JP2012116733A - Method for producing fibrous carbon - Google Patents
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- JP2012116733A JP2012116733A JP2010270318A JP2010270318A JP2012116733A JP 2012116733 A JP2012116733 A JP 2012116733A JP 2010270318 A JP2010270318 A JP 2010270318A JP 2010270318 A JP2010270318 A JP 2010270318A JP 2012116733 A JP2012116733 A JP 2012116733A
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- fibrous carbon
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- polyhydric alcohol
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 213
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 45
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 66
- 235000011187 glycerol Nutrition 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 239000012530 fluid Substances 0.000 description 98
- 239000007789 gas Substances 0.000 description 55
- 238000001816 cooling Methods 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- -1 propylene diglycol Chemical compound 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
本発明は繊維状炭素の製造方法に関する。 The present invention relates to a method for producing fibrous carbon.
多価アルコールのひとつであるグリセリンは、将来的に実用化が期待されるバイオディーゼルの製造において副生される原料であり、また、カーボンニュートラルと呼ばれる天然物に由来する環境保全を考えると化学品の原料として利用の意義が非常に高い物質である。 Glycerin, one of polyhydric alcohols, is a raw material by-produced in the production of biodiesel that is expected to be put to practical use in the future, and it is a chemical product considering environmental conservation derived from natural products called carbon neutral. It is a substance that has a very high significance as a raw material.
従って、グリセリンを利用して付加価値の高い素材を合成することは社会的意義が非常に高く、近年では他の化学原料に誘導して、例えばエピクロロヒドリンやプロピレンジグリコールなどを獲得する報告がなされている。 Therefore, synthesizing high-value-added materials using glycerin is highly socially significant, and in recent years it has been reported to be derived from other chemical raw materials, for example, epichlorohydrin or propylene diglycol. Has been made.
しかしながら、同炭素数を有する有用化学物質への変換に関する検討が多く、それ以外の用途の技術開発はあまり検討報告がなされていないのが実情であり、特に繊維状炭素を誘導する視点での報告は学術文献にもほとんど認められない。 However, there are many studies on conversion to useful chemicals having the same number of carbons, and there are few reports on the development of technology for other applications, especially from the perspective of inducing fibrous carbon. Is rarely found in academic literature.
繊維状炭素は、軽量で高強度、電気伝導性等の優れた性質を有しており、様々な用途で広く利用されている。繊維状炭素は例えば、特許文献１には、触媒微粒子を分散した耐熱性の基板に対して、不活性ガスで希釈した炭化水素ガスを暴露して熱処理し、炭化水素ガスの熱分解から繊維状炭素を気相中で生成する方法が開示されている。 Fibrous carbon is lightweight and has excellent properties such as high strength and electrical conductivity, and is widely used in various applications. For example, Patent Document 1 discloses that a heat-resistant substrate in which catalyst fine particles are dispersed is exposed to a heat treatment by exposing a hydrocarbon gas diluted with an inert gas to a fibrous carbon from the thermal decomposition of the hydrocarbon gas. A method for producing carbon in the gas phase is disclosed.
また、特許文献２には、原料にエタノールを用いて、触媒としてニッケル、コバルト若しくはこれらの混合物を大気圧下で作用させて、窒素雰囲気下で化学気相堆積法にて繊維状炭素を成長させる方法が開示されている。 In Patent Document 2, ethanol is used as a raw material, nickel, cobalt or a mixture thereof is allowed to act as a catalyst under atmospheric pressure, and fibrous carbon is grown by chemical vapor deposition under a nitrogen atmosphere. A method is disclosed.
特許文献３には、原料にケトン類およびエーテル類からなる群から選択される酸素含有炭素源化合物を用いて、触媒及び／又は触媒前駆体化合物と共に加熱帯域に導入し、気相法により繊維状炭素を成長される方法が開示されている。 In Patent Document 3, an oxygen-containing carbon source compound selected from the group consisting of ketones and ethers is used as a raw material, introduced into a heating zone together with a catalyst and / or a catalyst precursor compound, and fibrous by a gas phase method. A method for growing carbon is disclosed.
繊維状炭素が新素材として社会的にも注目されているが、その製造にあたっては多くの検討が石化原料を利用しており、環境側面で二酸化炭素負荷の課題を有する。 Fibrous carbon has attracted social attention as a new material, but many studies have used petrochemical raw materials for its production, and has a problem of carbon dioxide load from the environmental aspect.
本発明の課題は、多価アルコールを繊維状炭素に変換する技術を提供することである。 An object of the present invention is to provide a technique for converting polyhydric alcohol into fibrous carbon.
本発明は、多価アルコールと水とを含む混合ガスを、反応部に設けられた平滑面を有する触媒に４００〜１０００℃の加熱雰囲気下で接触させることにより、平均繊維径１０〜２００ｎｍの繊維状炭素を製造するものである。 In the present invention, a fiber having an average fiber diameter of 10 to 200 nm is obtained by bringing a mixed gas containing a polyhydric alcohol and water into contact with a catalyst having a smooth surface provided in a reaction section in a heated atmosphere at 400 to 1000 ° C. The carbon is produced.
本発明によれば、多価アルコールから繊維状炭素を製造することができる。 According to the present invention, fibrous carbon can be produced from a polyhydric alcohol.
以下、実施形態を図面に基づいて詳細に説明する。 Hereinafter, embodiments will be described in detail with reference to the drawings.
（実施形態１）
＜反応装置＞
図１は、実施形態に係る反応装置１０を示す。
(Embodiment 1)
<Reactor>
FIG. 1 shows a reaction apparatus 10 according to an embodiment.
この反応装置１０は、繊維状炭素を得る構成のものであり、原料流体供給源たる原料流体供給部１１からガス回収部１５まで延びる管が設けられており、また、その管に上流から下流に向かって順に流体供給ポンプ１２及び反応部１３が間隔をおいて直列に介設され、さらに、反応部１３を加熱可能なように加熱部１６が設けられている。 This reactor 10 is configured to obtain fibrous carbon, and is provided with a pipe extending from a raw material fluid supply section 11 as a raw material fluid supply source to a gas recovery section 15, and the pipe is provided from upstream to downstream. The fluid supply pump 12 and the reaction unit 13 are sequentially arranged in series with an interval therebetween, and a heating unit 16 is provided so that the reaction unit 13 can be heated.
