / G value of 1.0 or less obtained by Raman spectroscopic measurement can be produced with high activity.
本発明により製造されたＣＮＦは、純度を高めるために活性種および担体を除去してもよい。活性種および担体の除去は公知の方法が用いられるが、たとえば特開２００６−２９８７１３号公報等に記載された、ＣＮＦを塩酸、硝酸、硫酸等の酸に分散させた後、ろ過や遠心分離、水溶液と２相分離できる溶媒を激しく撹拌する等の手段によってＣＮＦを回収する方法により行うことができる。 The CNF produced according to the present invention may be free of active species and carriers to increase purity. A known method is used to remove the active species and the carrier. For example, as described in JP 2006-298713 A, CNF is dispersed in an acid such as hydrochloric acid, nitric acid, sulfuric acid, and then filtered, centrifuged, It can be performed by a method of recovering CNF by means such as vigorously stirring a solvent capable of two-phase separation from an aqueous solution.
本発明の実施に当たり、本発明の製造条件を満たす限り、公知の製造方法や公知の製造装置を用いることが出来る。例えば固定床反応装置や流動床反応装置、バッチ式あるいは回分式反応装置や連続式反応装置を用いることが出来る。 In carrying out the present invention, a known production method or a known production apparatus can be used as long as the production conditions of the present invention are satisfied. For example, a fixed bed reactor, a fluidized bed reactor, a batch type or batch type reactor, or a continuous reactor can be used.
＜ＣＮＦ＞
本発明では、上記最も好ましい製造条件を満たすことで、９．８ＭＰａの荷重下で測定した体積抵抗率が０．０３Ω・ｃｍ以下であり、ラマン分光測定で得られるＤ／Ｇ値が１．０以下であり、トルエン中の１０μｍ以下の分散粒子が９０体積％以上の全ての条件を満たすカーボンナノファイバーを製造することができる。
<CNF>
In the present invention, by satisfying the most preferable production conditions, the volume resistivity measured under a load of 9.8 MPa is 0.03 Ω · cm or less, and the D / G value obtained by Raman spectroscopy is 1.0. The carbon nanofibers satisfying all the conditions below, in which dispersed particles of 10 μm or less in toluene are 90% by volume or more, can be produced.
ＣＮＦのＤ／Ｇ値は、１．０以下が好ましい。ここでＤ／Ｇ値とは、ＣＮＦ粉体のラマン分光測定を行った際の、Ｄバンドピークに由来する面積の総和と、Ｇバンドピークに由来する面積の総和の比より求めることができる。Ｄ／Ｇ値が低いほどＣＮＦの結晶性が高いことを示し、ＣＮＦの導電性が高くなることを意味する。 The D / G value of CNF is preferably 1.0 or less. Here, the D / G value can be obtained from the ratio of the total area derived from the D band peak and the total area derived from the G band peak when the Raman spectroscopic measurement of the CNF powder is performed. It shows that the crystallinity of CNF is so high that D / G value is low, and the electroconductivity of CNF becomes high.
本発明の触媒を用い、反応温度を６００〜８００℃でＣＮＦを製造することで、分散処理を行わない状態で、ＣＮＦのトルエン中の１０μｍ以下の分散粒子は７０体積％以上である、分散性が良好なＣＮＦを得ることができる。反応温度を６５０〜８００℃でＣＮＦを製造することで、分散処理を行わない状態で、ＣＮＦのトルエン中の１０μｍ以下の分散粒子は９０体積％以上、好ましくは９５体積％以上である、分散性が極めて良好なＣＮＦを得ることができる。１０μｍ以上であると媒体中でも絡み合っていると考えられ、樹脂等に導電剤として混ぜる際には分散性が乏しいと考えられる。
ここで分散処理とは、粒度分布計での分散性測定前の機械的な分散、粉砕処理、例えば機械式ホモジナイザーやビーズミル、乳化分散機での処理を意味する。また超音波ホモジナイザーのような強力な超音波照射もこの範疇に入る。しかし、本願でも光散乱法による分散性測定の前処理として行っている、１０分間以下程度の市販のバス式の超音波洗浄機による測定液の懸濁化、均一化処理や、粒度分布計付属の超音波照射装置による、測定時の均一分散に使用する目的の超音波処理はこの範疇には入らない。
By using the catalyst of the present invention and producing CNF at a reaction temperature of 600 to 800 ° C., the dispersion particles having a particle size of 10 μm or less in toluene of CNF are 70% by volume or more in a state where dispersion treatment is not performed. Can obtain a good CNF. By producing CNF at a reaction temperature of 650 to 800 ° C., the dispersion particles having a particle size of 10 μm or less in toluene of CNF are not less than 90% by volume, preferably not less than 95% by volume. However, very good CNF can be obtained. If it is 10 μm or more, it is considered that the medium is entangled even in the medium, and it is considered that the dispersibility is poor when mixed as a conductive agent in a resin or the like.
Here, the dispersion treatment means mechanical dispersion and pulverization treatment before measurement of dispersibility with a particle size distribution meter, for example, treatment with a mechanical homogenizer, a bead mill, or an emulsifying disperser. In addition, powerful ultrasonic irradiation such as an ultrasonic homogenizer also falls into this category. However, in this application, as a pretreatment for the dispersibility measurement by the light scattering method, the measurement liquid is suspended and homogenized by a commercially available bath type ultrasonic cleaner for about 10 minutes or less, and a particle size distribution meter is attached. The ultrasonic treatment for the purpose of uniform dispersion at the time of measurement by the ultrasonic irradiator does not fall into this category.
以下、実施例により、本発明を説明するが、これらの実施例は本発明を限定するものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, these Examples do not limit this invention.
＜比表面積測定＞
ＣＮＦ粉体や触媒担体の比表面積は、Ｍｏｕｎｔｅｃｈ社製Ｍａｃｓｏｒｂ ＨＭ ｍｏｄｅｌ−１２０１を用い、ＪＩＳ Ｋ６２１７−２に従いＢＥＴ一点法で求めた。
<Specific surface area measurement>
The specific surface areas of the CNF powder and the catalyst support were determined by the BET single point method according to JIS K6217-2 using a Macsorb HM model-1201 manufactured by Mounttech.
＜体積抵抗率測定＞
ＣＮＦ粉体の体積抵抗率は、三菱化学アナリティック社製ロレスタＧＰを用い、２３℃、相対湿度５０％の雰囲気にて、荷重９．８ＭＰａの条件下、四探針法にて求めた。
<Volume resistivity measurement>
The volume resistivity of the CNF powder was obtained by a four-probe method using a Loresta GP manufactured by Mitsubishi Chemical Analytical Co., Ltd. in an atmosphere of 23 ° C. and a relative humidity of 50% under a load of 9.8 MPa.
＜ラマン分光測定＞
ＣＮＦ粉体のラマン分光測定は、顕微レーザーラマン分光分析装置(Niolet Almega-XR型、サーモフィッシャーサイエンティフィック社製、レーザー５３２ｎｍ)を用い行った。Ｄバンド（Ｄ１：ピーク位置１３３０ｃｍ−１、Ｄ３：１５００ｃｍ−１、Ｄ４：１１５０ｃｍ−１）とＧバンド（Ｇ＋：１６００ｃｍ−１、Ｇ−：１５７０ｃｍ−１）の波形分離を行った後、Ｄバンドピークに由来する面積の総和とＤバンドピークに由来する面積の総和の比（Ｄ／Ｇ値）を求めた。本Ｄ／Ｇ値が低いほどＣＮＦの結晶性が高いことを示している。
（参考）
Ｄ１：グラファイト結晶構造内の点欠陥、結晶端由来の欠陥に由来
Ｄ３：アモルファスカーボンに由来
Ｄ４：ポリエンやイオン性不純物に由来
Ｇ＋：グラファイトの結晶性ピーク：縦光学モード
Ｇ−：グラファイトの結晶性ピーク：横光学モード
<Raman spectroscopy measurement>
The Raman spectroscopic measurement of CNF powder was performed using a microscopic laser Raman spectroscopic analyzer (Niolet Almega-XR type, manufactured by Thermo Fisher Scientific, laser 532 nm). After performing waveform separation of D band (D1: peak position 1330 cm-1, D3: 1500 cm-1, D4: 1150 cm-1) and G band (G +: 1600 cm-1, G-: 1570 cm-1), D band The ratio (D / G value) of the total area derived from the peak and the total area derived from the D band peak was determined. The lower the D / G value, the higher the crystallinity of CNF.
(reference)
D1: Derived from point defects in the crystal crystal structure and defects derived from crystal edges D3: Derived from amorphous carbon D4: Derived from polyene or ionic impurities G +: Crystalline peak of graphite: Longitudinal optical mode G-: Crystallinity of graphite Peak: Transverse optical mode
＜光散乱法による粒度分布測定＞
（分散前処理）
粒度分布測定に先立ち、合成したＣＮＦ３００ｍｇを蒸留水１００ｍＬ、トルエン１００ｍＬの２層溶液に加え、超音波ホモジナイザー（小型デジタル超音波ホモジナイザー ＢＲＡＮＳＯＮ社製）を用い、２分間１００Ｗで超音波照射を実施した。分液ロートに移し、水層を捨て、蒸留水を１００ｍＬ加え、撹拌した。その後、蒸留水の除去、添加を８回繰り返し、トルエン層を回収して乾燥した。乾燥したＣＮＦを再度トルエンに分散させ、粒度分布測定用の０．１質量％のトルエン分散液を調製した。さらに、調製したトルエン分散液を、超音波洗浄器（ＵＳ ２Ａ アズワン社製、超音波出力８０Ｗ）で５分間超音波分散した。
<Measurement of particle size distribution by light scattering method>
(Distributed pre-processing)
Prior to the particle size distribution measurement, 300 mg of synthesized CNF was added to a two-layer solution of 100 mL of distilled water and 100 mL of toluene, and ultrasonic irradiation was performed at 100 W for 2 minutes using an ultrasonic homogenizer (compact digital ultrasonic homogenizer manufactured by BRANSON). It moved to the separating funnel, the water layer was thrown away, 100 mL of distilled water was added, and it stirred. Thereafter, removal and addition of distilled water were repeated 8 times, and the toluene layer was recovered and dried. The dried CNF was again dispersed in toluene to prepare a 0.1% by mass toluene dispersion for particle size distribution measurement. Furthermore, the prepared toluene dispersion was subjected to ultrasonic dispersion for 5 minutes with an ultrasonic cleaner (US 2A, manufactured by ASONE Corporation, ultrasonic output 80 W).