この反応装置１０は、反応流体供給部１１から原料である多価アルコールを含む反応流体を流体供給ポンプ１２により反応部１３に供給し、反応部１３で多価アルコールと水とを含む混合ガスとした後、反応部１３内に配置された触媒１７と反応作用することで、触媒表面上に繊維状炭素を生長させる構成としている。また反応後に存在するガスはガス回収部１５にて回収すると共に、生成した繊維状炭素は、連続、又は回分的に前述の運転処理で生長を施した後、反応を停止して反応部１３から触媒１７と共に取り出して回収する。 The reaction apparatus 10 supplies a reaction fluid containing polyhydric alcohol as a raw material from a reaction fluid supply unit 11 to a reaction unit 13 by a fluid supply pump 12, and a mixed gas containing polyhydric alcohol and water in the reaction unit 13 After that, by reacting with the catalyst 17 disposed in the reaction unit 13, the fibrous carbon is grown on the catalyst surface. In addition, the gas present after the reaction is recovered by the gas recovery unit 15, and the produced fibrous carbon is grown continuously or batchwise by the above-described operation process, and then the reaction is stopped and the reaction unit 13 is stopped. The catalyst 17 is taken out and collected.
尚、多価アルコールと共に水を原料に加えることで、反応部１３において繊維状炭素を良好に生長させると共に水性ガスを合成することもできる。副生した水性ガスはガス回収部にて回収し、別用途に供することもできる。 In addition, by adding water with a polyhydric alcohol to a raw material, fibrous carbon can be made to grow well in the reaction part 13, and water gas can also be synthesize | combined. The by-produced water gas can be recovered by the gas recovery unit and used for another purpose.
反応部１３は、触媒１７を内部に配置する構成であるが、その構造は槽、塔、配管など任意に選定することができる。この中で、繊維状炭素を生長させる触媒１７を簡便に設置すると共に、反応後に取り出す上で塔及び配管の構造が好適である。 Although the reaction part 13 is the structure which arrange | positions the catalyst 17 inside, the structure can be arbitrarily selected, such as a tank, a tower, and piping. Of these, the structure of the tower and the piping is suitable for easily installing the catalyst 17 for growing the fibrous carbon and taking it out after the reaction.
反応部１３は、多価アルコールから繊維状炭素を加熱雰囲気下で製造する上で高温に曝すこともあり、耐熱性を有する材料を選定すると共に、放熱を抑えるための装置設計に配慮が必要である。 The reaction unit 13 may be exposed to high temperatures when producing fibrous carbon from polyhydric alcohol in a heated atmosphere, and it is necessary to select a heat-resistant material and to consider the device design for suppressing heat dissipation. is there.
反応流路１３ａの断面外周で囲われる部分の面積は特に限定されないが、等価直径に換算して１〜１００００ｍｍであることが好ましく、本反応処理が吸熱性を有することを考えて繊維状炭素の生長を好適に進めるには伝熱性が向上できる５〜５０００ｍｍであることがより好ましく、１０〜１０００ｍｍであることが特に好ましい。なお、等価直径とは、反応流路１３ａの上記面積と同面積の正円の直径である。 The area of the portion surrounded by the outer periphery of the cross section of the reaction channel 13a is not particularly limited, but is preferably 1 to 10,000 mm in terms of equivalent diameter, and considering that this reaction treatment has endothermic properties, In order to favor the growth, the thickness is more preferably from 5 to 5000 mm, particularly preferably from 10 to 1000 mm, which can improve the heat conductivity. The equivalent diameter is a diameter of a perfect circle having the same area as the area of the reaction channel 13a.
反応場１４を構成する反応流路１３ａには、触媒１７が設けられている。この触媒１７は、表面が平滑面であり、反応流体の流動方向に沿って延びるように形成された平滑な表面を有することが好ましい。尚、平滑面の指標として、ＪＩＳ Ｂ ０６０１で規定している中心線平均粗さＲａで評価することができる。中心線平均粗さＲａが５．０μｍ以下であることが好ましく、１．０μｍ以下であることがより好ましく、０．５μｍ以下であることが更に好ましい。 A catalyst 17 is provided in the reaction flow path 13 a constituting the reaction field 14. The catalyst 17 preferably has a smooth surface and a smooth surface formed so as to extend along the flow direction of the reaction fluid. In addition, it can evaluate by the centerline average roughness Ra prescribed | regulated by JISB0601 as a parameter | index of a smooth surface. The center line average roughness Ra is preferably 5.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.5 μm or less.
触媒１７としては、８〜１２族、好ましくは８〜１０族のいずれかの金属を工業的に好適に利用できる。例えば、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔなどが挙げられ、これらの中でも８〜１０族のものが工業的なコスト、入手容易性、安全性の面から好適であり、更に、Ｎｉ、Ｒｕ、Ｐｄ、Ｐｔがより好ましい。これらは、無論、複合的に利用することも可能であり、例えば、Ｎｉを含む混合物が好適に使用でき、また水素などを用いた還元処理や酸素や空気を用いた酸化処理などの事前な処理を施して、その表面の酸化状態を制御した利用も可能である。また、９９％以上の純度を有する純金属状態で触媒表面を構成することが製作や経済面に有利である。 As the catalyst 17, any metal of Group 8-12, preferably Group 8-10 can be used industrially. For example, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Os, Ir, Pt and the like can be mentioned. Among these, those of group 8 to 10 are industrial cost, availability, and safety. From the surface, Ni, Ru, Pd, and Pt are more preferable. Of course, these can also be used in combination. For example, a mixture containing Ni can be suitably used, and a pretreatment such as a reduction treatment using hydrogen or an oxidation treatment using oxygen or air can be used. It is possible to use the surface by controlling the oxidation state of the surface. In addition, it is advantageous in terms of production and economy to construct the catalyst surface in a pure metal state having a purity of 99% or more.