（粒度分布測定）
調製したトルエン分散液を用い、粒度分布を測定した。粒度分布の測定はレーザ回折・散乱法（ＩＳＯ １３３２０：２００９）に準拠して実施した。すなわち粒度分布計(「ＬＳ １３ ３２０ ユニバーサルリキッドモジュール」 ＢＥＣＫＭＡＮ ＣＯＵＬＴＥＲ社製)を用いた。まず、同装置の光学モデルをトルエンの屈折率に設定し、トルエンを充填し、ポンプスピード１００％の条件でオフセット測定、光軸調整、バックグラウンド測定を行った。次に、粒度分布計に調製したトルエン分散液を適正濃度８〜１２％、もしくはＰＩＤＳ４０％〜５５％になるように加え、７３Ｗ、２分間超音波照射を行い、３０秒循環し気泡を除いた後に粒度分布測定を行った。粒度に対する体積％表示のグラフを得、粒度分布を解析した。
(Particle size distribution measurement)
The particle size distribution was measured using the prepared toluene dispersion. The particle size distribution was measured according to the laser diffraction / scattering method (ISO 13320: 2009). That is, a particle size distribution meter (“LS 13 320 Universal Liquid Module” manufactured by BECKMAN COULTER) was used. First, the optical model of the apparatus was set to the refractive index of toluene, filled with toluene, and offset measurement, optical axis adjustment, and background measurement were performed under conditions of a pump speed of 100%. Next, the toluene dispersion prepared in the particle size distribution meter was added so as to have an appropriate concentration of 8 to 12% or PIDS of 40% to 55%, and 73 W was irradiated with ultrasonic waves for 2 minutes and circulated for 30 seconds to remove bubbles. Later, the particle size distribution was measured. The graph of volume% display with respect to the particle size was obtained, and the particle size distribution was analyzed.
＜担持触媒の調製＞
（触媒合成例１）
アナタース構造とルチル構造の比が８０対２０である酸化チタン（ＡＥＲＯＸＩＤＥ（登録商標） 「ＴｉＯ２ Ｐ２５」、日本アエロジル社製 比表面積５２ｍ２／ｇ）２．５gと、硝酸コバルト・６水和物（３Ｎ５、関東化学社製)０．６ｇを蒸留水３０ｍLに溶解した。ロータリーエバポレータ(Ｎ１０００、東京理化器械社製)にセットし、ウォーターバスで５０℃に加温し１時間撹拌した。水を除去後、さらに真空下６０℃で１２時間乾燥し、固体成分を得た。
<Preparation of supported catalyst>
(Catalyst synthesis example 1)
Titanium oxide having a ratio of anatase structure to rutile structure of 80:20 (AEROXIDE (registered trademark) “TiO 2 P25”, specific surface area 52 m 2 / g manufactured by Nippon Aerosil Co., Ltd.) and cobalt nitrate hexahydrate 0.6 g (3N5, manufactured by Kanto Chemical Co., Inc.) was dissolved in 30 mL of distilled water. This was set on a rotary evaporator (N1000, manufactured by Tokyo Rika Kikai Co., Ltd.), heated to 50 ° C. with a water bath, and stirred for 1 hour. After removing water, it was further dried under vacuum at 60 ° C. for 12 hours to obtain a solid component.
得られた固体成分をセラミック製の坩堝に移し、マッフル炉（ＦＯ２００ヤマト科学株式会社製）で空気中４００℃の条件下５時間焼成し、コバルト担持率５％のコバルト／チタン系触媒を得た。 The obtained solid component was transferred to a ceramic crucible and baked in a muffle furnace (FO200 Yamato Scientific Co., Ltd.) in air at 400 ° C. for 5 hours to obtain a cobalt / titanium catalyst with a cobalt loading rate of 5%. .
（触媒合成例２）
硝酸コバルト・６水和物の量を１．２ｇに変更した以外は、触媒合成例１と同様な方法でコバルト担持率１０％のコバルト／チタン系触媒を調製した。
(Catalyst synthesis example 2)
A cobalt / titanium catalyst having a cobalt loading rate of 10% was prepared in the same manner as in Catalyst Synthesis Example 1, except that the amount of cobalt nitrate hexahydrate was changed to 1.2 g.
（触媒合成例３）
硝酸コバルト・６水和物の量を２．４ｇに変更した以外は、触媒合成例１と同様な方法でコバルト担持率２０％のコバルト／チタン系触媒を調製した。
(Catalyst synthesis example 3)
A cobalt / titanium catalyst having a cobalt loading rate of 20% was prepared in the same manner as in Catalyst Synthesis Example 1, except that the amount of cobalt nitrate hexahydrate was changed to 2.4 g.
（触媒合成例４）
硝酸コバルト・６水和物の量を３．６ｇに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５０％のコバルト／チタン系触媒を調製した。
(Catalyst synthesis example 4)
A cobalt / titanium catalyst having a cobalt loading of 50% was prepared in the same manner as in Catalyst Synthesis Example 1 except that the amount of cobalt nitrate hexahydrate was changed to 3.6 g.
（触媒合成例５）
酸化チタン２．５ｇを、チタン酸バリウム（ＹＫＴ−０５、堺化学工業社製 比表面積２５ｍ２／ｇ）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／チタン系担持触媒を調製した。
(Catalyst synthesis example 5)
Except for changing 2.5 g of titanium oxide to 2.5 g of barium titanate (YKT-05, Sakai Chemical Industry Co., Ltd., specific surface area 25 m 2 / g), the cobalt loading rate is 5% in the same manner as in Catalyst Synthesis Example 1. A cobalt / titanium-based supported catalyst was prepared.
（触媒合成例６）
酸化チタン２．５ｇを、結晶構造がルチル構造のみからなる酸化チタン（ＳＴＲ−１００Ｎ、堺化学工業社製 比表面積９７ｍ２／ｇ）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／チタン系担持触媒を調製した。
(Catalyst synthesis example 6)
Except for changing 2.5 g of titanium oxide to 2.5 g of titanium oxide (STR-100N, Sakai Chemical Industry Co., Ltd., specific surface area 97 m 2 / g) whose crystal structure is composed only of the rutile structure, the same as in Catalyst Synthesis Example 1 A cobalt / titanium-based supported catalyst having a cobalt loading rate of 5% was prepared by this method.