触媒１７は、例えば、図２（ａ）及び（ｂ）に示すように、金属ワイヤーやワイヤー束或いは撚線といった線状構造体、板状構造体などの細長構造体、図２（ｃ）に示すように、反応部１３内部の反応流路１３ａの内壁等で構成される。触媒１７は、平滑面を有することから、繊維状炭素が生長して堆積した後に回収が容易である。多孔質な粒状触媒では反応性は高いものの、その細孔内に繊維状炭素が堆積し、取り出しが困難となる。触媒の平滑面に堆積した繊維状炭素は、反応部１３より触媒を取り出した後、掻き落とすなどして回収することができる。 The catalyst 17 is, for example, as shown in FIGS. 2 (a) and 2 (b), a linear structure such as a metal wire, a wire bundle or a stranded wire, an elongated structure such as a plate-like structure, and FIG. 2 (c). As shown, it is constituted by the inner wall of the reaction flow path 13a inside the reaction section 13 and the like. Since the catalyst 17 has a smooth surface, it can be easily recovered after the fibrous carbon has grown and deposited. Although the porous granular catalyst has high reactivity, fibrous carbon accumulates in the pores, making it difficult to take out. The fibrous carbon deposited on the smooth surface of the catalyst can be recovered by removing the catalyst from the reaction section 13 and then scraping it off.
細長構造体の触媒１７の場合、外周表面が反応流体の流動方向に沿って延びるように形成された表面に相当する。この場合、面体の組立で反応流路１３ａが構成される反応部１３については、一方の面体の溝に触媒１７を配置すればよく、既成の管で反応流路１３ａが構成される反応部１３については、反応流路１３ａに触媒１７を挿入すればよい。なお、反応流体の流動方向に沿って間欠的に複数の触媒金属が設けられ、それらが全体として反応流体の流動方向に沿って延びるように形成された表面を構成していてもよい。また、触媒１７は、反応部１３の流入部から流出部まで至るように全部に設けられていても、その一部にだけ設けられていてもいずれでもよい。 In the case of the elongated catalyst 17, the outer peripheral surface corresponds to a surface formed so as to extend along the flow direction of the reaction fluid. In this case, with respect to the reaction part 13 in which the reaction channel 13a is configured by the assembly of the face pieces, the catalyst 17 may be disposed in the groove of one face piece, and the reaction part 13 in which the reaction channel 13a is configured by an existing tube. For the above, the catalyst 17 may be inserted into the reaction channel 13a. In addition, a plurality of catalyst metals may be provided intermittently along the flow direction of the reaction fluid, and they may constitute a surface formed so as to extend along the flow direction of the reaction fluid as a whole. Further, the catalyst 17 may be provided in the whole from the inflow part to the outflow part of the reaction part 13 or may be provided only in a part thereof.
反応流路１３ａの内壁が触媒１７の場合、形成する金属に触媒金属を適用する、或いは、反応流路１３ａの内壁を鍍金、スパッタ、塗布乾燥等の手法により事後的に触媒１７で形成すればよい。なお、内壁が反応流体の流動方向に沿って間欠的に触媒金属で形成されていてもよい。また、触媒１７は、反応部１３の流入部から流出部まで至るように全部に設けられていても、その一部にだけ設けられていてもいずれでもよい。 When the inner wall of the reaction channel 13a is the catalyst 17, a catalytic metal is applied to the metal to be formed, or the inner wall of the reaction channel 13a is formed later with the catalyst 17 by a technique such as plating, sputtering, coating and drying. Good. The inner wall may be formed of a catalytic metal intermittently along the flow direction of the reaction fluid. Further, the catalyst 17 may be provided in the whole from the inflow part to the outflow part of the reaction part 13 or may be provided only in a part thereof.
また、複数の触媒構成単位からなる触媒１７が設けられた反応流路１３ａは、反応流体が触媒１７近傍においてよどみのない状態で流動するように構成することで、繊維状炭素を均一に成長させながら同時に水性ガスを効率的に合成することができる。また、触媒１７近傍においてよどみの領域（いわゆるデッドスペース）が無ければ、反応流体の反応滞留時間分布がより均一となり、それによって安定した繊維状炭素の生長を促すことにもなる。 In addition, the reaction flow path 13a provided with the catalyst 17 composed of a plurality of catalyst constituent units is configured so that the reaction fluid flows in a stagnation state in the vicinity of the catalyst 17, thereby allowing the fibrous carbon to grow uniformly. At the same time, water gas can be efficiently synthesized. Further, if there is no stagnation region (so-called dead space) in the vicinity of the catalyst 17, the reaction residence time distribution of the reaction fluid becomes more uniform, thereby promoting stable growth of fibrous carbon.
流体供給ポンプ１２は、反応流体供給部１１からの反応流体を反応部１３に供給する。流体供給ポンプ１２としては、例えば、反応流体が液体の場合、渦巻きポンプ、ディフューザーポンプ、渦巻き斜流ポンプ、斜流ポンプ、軸流ポンプ、ギヤポンプ、スクリューポンプ、カムポンプ、ベーンポンプ、ピストンポンプ、プランジャーポンプ、ダイヤフラムポンプ、渦流ポンプ、粘性ポンプ、気泡ポンプ、ジェットポンプ、電磁ポンプ等が挙げられる。これらの中でも脈流の少ない型式のものが好ましい。その理由は、反応流体等を脈流を伴わずに流路に流通させた場合、流路内の各部位で均一で安定した流れが保持され、安定した混合現象が行われ、反応に不具合を生ずることがなく、所望する反応性及び選択性の高い化学量論条件が均一に達せられるという反応上の利点が得られるためである。なお、流体供給ポンプ１２を用いる方法の他、圧力差を利用した方法により反応流体を反応部１３に供給してもよい。 The fluid supply pump 12 supplies the reaction fluid from the reaction fluid supply unit 11 to the reaction unit 13. As the fluid supply pump 12, for example, when the reaction fluid is a liquid, a vortex pump, a diffuser pump, a vortex mixed flow pump, a mixed flow pump, an axial flow pump, a gear pump, a screw pump, a cam pump, a vane pump, a piston pump, a plunger pump , Diaphragm pumps, vortex pumps, viscosity pumps, bubble pumps, jet pumps, electromagnetic pumps and the like. Among these, the type with less pulsating flow is preferable. The reason is that when a reaction fluid or the like is circulated in the flow path without pulsating flow, a uniform and stable flow is maintained in each part in the flow path, a stable mixing phenomenon is performed, and the reaction is troubled. This is because there is a reaction advantage that the stoichiometric conditions of the desired reactivity and high selectivity can be achieved uniformly. In addition to the method using the fluid supply pump 12, the reaction fluid may be supplied to the reaction unit 13 by a method using a pressure difference.