（触媒合成例７）
酸化チタン２．５ｇを、結晶構造がアナタース構造のみからなる酸化チタン（ＳＳＰ―Ｍ、堺化学工業社製 比表面積９３ｍ２／ｇ）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／チタン系担持触媒を調製した。
(Catalyst synthesis example 7)
Except for changing 2.5 g of titanium oxide to 2.5 g of titanium oxide (SSP-M, specific surface area 93 m 2 / g manufactured by Sakai Chemical Industry Co., Ltd.) whose crystal structure is only an anatase structure, the same as in Catalyst Synthesis Example 1 A cobalt / titanium-based supported catalyst having a cobalt loading rate of 5% was prepared by this method.
（触媒合成例８）
酸化チタン２．５ｇを、結晶構造がルチル構造のみからなる酸化チタン（Ｒ−３１０、堺化学工業社製 比表面積９ｍ２／ｇ）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／チタン系担持触媒を調製した。
(Catalyst synthesis example 8)
Except for changing 2.5 g of titanium oxide to 2.5 g of titanium oxide (R-310, specific surface area 9 m 2 / g manufactured by Sakai Chemical Industry Co., Ltd.) whose crystal structure is only a rutile structure, the same as in Catalyst Synthesis Example 1 A cobalt / titanium-based supported catalyst having a cobalt loading rate of 5% was prepared by this method.
（触媒合成例９）
酸化チタン２．５ｇを、結晶構造がアナタース構造のみからなる酸化チタン（Ａ−１１０、堺化学工業社製 比表面積１１ｍ２／ｇ）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／酸化チタン担持触媒を調製した。
(Catalyst synthesis example 9)
Except for changing 2.5 g of titanium oxide to 2.5 g of titanium oxide (A-110, specific surface area 11 m 2 / g, manufactured by Sakai Chemical Industry Co., Ltd.) whose crystal structure consists only of anatase structure, the same as in Catalyst Synthesis Example 1 A cobalt / titanium oxide supported catalyst having a cobalt loading rate of 5% was prepared by this method.
（触媒合成例１０）
酸化チタン２．５ｇを、アナタース構造とルチル構造の比が８５対１５である酸化チタン（堺化学工業社製 比表面積４ｍ２／ｇ）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／酸化チタン担持触媒を調製した。
(Catalyst synthesis example 10)
Except for changing 2.5 g of titanium oxide to 2.5 g of titanium oxide (having a specific surface area of 4 m 2 / g manufactured by Sakai Chemical Industry Co., Ltd.) having an anatase / rutile structure ratio of 85:15, the same as in Catalyst Synthesis Example 1 In this manner, a cobalt / titanium oxide supported catalyst having a cobalt loading rate of 5% was prepared.
（触媒合成例１１）
酸化チタン２．５ｇを、アナタース構造とルチル構造の比が３７対６３である酸化チタン（堺化学工業社製 比表面積２ｍ２／ｇ）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／酸化チタン担持触媒を調製した。
(Catalyst synthesis example 11)
Except for changing 2.5 g of titanium oxide to 2.5 g of titanium oxide having a ratio of anatase structure to rutile structure of 37:63 (specific surface area 2 m 2 / g manufactured by Sakai Chemical Industry Co., Ltd.), the same as in Catalyst Synthesis Example 1 In this manner, a cobalt / titanium oxide supported catalyst having a cobalt loading rate of 5% was prepared.
（触媒合成例１２）
酸化チタン２．５ｇを、シリカ（ＡＥＲＯＳＩＬ ２００、日本アエロジル社製）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／シリカ担持触媒を調製した。
(Catalyst synthesis example 12)
A cobalt / silica supported catalyst having a cobalt loading rate of 5% was prepared in the same manner as in Catalyst Synthesis Example 1, except that 2.5 g of titanium oxide was changed to 2.5 g of silica (AEROSIL 200, manufactured by Nippon Aerosil Co., Ltd.).
（触媒合成例１３）
酸化チタン２．５ｇを、アルミナ（ＤＡＷ７０、電気化学工業社製）２．５gに変更した以外は、触媒合成例１と同様な方法でコバルト担持率５％のコバルト／アルミナ担持触媒を調製した。
(Catalyst synthesis example 13)
A cobalt / alumina supported catalyst having a cobalt loading rate of 5% was prepared in the same manner as in Catalyst Synthesis Example 1 except that 2.5 g of titanium oxide was changed to 2.5 g of alumina (DAW70, manufactured by Denki Kagaku Kogyo).
（触媒合成例１４）
硝酸コバルト・６水和物０．６ｇを、硝酸鉄・９水和物(関東化学社製)０．９ｇに変更した以外は、触媒合成例１と同様な方法で鉄担持率５％の鉄／チタン系担持触媒を調製した。
(Catalyst synthesis example 14)
Iron with 5% iron loading is the same as in Catalyst Synthesis Example 1 except that 0.6 g of cobalt nitrate hexahydrate is changed to 0.9 g of iron nitrate nonahydrate (manufactured by Kanto Chemical Co., Inc.). / Titanium-based supported catalyst was prepared.
（触媒合成例１５）
硝酸コバルト・６水和物０．６ｇを、硝酸ニッケル・６水和物(関東化学社製)０．６ｇに変更した以外は、触媒合成例１と同様な方法でニッケル担持率５％のニッケル／チタン系担持触媒を調製した。
(Catalyst synthesis example 15)
Nickel with 5% nickel loading in the same manner as in Catalyst Synthesis Example 1 except that 0.6 g of cobalt nitrate hexahydrate was changed to 0.6 g of nickel nitrate hexahydrate (manufactured by Kanto Chemical Co., Inc.) / Titanium-based supported catalyst was prepared.