加熱部１６による加熱方式としては、例えば、熱油や蒸気等の加熱媒体による熱交換法、電気ヒータ等の発熱体との接触伝熱や輻射伝熱による方法、ヒートポンプを利用する方法などが挙げられる。 Examples of the heating method by the heating unit 16 include a heat exchange method using a heating medium such as hot oil or steam, a method using contact heat transfer or radiation heat transfer with a heating element such as an electric heater, or a method using a heat pump. It is done.
以上の反応装置１０を構成する各部材は、高温で反応が行われることを考慮すると、反応温度よりも融点の高い材質で形成されたものである必要がある。また、反応温度に早期に到達させることを考慮すると、熱伝導性に優れる材質で形成されたものであることが好ましい。これらのことから、反応装置１０を構成する各部材の材質としては、金属であることが好ましく。かかる金属としては、例えば、アルミニウム、チタン、クロム、鉄、コバルト、ニッケル、銅、亜鉛、ジルコニウム等の単組成金属、これらを複合的に含有する合金等が挙げられる。合金としては、具体的に、例えば、ＳＵＳ３０４やＳＵＳ３１６に代表されるオーステナイト鋼、ＳＵＳ４２０に代表されるマルテンサイト鋼、ＳＵＳ３２９に代表されるフェライトとオーステナイトとの２相ステンレス鋼、ハステロイＣ２７６やインコネル６００に代表されるＮｉ合金、６−４チタン合金に代表されるチタン合金等が挙げられる。無論、各部材は、これらの素材を単独で又は２種以上を混在させて形成することができる。 Considering that the reaction is performed at a high temperature, each member constituting the reaction apparatus 10 needs to be formed of a material having a melting point higher than the reaction temperature. Further, considering that the reaction temperature is reached at an early stage, it is preferably made of a material having excellent thermal conductivity. From these things, it is preferable that the material of each member constituting the reaction apparatus 10 is a metal. Examples of such metals include single-composition metals such as aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, and zirconium, and alloys containing these in combination. Specific examples of the alloy include, for example, austenitic steel typified by SUS304 and SUS316, martensitic steel typified by SUS420, duplex stainless steel of ferrite and austenite typified by SUS329, Hastelloy C276 and Inconel 600. Examples thereof include a Ni alloy, a titanium alloy represented by a 6-4 titanium alloy, and the like. Of course, each member can be formed of these materials singly or in combination of two or more.
＜繊維状炭素の製造方法＞
次に、この反応装置１０を用いた繊維状炭素の製造方法について説明する。
<Method for producing fibrous carbon>
Next, the manufacturing method of fibrous carbon using this reaction apparatus 10 is demonstrated.
この繊維状炭素の製造方法は、多価アルコールと水とを、反応部１３に設けられた平滑面を有する触媒１７に４００〜１０００℃の加熱雰囲気下で接触させることにより、煤の外観を有する固体物質を生成させるものである。 This method for producing fibrous carbon has a soot appearance by bringing polyhydric alcohol and water into contact with a catalyst 17 having a smooth surface provided in the reaction section 13 in a heated atmosphere at 400 to 1000 ° C. A solid substance is generated.
ここで、多価アルコールとは、炭素数が２以上で且つ水酸基が２つ以上結合した構造を有する化合物をいう。当該条件を満たせば、水酸基以外にカルボン酸基やアルデヒド基などが結合してもよい。具体的には、多価アルコールとしては、例えば、２価のアルコールとして、エチレンジグリコール、１，２−プロパンジオール、１，３−プロパンジオール、２，３−ヒドロキシプロパナール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、酒石酸などが挙げられ、３価のアルコールとして、グリセリン、１，２，４−ブタントリオール、１，２，６−ヘキサントリオールなどが挙げられ、４価のアルコールとして、ペンタエリスリトールなどが挙げられる。これらの中でもエチレンジグリコールやグリセリンの利用が経済性の観点より望ましく、更に環境視点においても将来的に実用化が期待されるバイオディーゼルの製造において副生される原料であり、また、カーボンニュートラルと呼ばれる天然物に由来する環境保全を考えると化学品の原料として利用の意義が非常に高く、グリセリンが最も好ましい。 Here, the polyhydric alcohol refers to a compound having a structure having 2 or more carbon atoms and two or more hydroxyl groups bonded. If the conditions are satisfied, a carboxylic acid group or an aldehyde group may be bonded in addition to the hydroxyl group. Specifically, as the polyhydric alcohol, for example, as divalent alcohol, ethylene diglycol, 1,2-propanediol, 1,3-propanediol, 2,3-hydroxypropanal, 1,2-butane Examples include diol, 1,3-butanediol, 1,4-butanediol, and tartaric acid. Examples of the trivalent alcohol include glycerin, 1,2,4-butanetriol, and 1,2,6-hexanetriol. Examples of the tetravalent alcohol include pentaerythritol. Among these, the use of ethylene diglycol and glycerin is desirable from the viewpoint of economy, and is a raw material by-produced in the production of biodiesel that is expected to be put to practical use in the future from the viewpoint of the environment. Considering environmental conservation derived from a natural product called, it is highly useful as a raw material for chemicals, and glycerin is most preferable.
この繊維状炭素の製造方法では、反応流体供給部１１から原料である多価アルコール及び水の混合物である反応流体を流体供給ポンプ１２を介して反応部１３に混合ガスとして供給する。 In this method for producing fibrous carbon, a reaction fluid, which is a mixture of polyhydric alcohol and water as raw materials, is supplied from the reaction fluid supply unit 11 to the reaction unit 13 through the fluid supply pump 12 as a mixed gas.
反応部１３に供給する反応流体の相状態は、炭素析出を好適に促す観点から気体とする。この反応流体の相状態は、加熱部１６による反応部１３の加熱温度設定及びガス回収部１５の手前に設けられた圧力調整器による反応流体の排圧設定により調整する。多価アルコールと水とを含む混合ガスの反応部１３への供給時の温度は、４００℃以上が好ましく、５００℃以上がより好ましく、また、１０００℃以下が好ましく、８００℃以下がより好ましい。 The phase state of the reaction fluid supplied to the reaction unit 13 is a gas from the viewpoint of suitably promoting carbon deposition. The phase state of the reaction fluid is adjusted by setting the heating temperature of the reaction unit 13 by the heating unit 16 and setting the exhaust pressure of the reaction fluid by the pressure regulator provided in front of the gas recovery unit 15. The temperature at the time of supply to the reaction part 13 of the mixed gas containing a polyhydric alcohol and water is preferably 400 ° C or higher, more preferably 500 ° C or higher, more preferably 1000 ° C or lower, and more preferably 800 ° C or lower.