（触媒合成例１６）
コバルトナノ粒子（ｃｏｂａｌｔ ｎａｎｏ ｐｏｗｄｅｒ ＡＰＳ ５−１５ｎｍ Ａｌｆａ Ａｅｓａｒ社製）５ｍｇと、酸化チタン（ＡＥＲＯＸＩＤＥ（登録商標） 「ＴｉＯ２ Ｐ２５」、日本アエロジル社製 比表面積５２ｍ２／ｇ）１００ｍｇを乳鉢で混合することで、混合触媒を調製した。
(Catalyst synthesis example 16)
Cobalt nano particles (cobalt nano powder APS 5-15 nm, manufactured by Alfa Aesar) 5 mg, titanium oxide (AEROXIDE (registered trademark) “TiO 2 P25”, Nippon Aerosil Co., Ltd., specific surface area 52 m 2 / g) are mixed in a mortar. Thus, a mixed catalyst was prepared.
（触媒合成例１７）
特許５００３９２３号に準じ、以下のようにして触媒を調製した。イオン交換水２５ｍＬに硝酸コバルト〔Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ：分子量２９１．０３〕５．７５ｇ（０．０２モル）、硝酸マグネシウム〔Ｍｇ（ＮＯ３）２・６Ｈ２Ｏ：分子量２５６．４１〕５．１０ｇ（０．０２モル）を溶解させ、原料溶液（１）を調製した。また、重炭酸アンモニウム〔（ＮＨ４）ＨＣＯ３：分子量７９．０６〕粉末１１ｇ（０．１３９モル）をイオン交換水５５ｍＬに溶解させ、原料溶液（２）を調製した。次に、反応温度４０℃で原料溶液（１）と（２）を混合し、その後４時間攪拌した。生成した沈殿物のろ過、洗浄を行い、乾燥した。これを６００℃で４時間焼成した後、乳鉢で粉砕し、触媒を取得した。
(Catalyst synthesis example 17)
According to Japanese Patent No. 5003923, a catalyst was prepared as follows. In 25 mL of ion-exchanged water, 5.75 g (0.02 mol) of cobalt nitrate [Co (NO 3 ) 2 .6H 2 O: molecular weight 291.03], magnesium nitrate [Mg (NO 3 ) 2 .6H 2 O: molecular weight 256 .41] 5.10 g (0.02 mol) was dissolved to prepare a raw material solution (1). Also, 11 g (0.139 mol) of ammonium bicarbonate [(NH 4 ) HCO 3 : molecular weight 79.06] powder was dissolved in 55 mL of ion-exchanged water to prepare a raw material solution (2). Next, the raw material solutions (1) and (2) were mixed at a reaction temperature of 40 ° C., and then stirred for 4 hours. The produced precipitate was filtered, washed and dried. This was calcined at 600 ° C. for 4 hours and then pulverized in a mortar to obtain a catalyst.
＜ＣＮＦ合成＞
（実施例１）
原料の一酸化炭素は、(株)鈴木商館から購入した，Ｇ１グレード（純度９９．９５％）を使用した。
石英製の反応管内に、触媒合成例１で得られた担持触媒１００ｍｇを仕込んだ触媒ホルダーを設置し、窒素を十分流して窒素置換した。さらに、窒素８０％、水素２０％の還元ガスを大気圧（１０１ｋＰａ）下、表１に示す反応温度に昇温し、反応温度に達してから３０分間保持して触媒の還元を行った。引き続き原料ガスを、表１に示す原料ガス組成、全原料ガス流速にて触媒層に通過させ、ＣＮＦの製造を１時間行った。所定の時間反応を行った後に、原料ガスを窒素ガスに切り替え、直ちに冷却した。得られたＣＮＦ質量と用いた触媒質量、反応時間から、単位触媒、単位時間あたりのＣＮＦ合成活性を計算し、さらに得られたＣＮＦの体積抵抗率、Ｄ／Ｇ値および粒度分布を測定した。結果を表１に示す。
<CNF synthesis>
Example 1
The raw material carbon monoxide used was G1 grade (purity 99.95%) purchased from Suzuki Shokan Co., Ltd.
A catalyst holder charged with 100 mg of the supported catalyst obtained in Catalyst Synthesis Example 1 was placed in a quartz reaction tube, and the nitrogen was purged sufficiently by flowing nitrogen. Further, a reducing gas of 80% nitrogen and 20% hydrogen was heated to the reaction temperature shown in Table 1 under atmospheric pressure (101 kPa), and the catalyst was reduced by holding for 30 minutes after reaching the reaction temperature. Subsequently, the source gas was passed through the catalyst layer at the source gas composition and the total source gas flow rate shown in Table 1, and CNF was produced for 1 hour. After performing the reaction for a predetermined time, the raw material gas was switched to nitrogen gas and immediately cooled. From the obtained CNF mass, the used catalyst mass, and the reaction time, the CNF synthesis activity per unit catalyst and unit time was calculated, and the volume resistivity, D / G value and particle size distribution of the obtained CNF were measured. The results are shown in Table 1.
（実施例２）
触媒合成例２で作製した担持触媒５０ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
(Example 2)
CNF was synthesized in the same manner as in Example 1 except that 50 mg of the supported catalyst prepared in Catalyst Synthesis Example 2 was used. The results are shown in Table 1.
（実施例３）
触媒合成例３で作製した担持触媒２５ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に、透過型電子顕微鏡写真を図２に示す。
(Example 3)
CNF was synthesized in the same manner as in Example 1 except that 25 mg of the supported catalyst prepared in Catalyst Synthesis Example 3 was used. The results are shown in Table 1, and a transmission electron micrograph is shown in FIG.
（実施例４）
触媒合成例４で作製した担持触媒１０ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
Example 4
CNF was synthesized in the same manner as in Example 1 except that 10 mg of the supported catalyst prepared in Catalyst Synthesis Example 4 was used. The results are shown in Table 1.
（実施例５）
反応温度を５５０℃に変更した以外は、実施例１と同様な方法でＣＮＦを合成した。結果を表１に示す。
(Example 5)
CNF was synthesized in the same manner as in Example 1 except that the reaction temperature was changed to 550 ° C. The results are shown in Table 1.
（実施例６）
反応温度を７００℃に変更し、ガス組成をＣＯ／Ｈ２／Ｎ２＝７０／３０／０に変更した以外は、実施例１と同様な方法でＣＮＦを合成した。結果を表１に示す。なお、図１に得られたＣＮＦの粒度分布曲線を示す。１０μｍ以下の分散粒子は、９８体積％であることが示され、良好な分散状態にあるＣＮＦが得られたことを確認した。
(Example 6)
CNF was synthesized in the same manner as in Example 1 except that the reaction temperature was changed to 700 ° C. and the gas composition was changed to CO / H 2 / N 2 = 70/30/0. The results are shown in Table 1. In addition, the particle size distribution curve of CNF obtained in FIG. 1 is shown. The dispersed particles of 10 μm or less were shown to be 98% by volume, and it was confirmed that CNF in an excellent dispersed state was obtained.
（実施例７）
反応温度を７５０℃に変更し、ガス組成をＣＯ／Ｈ２／Ｎ２＝７０／３０／０に変更した以外は、実施例１と同様な方法でＣＮＦを合成した。結果を表１に示す。
(Example 7)
CNF was synthesized in the same manner as in Example 1 except that the reaction temperature was changed to 750 ° C. and the gas composition was changed to CO / H 2 / N 2 = 70/30/0. The results are shown in Table 1.
（実施例８）
反応温度を８００℃に変更し、ガス組成をＣＯ／Ｈ２／Ｎ２＝７０／３０／０に変更した以外は、実施例１と同様な方法でＣＮＦを合成した。結果を表１に示す。
(Example 8)
CNF was synthesized in the same manner as in Example 1 except that the reaction temperature was changed to 800 ° C. and the gas composition was changed to CO / H 2 / N 2 = 70/30/0. The results are shown in Table 1.
（実施例９）
ガス流速を２１［ＮＬ／ｇ−活性種・分］に変更し、触媒合成例３で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
Example 9
CNF was synthesized in the same manner as in Example 1 except that the gas flow rate was changed to 21 [NL / g-active species / min] and 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 3 was used. The results are shown in Table 1.
（実施例１０）
ガス流速を７［ＮＬ／ｇ−活性種・分］に変更し、触媒合成例３で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
(Example 10)
CNF was synthesized in the same manner as in Example 1 except that the gas flow rate was changed to 7 [NL / g-active species / min] and 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 3 was used. The results are shown in Table 1.
（実施例１１）
ガス組成をＣＯ／Ｈ２／Ｎ２＝９０／１０／０に変更し、触媒合成例３で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
(Example 11)
CNF was synthesized in the same manner as in Example 1 except that the gas composition was changed to CO / H 2 / N 2 = 90/10/0 and 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 3 was used. . The results are shown in Table 1.
（実施例１２）
ガス組成をＣＯ／Ｈ２／Ｎ２＝３０／２０／５０に変更し、触媒合成例３で製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
(Example 12)
CNF was synthesized in the same manner as in Example 1 except that the gas composition was changed to CO / H 2 / N 2 = 30/20/50 and 100 mg of the supported catalyst produced in Catalyst Synthesis Example 3 was used. . The results are shown in Table 1.
（実施例１３）
触媒合成例５で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
(Example 13)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 5 was used. The results are shown in Table 1.
（実施例１４）
触媒合成例６で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
(Example 14)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 6 was used. The results are shown in Table 1.
（実施例１５）
触媒合成例７で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。結果を表１に示す。
各実施例で得られたＣＮＦのＴＥＭ（透過型電子顕微鏡）観察を行ったところ、いずれも平均径約１０ｎｍ〜４０ｎｍの範囲の、平均アスペクト比が１０以上の多層カーボンナノチューブであることが確認できた。
(Example 15)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 7 was used. The results are shown in Table 1.
When TEM (transmission electron microscope) observation of CNF obtained in each example was performed, it was confirmed that all were multi-walled carbon nanotubes having an average diameter of about 10 nm to 40 nm and an average aspect ratio of 10 or more. It was.
（比較例１）
触媒合成例８で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例１では、本願の条件を満たさない、比表面積が９ｍ２／ｇである酸化チタンを担体とした触媒用いてＣＮＦの合成を試みたが、ＣＮＦ合成活性が出ず、各種評価に必要なＣＮＦを得ることはできなかった。
(Comparative Example 1)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 8 was used. In Comparative Example 1, synthesis of CNF was attempted using a catalyst using titanium oxide having a specific surface area of 9 m 2 / g, which does not satisfy the conditions of the present application, but CNF synthesis activity did not appear, and various evaluations were made. The necessary CNF could not be obtained.
（比較例２）
触媒合成例９で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例２では、本願の条件を満たさない、比表面積が１１ｍ２／ｇである酸化チタンを担体とした触媒用いてＣＮＦの合成を試みたが、ＣＮＦ合成活性は低い値にとどまり、反応時間１時間では体積抵抗率測定に十分な収量のＣＮＦは得られなかった。
(Comparative Example 2)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 9 was used. In Comparative Example 2, synthesis of CNF was attempted using a catalyst that supported titanium oxide having a specific surface area of 11 m 2 / g, which did not satisfy the conditions of the present application. However, the CNF synthesis activity remained at a low value. In 1 hour, CNF with a yield sufficient for volume resistivity measurement could not be obtained.