反応部１３に供給する多価アルコールと水とのモル比率は、繊維状炭素の生長を好適に促すためには、多価アルコールの炭素原子数に対して水を０．０１〜６モル倍とすることが好ましく、０．１〜４モル倍とするのがより好ましい。このモル比率は好適には１〜３モル倍である。例えば、多価アルコールがグリセリンの場合、反応流体中のグリセリンと水との混合比率は、反応を好適に行わせるためには、グリセリンに対する水のモル倍率を０．００３３〜２．０とすることが好ましく、０．０３３〜１．３３３とするのがさらに好ましい。多価アルコールがペンタエリスリトールの場合、反応流体中のペンタエリスリトールと水との混合比率は、反応を好適に行わせるためには、ペンタエリスリトールに対する水のモル倍率を０．００２５〜１．５０とすることが好ましく、０．０２５〜１．０とするのがさらに好ましい。 The molar ratio of the polyhydric alcohol and water supplied to the reaction unit 13 is preferably 0.01 to 6 moles of water with respect to the number of carbon atoms of the polyhydric alcohol in order to favor the growth of fibrous carbon. It is preferable to make it 0.1 to 4 mole times. This molar ratio is preferably 1 to 3 molar times. For example, when the polyhydric alcohol is glycerin, the mixing ratio of glycerin and water in the reaction fluid is such that the molar ratio of water to glycerin is 0.0033 to 2.0 in order to allow the reaction to be performed appropriately. Is preferable, and 0.033 to 1.333 is more preferable. When the polyhydric alcohol is pentaerythritol, the mixing ratio of pentaerythritol and water in the reaction fluid is such that the molar ratio of water to pentaerythritol is 0.0025 to 1.50 in order to carry out the reaction suitably. It is preferably 0.025 to 1.0, and more preferably 0.025 to 1.0.
なお、反応性や収率を損なわない範囲で、反応流体に多価アルコール及び水以外の物質を適宜混合させてもよい。かかる物質としては、例えば、窒素、アルゴン、ヘリウム、酸素、二酸化炭素等のガスが挙げられる。また、反応流体には、多価アルコール及び水の他に本質的な反応性を損なわない有機酸、炭化水素、アルコール、アルデヒドなどの有機物やその塩類、或いは、無機塩類等を含有させてもよい。 In addition, a substance other than polyhydric alcohol and water may be appropriately mixed in the reaction fluid as long as reactivity and yield are not impaired. Examples of such a substance include gases such as nitrogen, argon, helium, oxygen, and carbon dioxide. In addition to the polyhydric alcohol and water, the reaction fluid may contain organic substances such as organic acids, hydrocarbons, alcohols, aldehydes, salts thereof, or inorganic salts that do not impair the essential reactivity. .
また、この繊維状炭素の製造方法では、反応部１３で多価アルコールと水とが反応して繊維状炭素が生成するだけでなく、水性ガスも副生する。 Further, in this method for producing fibrous carbon, not only does the reaction unit 13 react with the polyhydric alcohol and water to produce fibrous carbon, but also water gas is by-produced.
反応流体の多価アルコールと水との反応時間は、０．１秒〜１時間程度が好ましく、１秒〜１０分がより好ましい。例えば、多価アルコールがグリセリンの場合、反応流体のグリセリンと水との反応時間は、０．１秒〜１時間程度が好ましく、１秒〜１０分がより好ましい。多価アルコールがプロパンジオールの場合、反応流体のプロパンジオールと水との反応時間は、０．１秒〜１時間程度が好ましく、１秒〜１０分がより好ましい。反応流体の多価アルコールと水との反応時間は、反応流体の反応部１３での滞留時間として規定されるので、反応場１４の容積に応じて、流体供給ポンプ１２による反応流体の送液速度の設定により適宜調整する。 The reaction time between the polyhydric alcohol of the reaction fluid and water is preferably about 0.1 second to 1 hour, more preferably 1 second to 10 minutes. For example, when the polyhydric alcohol is glycerin, the reaction time between glycerin and water of the reaction fluid is preferably about 0.1 second to 1 hour, and more preferably 1 second to 10 minutes. When the polyhydric alcohol is propanediol, the reaction time between propanediol and water in the reaction fluid is preferably about 0.1 second to 1 hour, more preferably 1 second to 10 minutes. Since the reaction time between the polyhydric alcohol of the reaction fluid and water is defined as the residence time of the reaction fluid in the reaction unit 13, the liquid supply speed of the reaction fluid by the fluid supply pump 12 depends on the volume of the reaction field 14. Adjust appropriately according to the settings.
反応流体の多価アルコールと水との反応温度は、４００〜１０００℃であり、５００〜８００℃がより好ましい。この温度領域では、繊維形状を有する炭素が良好に生成し、極端に高い温度設定でもないためエネルギーコストも低く経済性の観点から好ましい。反応流体の多価アルコールと水との反応温度は、加熱部１６による反応部１３の加熱温度設定により調整する。 The reaction temperature of the polyhydric alcohol and water of the reaction fluid is 400 to 1000 ° C, more preferably 500 to 800 ° C. In this temperature range, carbon having a fiber shape is generated satisfactorily, and since it is not an extremely high temperature setting, the energy cost is low, which is preferable from the viewpoint of economy. The reaction temperature between the polyhydric alcohol of the reaction fluid and water is adjusted by setting the heating temperature of the reaction unit 13 by the heating unit 16.
この繊維状炭素の製造方法では、副生した水性ガスを含む反応流体をガス回収部１５で回収する。 In this fibrous carbon manufacturing method, the reaction fluid containing the by-produced water gas is recovered by the gas recovery unit 15.
回収した水性ガスは、燃料電池、水素エンジン燃料、化学原料等の用途に応じて、必要な品質を達し得る精製を行うこともできる。これらの精製法としては、例えば、ガス透過膜、ＰＳＡ等を用いた方法が挙げられる。 The recovered water gas can be purified to achieve the required quality according to the use of the fuel cell, hydrogen engine fuel, chemical raw material and the like. Examples of these purification methods include a method using a gas permeable membrane, PSA and the like.
以上のような構成の反応装置１０を用いて繊維状炭素を製造すれば、反応場１３に設けられている触媒１７の表面上より、多価アルコールから形状のよい繊維状炭素を効率的に得ることができる。 If fibrous carbon is manufactured using the reactor 10 having the above-described configuration, good-shaped fibrous carbon is efficiently obtained from polyhydric alcohol from the surface of the catalyst 17 provided in the reaction field 13. be able to.
製造される繊維状炭素は、形状として、平均繊維径１０ｎｍ〜２００ｎｍのものを得ることができる。ここで、平均繊維径は、走査型電子顕微鏡や透過型電子顕微鏡による観察から得た画像を基に各繊維状炭素を目視的に採寸することや、レーザー走査型顕微鏡による画像解析処理すること等で測定することができる。この平均繊維径を得る観点から、具体的には、多価アルコールと水とを含む混合ガスを、流速０．００１〜０．０５ｍ/ｓで連続的に反応部１３に供給した後、該反応部１３に内在する触媒の総表面積に対する多価アルコールの供給量が０．１〜２０ｋｇ/ｍ２のときに運転を停止し、該触媒の表面に生長した繊維状炭素を回収することが望ましい。より細い平均繊維径として１００ｎｍ以下を求める場合には、更に０．５〜５ｋｇ/ｍ２以下のときに繊維状炭素を回収することが望ましい。 The produced fibrous carbon can be obtained with a mean fiber diameter of 10 nm to 200 nm. Here, the average fiber diameter is determined by visually measuring each fibrous carbon based on an image obtained by observation with a scanning electron microscope or a transmission electron microscope, or performing image analysis processing with a laser scanning microscope. Can be measured. Specifically, from the viewpoint of obtaining this average fiber diameter, a mixed gas containing polyhydric alcohol and water is continuously supplied to the reaction unit 13 at a flow rate of 0.001 to 0.05 m / s, and then the reaction is performed. It is desirable to stop the operation when the amount of polyhydric alcohol supplied relative to the total surface area of the catalyst in the portion 13 is 0.1 to 20 kg / m 2 and to recover the fibrous carbon grown on the surface of the catalyst. When a thinner average fiber diameter of 100 nm or less is desired, it is desirable to collect fibrous carbon when the average fiber diameter is 0.5 to 5 kg / m 2 or less.
（実施形態２）
＜反応装置＞
図３は、実施形態２に係る反応装置１０を示す。なお、実施形態１と同一名称の部位は実施形態１と同一符号で示す。
(Embodiment 2)
<Reactor>
FIG. 3 shows the reaction apparatus 10 according to the second embodiment. In addition, the site | part of the same name as Embodiment 1 is shown with the same code | symbol as Embodiment 1. FIG.
この反応装置１０は、連続的に反応生成物を得る連続式のものであり、反応流体供給部１１から生成物回収部１５まで延びる管が設けられており、また、その管に上流から下流に向かって順に流体供給ポンプ１２、予熱部１８、反応部１３及び冷却部１９が間隔をおいて直列に介設され、さらに、予熱部１８及び反応部１３を加熱可能なように加熱部１６が設けられている。 The reactor 10 is a continuous type that continuously obtains a reaction product, and is provided with a pipe extending from the reaction fluid supply unit 11 to the product recovery unit 15, and the pipe is provided from upstream to downstream. The fluid supply pump 12, the preheating unit 18, the reaction unit 13, and the cooling unit 19 are arranged in series at intervals, and a heating unit 16 is provided so that the preheating unit 18 and the reaction unit 13 can be heated. It has been.
この反応装置１０は、反応流体供給部１１から原料である多価アルコール（例えば、グリセリンやプロパンジオール等）及び水の混合物である反応流体を流体供給ポンプ１２を介して予熱部１８に供給し、予熱部１８で予熱した反応流体を反応部１３に供給し、反応部１３で多価アルコールと水とが反応して繊維状炭素を生成し、副生する水性ガスを含む反応流体を冷却部１９に供給して冷却し、冷却した反応流体を生成物回収部１５で回収すると共に、運転終了後に反応部１３から繊維状炭素を回収するものである。 The reaction apparatus 10 supplies a reaction fluid that is a mixture of polyhydric alcohol (for example, glycerin, propanediol, etc.) and water as a raw material from a reaction fluid supply unit 11 to a preheating unit 18 via a fluid supply pump 12. The reaction fluid preheated by the preheating unit 18 is supplied to the reaction unit 13. The reaction unit 13 reacts with polyhydric alcohol and water to produce fibrous carbon, and the reaction fluid containing the by-produced water gas is cooled by the cooling unit 19. And cooled, the reaction fluid cooled is recovered by the product recovery unit 15, and fibrous carbon is recovered from the reaction unit 13 after the operation is completed.
＜繊維状炭素の製造方法＞
次に、この反応装置１０を用いた繊維状炭素の製造方法について説明する。
<Method for producing fibrous carbon>
Next, the manufacturing method of fibrous carbon using this reaction apparatus 10 is demonstrated.
この繊維状炭素の製造方法も、実施形態１と同様に多価アルコールと水とから煤の外見を有する固形物を生成すると共に、水性ガスと称される水素と一酸化炭素との混合ガスを副生させるものである。 This method for producing fibrous carbon also produces a solid substance having the appearance of soot from polyhydric alcohol and water, as in the first embodiment, and a mixed gas of hydrogen and carbon monoxide, which is called a water gas. It is a by-product.
この水性ガスの製造方法では、予熱部１８で予熱した多価アルコールと水との混合ガスの反応流体を反応部１３に供給する。 In this water gas production method, a reaction fluid of a mixed gas of polyhydric alcohol and water preheated in the preheating unit 18 is supplied to the reaction unit 13.