（比較例３）
触媒合成例１０で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例３では、本願の条件を満たさない、比表面積が４ｍ２／ｇである酸化チタンを担体とした触媒用いてＣＮＦの合成を試みたが、ＣＮＦ合成活性は低い値にとどまり、反応時間１時間では体積抵抗率測定に十分な収量のＣＮＦは得られなかった。
(Comparative Example 3)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 10 was used. In Comparative Example 3, synthesis of CNF was attempted using a catalyst that supported titanium oxide having a specific surface area of 4 m 2 / g, which did not satisfy the conditions of the present application, but the CNF synthesis activity remained at a low value. In 1 hour, CNF with a yield sufficient for volume resistivity measurement could not be obtained.
（比較例４）
触媒合成例１１で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例４では、本願の条件を満たさない、比表面積が２ｍ２／ｇである酸化チタンを担体とした触媒用いてＣＮＦの合成を試みたが、ＣＮＦ合成活性は低い値にとどまり、反応時間１時間では体積抵抗率測定に十分な収量のＣＮＦは得られなかった。
(Comparative Example 4)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 11 was used. In Comparative Example 4, synthesis of CNF was attempted using a catalyst using a titanium oxide support with a specific surface area of 2 m 2 / g, which did not satisfy the conditions of the present application, but the CNF synthesis activity remained at a low value. In 1 hour, CNF with a yield sufficient for volume resistivity measurement could not be obtained.
（比較例５）
触媒合成例１２で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例５では、本願の条件を満たさない、コバルト担持率５％のコバルト−シリカ担持触媒でＣＮＦの合成を行ったが、ＣＮＦ合成活性は低い値にとどまり、反応時間１時間では体積抵抗率測定に十分な収量のＣＮＦは得られなかった。
(Comparative Example 5)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 12 was used. In Comparative Example 5, CNF was synthesized with a cobalt-silica-supported catalyst having a cobalt loading rate of 5%, which did not satisfy the conditions of the present application. However, the CNF synthesis activity remained at a low value, and the volume resistance was 1 hour in the reaction time. A yield of CNF sufficient for rate measurement could not be obtained.
（比較例６）
触媒合成例１３で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例６では、本願の条件を満たさない、コバルト担持率５％のコバルト−アルミナ担持触媒でＣＮＦの合成を行ったが、ＣＮＦ合成活性は低い値にとどまり、反応時間１時間では体積抵抗率測定に十分な収量のＣＮＦは得られなかった。
(Comparative Example 6)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 13 was used. In Comparative Example 6, CNF was synthesized with a cobalt-alumina supported catalyst having a cobalt loading rate of 5%, which did not satisfy the conditions of the present application. However, the CNF synthesis activity remained at a low value, and the volume resistance was 1 hour in the reaction time. A yield of CNF sufficient for rate measurement could not be obtained.
（比較例７）
触媒合成例１４で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例７では、本願の条件を満たさない、鉄担持率５％の鉄−酸化チタン担持触媒でＣＮＦの合成を行ったが、ＣＮＦ合成活性は低い値にとどまり、反応時間１時間では体積抵抗率測定に十分な収量のＣＮＦは得られなかった。
(Comparative Example 7)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 14 was used. In Comparative Example 7, CNF was synthesized with an iron-titanium oxide supported catalyst having an iron loading rate of 5%, which did not satisfy the conditions of the present application. However, the CNF synthesis activity remained low, and the reaction time was 1 hour. A yield of CNF sufficient for resistivity measurement could not be obtained.
（比較例８）
触媒合成例１５で作製した担持触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例８では、本願の条件を満たさない、ニッケル担持率５％のニッケル−酸化チタン担持触媒でＣＮＦの合成を行ったが、高いＣＮＦ合成活性は得られたものの、高い体積抵抗値を示し、導電性に劣る結果となった。
(Comparative Example 8)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the supported catalyst prepared in Catalyst Synthesis Example 15 was used. In Comparative Example 8, CNF was synthesized with a nickel-titanium oxide supported catalyst having a nickel loading rate of 5%, which did not satisfy the conditions of the present application. However, although a high CNF synthesis activity was obtained, a high volume resistance value was obtained. As a result, the conductivity was inferior.
（比較例９）
触媒合成例１６で作製した混合触媒１００ｍｇを用いた以外は、実施例１と同様な方法でＣＮＦの合成を行なった。尚、比較例９では、本願の条件を満たさない、担持触媒ではなく、混合触媒でＣＮＦの合成を行ったが、ＣＮＦ合成活性は低い値にとどまり、物性を得ることはできなかった。
(Comparative Example 9)
CNF was synthesized in the same manner as in Example 1 except that 100 mg of the mixed catalyst prepared in Catalyst Synthesis Example 16 was used. In Comparative Example 9, CNF was synthesized with a mixed catalyst instead of a supported catalyst, which did not satisfy the conditions of the present application, but the CNF synthesis activity remained at a low value, and physical properties could not be obtained.
（比較例１０）
石英製の反応管内に、触媒合成例１７で得られた沈殿法触媒５ｍｇを仕込んだ触媒ホルダーを設置し、窒素を十分流して窒素置換した後に、窒素８０％、水素２０％の還元ガスを大気圧（１０１ｋＰａ）下、３０ＮＬ／ｇ−触媒・分で流しながら６００℃まで昇温し、反応温度に達してから３０分間保持して触媒の還元を行った。その後に表１に示す原料ガス組成、流速で触媒層を通過させ１時間反応を行った。結果を表１に示す。
(Comparative Example 10)
A catalyst holder charged with 5 mg of the precipitation catalyst obtained in Catalyst Synthesis Example 17 was placed in a quartz reaction tube, and after sufficiently flowing nitrogen to replace the nitrogen, a large amount of reducing gas of 80% nitrogen and 20% hydrogen was added. While flowing at 30 NL / g-catalyst · minute under atmospheric pressure (101 kPa), the temperature was raised to 600 ° C., and after reaching the reaction temperature, the catalyst was reduced for 30 minutes. Thereafter, the reaction was carried out for 1 hour through the catalyst layer at the raw material gas composition and flow rate shown in Table 1. The results are shown in Table 1.