反応流体の予熱時間は、０．１秒〜１時間が好ましく、１秒〜１０分がより好ましい。例えば、多価アルコールがグリセリンの場合、反応流体の予熱時間は、０．１秒〜１時間が好ましく、１秒〜１０分がより好ましい。多価アルコールがプロパンジオールの場合、反応流体の予熱時間は、０．１秒〜１時間が好ましく、１秒〜１０分がより好ましい。反応流体の予熱時間は、反応流体の予熱部１８での滞留時間で規定されるので、予熱部１８の容量の選定により調整できるが、予熱部１８の容量が決まっている場合には、流体供給ポンプ１２による反応流体の送液速度の設定により決まることになる。 The preheating time of the reaction fluid is preferably 0.1 second to 1 hour, and more preferably 1 second to 10 minutes. For example, when the polyhydric alcohol is glycerin, the preheating time of the reaction fluid is preferably 0.1 second to 1 hour, and more preferably 1 second to 10 minutes. When the polyhydric alcohol is propanediol, the preheating time of the reaction fluid is preferably 0.1 second to 1 hour, more preferably 1 second to 10 minutes. Since the preheating time of the reaction fluid is defined by the residence time of the reaction fluid in the preheating unit 18, it can be adjusted by selecting the capacity of the preheating unit 18, but when the capacity of the preheating unit 18 is determined, fluid supply This is determined by the setting of the feeding speed of the reaction fluid by the pump 12.
反応流体の予熱温度、つまり、多価アルコールと水とを含む混合ガスの反応部１３への供給時の温度は、４００℃以上が好ましく、５００℃以上がより好ましく、また、１０００℃以下が好ましく、８００℃以下がより好ましい。反応流体の予熱温度は、加熱部１６による反応部１３の加熱温度設定により同時に調整される。 The preheating temperature of the reaction fluid, that is, the temperature at the time of supplying the mixed gas containing polyhydric alcohol and water to the reaction section 13 is preferably 400 ° C. or higher, more preferably 500 ° C. or higher, and preferably 1000 ° C. or lower. 800 ° C. or lower is more preferable. The preheating temperature of the reaction fluid is adjusted simultaneously by setting the heating temperature of the reaction unit 13 by the heating unit 16.
この水性ガスの製造方法では、反応部１３で生成した水性ガスを含む反応流体を冷却部１９に供給して冷却する。 In this water gas production method, the reaction fluid containing the water gas generated in the reaction unit 13 is supplied to the cooling unit 19 to be cooled.
反応流体の冷却時間は、０．１秒〜１時間が好ましく、１秒〜１０分がより好ましい。反応流体の冷却時間は、反応流体の冷却部１９での滞留時間で規定されるので、冷却部１９の容量の選定により調整できるが、冷却部１９の容量が決まっている場合には、流体供給ポンプ１２による反応流体の送液速度の設定により決まることになる。 The cooling time of the reaction fluid is preferably 0.1 second to 1 hour, and more preferably 1 second to 10 minutes. Since the cooling time of the reaction fluid is defined by the residence time of the reaction fluid in the cooling unit 19, it can be adjusted by selecting the capacity of the cooling unit 19, but if the capacity of the cooling unit 19 is determined, the fluid supply This is determined by the setting of the feeding speed of the reaction fluid by the pump 12.
反応流体の冷却後温度は、０〜２００℃が好ましく、２０〜１００℃がより好ましい。反応流体の冷却後温度は、冷却部１９による反応流体の冷却温度設定により調整する。 0-200 degreeC is preferable and the temperature after cooling of the reaction fluid has more preferable 20-100 degreeC. The temperature after cooling of the reaction fluid is adjusted by setting the cooling temperature of the reaction fluid by the cooling unit 19.
その他の構成及び作用・効果は実施形態１と同一である。 Other configurations, operations, and effects are the same as those of the first embodiment.
以下に説明する実施例及び比較例の繊維状炭素の製造実験のそれぞれについて、反応部における繊維状炭素の生成量を求めた。 The production amount of fibrous carbon in the reaction part was determined for each of the fibrous carbon production experiments of Examples and Comparative Examples described below.
−繊維状炭素の形状観察−
反応終了後、触媒に堆積した繊維状炭素は走査型電子顕微鏡（日立製作所製ＦＥＳＥＭ）を用いて繊維状炭素の外観を観察すると共に、得られた写真画像から任意に１５箇所の繊維状炭素を選出して繊維径及び繊維長を計測し、その平均値とした。
-Observation of the shape of fibrous carbon-
After completion of the reaction, the fibrous carbon deposited on the catalyst is observed with a scanning electron microscope (FESEM manufactured by Hitachi, Ltd.) and the appearance of the fibrous carbon is arbitrarily determined from the obtained photographic image. The fiber diameter and fiber length were selected and averaged.
−水性ガスの副生収量−
捕集された気体についてＴＣＤ型のガスクロマトグラフ分析装置（ＶＡＲＩＡＮ社マイクロＧＣ、ＣＰ４９００）にて水素、一酸化炭素、二酸化炭素等のそれぞれのガス成分濃度を定量した。
-By-product yield of water gas-
Each gas component concentration of hydrogen, carbon monoxide, carbon dioxide, etc. was quantified about the collected gas with a TCD type gas chromatograph analyzer (Varian Micro GC, CP4900).
−炭素析出量−
捕集された気体についてガスクロマトグラフ分析にて一酸化炭素、二酸化炭素、メタン、エタン、エチレン、プロパン、プロピレン等、炭素原子を含むそれぞれのガス成分濃度を定量し、気体捕集量との積からそれぞれのモル数を算出した。また捕集された液体についてガスクロマトグラフ分析にて未反応原料及び反応生成物のそれぞれの定量を行ってモル数を算出した。そして、各成分の分子構造から換算される炭素原子のモル重量を合計し、反応原料の投入量から算出される炭素原子のモル重量から減じた数値を炭素析出量とした。なお、この炭素析出量は、その値が大きいほど触媒表面上に炭素析出が効果的に進行していることを意味する。
-Carbon deposition amount-
Quantify the concentration of each gas component containing carbon atoms, such as carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, propylene, etc. in the gas chromatographic analysis of the collected gas. Each number of moles was calculated. The collected liquid was subjected to gas chromatographic analysis to determine the unreacted raw material and the reaction product, and the number of moles was calculated. And the molar weight of the carbon atom converted from the molecular structure of each component was totaled, and the numerical value subtracted from the molar weight of the carbon atom calculated from the input amount of the reaction raw material was defined as the carbon deposition amount. Note that the larger the value of the carbon deposition amount, the more effectively the carbon deposition proceeds on the catalyst surface.
（実施例１）
図３に示すのと同一構成であって、流体供給ポンプがマイクロフィーダーであり、予熱部が内径１．０ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製のものであり、反応部が内径７．５ｍｍ及び長さ２００ｍｍの内壁が平滑面の円管流路を有するニッケル材製のもの（ニッケル純度＞９９．０％、中心線平均粗さＲａ０．４μｍ）であり、冷却部が内径１．８ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製で空冷方式のものであり、加熱部として輻射伝熱形式で６００℃に昇温及び恒温する電気炉を配置した反応装置を構成した。この反応装置では、反応部の内壁が金属触媒を構成する（触媒総表面積０．００４７３１ｍ２）。
Example 1
3, the fluid supply pump is a microfeeder, the preheating part is made of SUS316 material having an inner diameter of 1.0 mm and a length of 1000 mm, and the reaction part is The inner wall is 7.5 mm in inner diameter and 200 mm in length and is made of nickel material having a smooth circular pipe channel (nickel purity> 99.0%, centerline average roughness Ra 0.4 μm), and the cooling part has an inner diameter It is made of SUS316 material having a circular pipe flow path of 1.8 mm and length of 1000 mm, and is an air-cooling type, and constitutes a reactor equipped with an electric furnace that raises and keeps the temperature up to 600 ° C. in a radiant heat transfer type as a heating part did. In this reactor, the inner wall of the reaction part constitutes a metal catalyst (total catalyst surface area 0.004731 m 2 ).
この反応装置に、反応前処理Ａとして、水素を流通させつつ６００℃に昇温し１時間保持する処理を施した。 This reaction apparatus was subjected to a pre-reaction treatment A in which the temperature was raised to 600 ° C. and kept for 1 hour while circulating hydrogen.
そして、この反応前処理Ａ後の反応装置を用い、グリセリン（キシダ化学（株）製、特級）３６．２ｇ及び蒸留水（和光純薬工業（株）製）６３．８ｇを予め混合調製した溶液を反応流体（比重１．０９６）として、マイクロフィードポンプにより１．３０ｍＬ／ｈで連続的に予熱部に供給し、２０℃から６００℃に昇温した。反応流体の反応部への供給時の流速は０．０２５ｍ/ｓであった。反応部での反応流体の温度は６００℃とした。反応部での反応流体の滞留時間（反応時間）は２秒であった。反応部に供給するグリセリンと水とのモル比率は、グリセリンの炭素原子数に対して水９モル倍であった。冷却部では、反応流体を６００℃から２０℃に冷却した。 Then, using the reaction apparatus after the pretreatment A, a solution prepared by previously mixing and preparing 36.2 g of glycerin (made by Kishida Chemical Co., Ltd., special grade) and 63.8 g of distilled water (made by Wako Pure Chemical Industries, Ltd.) As a reaction fluid (specific gravity 1.096) was continuously supplied to the preheating section at 1.30 mL / h by a microfeed pump, and the temperature was raised from 20 ° C to 600 ° C. The flow rate when supplying the reaction fluid to the reaction section was 0.025 m / s. The temperature of the reaction fluid in the reaction part was 600 ° C. The residence time (reaction time) of the reaction fluid in the reaction part was 2 seconds. The molar ratio of glycerin and water supplied to the reaction part was 9 moles of water with respect to the number of carbon atoms of glycerin. In the cooling section, the reaction fluid was cooled from 600 ° C. to 20 ° C.
２０時間の運転後、反応部を解体し、内部に生長した黒色堆積物を１３２ｍｇ回収することができた。また、黒色堆積物はＳＥＭにて確認を行い、図４に示すように繊維状炭素の形状を有し、３９ｎｍの平均繊維径、５８９ｎｍ以上の平均繊維長であることが観察された。尚、運転終了時点における触媒総表面積に対するグリセリンの総供給量は２．２ｋｇ−グリセリン／ｍ２−触媒表面積にあった。 After 20 hours of operation, the reaction part was disassembled and 132 mg of black deposits grown inside could be recovered. Further, the black deposit was confirmed by SEM, and as shown in FIG. 4, it was observed that it had a fibrous carbon shape and an average fiber diameter of 39 nm and an average fiber length of 589 nm or more. In addition, the total supply amount of glycerin relative to the total surface area of the catalyst at the end of the operation was 2.2 kg-glycerin / m 2 -catalyst surface area.
冷却部から得られた気液混合状態の反応流体をテドラーバックに捕集し、ガス量、ガス組成をそれぞれ分析した。 The reaction fluid in a gas-liquid mixed state obtained from the cooling part was collected in a Tedlar bag, and the gas amount and gas composition were analyzed.
その結果、回収ガス量は９．８Ｌであり、終了直前で捕集されたガスは水素６６％、一酸化炭素１０％を含む組成であった。 As a result, the amount of recovered gas was 9.8 L, and the gas collected immediately before the end had a composition containing 66% hydrogen and 10% carbon monoxide.
（実施例２）
図３に示すのと同一構成であって、流体供給ポンプがマイクロフィーダーであり、予熱部が内径１．０ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製のものであり、反応部が内径７．５ｍｍ及び長さ２００ｍｍの内壁が平滑面の円管流路を有するニッケル材製のもの（ニッケル純度＞９９．０％、中心線平均粗さＲａ０．４μｍ）であり、冷却部が内径１．８ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製で空冷方式のものであり、加熱部として輻射伝熱形式で６００℃に昇温及び恒温する電気炉を配置した反応装置を構成した。この反応装置では、反応部の内壁が金属触媒を構成する（触媒総表面積０．００４７３１ｍ２）。
(Example 2)
3, the fluid supply pump is a microfeeder, the preheating part is made of SUS316 material having an inner diameter of 1.0 mm and a length of 1000 mm, and the reaction part is The inner wall is 7.5 mm in inner diameter and 200 mm in length and is made of nickel material having a smooth circular pipe channel (nickel purity> 99.0%, centerline average roughness Ra 0.4 μm), and the cooling part has an inner diameter It is made of SUS316 material having a circular pipe flow path of 1.8 mm and length of 1000 mm, and is an air-cooling type, and constitutes a reactor equipped with an electric furnace that raises and keeps the temperature up to 600 ° C. in a radiant heat transfer type as a heating part did. In this reactor, the inner wall of the reaction part constitutes a metal catalyst (total catalyst surface area 0.004731 m 2 ).
この反応装置に、反応前処理Ａとして、水素を流通させつつ６００℃に昇温