コバルト／チタン系担持触媒を用いた場合、高い活性でＣＮＦが得られた。体積抵抗値も低く、Ｄ／Ｇ値も低く、高結晶性を示すＣＮＦが得られ得られた。
本願における最も好ましい反応条件下である実施例６、７ではさらに高い電気伝導率（低い体積抵抗率）、かつ低いＤ／Ｇ値（高結晶性）を示すＣＮＦが得られ得られた。
When a cobalt / titanium-based supported catalyst was used, CNF was obtained with high activity. CNFs having a low volume resistance value, a low D / G value, and high crystallinity were obtained.
In Examples 6 and 7, which are the most preferable reaction conditions in the present application, CNFs having higher electric conductivity (low volume resistivity) and low D / G value (high crystallinity) were obtained.
一酸化炭素を炭素源としＣＮＦを合成する際、コバルトを主成分とする金属を、チタンを含有する酸化物もしくは複合酸化物を触媒として用いることで、より高い活性で、高い結晶性、高い導電性、さらには高い分散性のＣＮＦを製造することが出来る。得られたＣＮＦは、導電性樹脂および導電性ゴムの導電性フィラーとして好適に使用することができる。 When synthesizing CNF using carbon monoxide as a carbon source, a metal having cobalt as a main component is used as an oxide or composite oxide containing titanium as a catalyst, so that it has higher activity, high crystallinity, and high conductivity. In addition, it is possible to produce a highly dispersible CNF. The obtained CNF can be suitably used as a conductive filler for conductive resins and conductive rubbers.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014192628 | 2014-09-22 | ||
| JP2014192628 | 2014-09-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016064972A true JP2016064972A (en) | 2016-04-28 |
| JP6600182B2 JP6600182B2 (en) | 2019-10-30 |
Family
ID=55803932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015128444A Active JP6600182B2 (en) | 2014-09-22 | 2015-06-26 | Carbon nanofiber manufacturing method and carbon nanofiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6600182B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004300631A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanofiber and method for producing the same |
| JP2005314204A (en) * | 2003-09-02 | 2005-11-10 | Toray Ind Inc | Method of manufacturing carbon nanotube, and composition containing carbon nanotube |
| JP2009249206A (en) * | 2008-04-02 | 2009-10-29 | Daicel Chem Ind Ltd | Titanium oxide particle surface-modified by carbon nanotube whose tip is carried with metallic element |
| JP2010024131A (en) * | 2008-06-18 | 2010-02-04 | Showa Denko Kk | Method for producing carbon fiber |
| WO2013099256A1 (en) * | 2011-12-27 | 2013-07-04 | 昭和電工株式会社 | Method for producing carbon fiber |
-
2015
- 2015-06-26 JP JP2015128444A patent/JP6600182B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004300631A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanofiber and method for producing the same |
| JP2005314204A (en) * | 2003-09-02 | 2005-11-10 | Toray Ind Inc | Method of manufacturing carbon nanotube, and composition containing carbon nanotube |
| JP2009249206A (en) * | 2008-04-02 | 2009-10-29 | Daicel Chem Ind Ltd | Titanium oxide particle surface-modified by carbon nanotube whose tip is carried with metallic element |
| JP2010024131A (en) * | 2008-06-18 | 2010-02-04 | Showa Denko Kk | Method for producing carbon fiber |
| WO2013099256A1 (en) * | 2011-12-27 | 2013-07-04 | 昭和電工株式会社 | Method for producing carbon fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6600182B2 (en) | 2019-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6604854B2 (en) | Carbon nanofiber manufacturing method and carbon nanofiber | |
| JP5573815B2 (en) | Fine carbon fiber, fine short carbon fiber and method for producing them | |
| KR101446116B1 (en) | Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof | |
| CN106661333B (en) | Conductive polymer material and molded article thereof | |
| US20220048772A1 (en) | Carbon-Carbon Nanotube Hybrid Materials and Methods of Producing Same | |
| JP7028393B2 (en) | An co-catalyst for an oxygen-generating photocatalyst, an oxygen-generating photocatalyst carrying the co-catalyst, and a complex and a method for producing the complex. | |
| JP6600182B2 (en) | Carbon nanofiber manufacturing method and carbon nanofiber | |
| JP5845515B2 (en) | Method for producing catalyst for carbon nanotube synthesis, method for producing aggregate of carbon nanotubes using the same, and aggregate of carbon nanotubes | |
| JP5909777B2 (en) | Dispersion | |
| JP5909778B2 (en) | Dispersion | |
| JP2017006888A (en) | Catalyst for producing carbon nanofiber, method for producing carbon nanofiber, and carbon nanofiber | |
| CN111465579A (en) | Method for preparing carbon nano tube from natural rubber | |
| US10087557B2 (en) | Method for producing carbon nanofibers | |
| KR101608477B1 (en) | Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof | |
| KR20230134126A (en) | Carbon nanotube hybrid material and hybrid material manufacturing method | |
| JP4962545B2 (en) | Fine hollow carbon fiber | |
| JP6600180B2 (en) | Method for producing carbon nanofiber-carbon material composite and carbon nanofiber-carbon material composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180621 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190215 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190226 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190423 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20191001 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191004 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6600182 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |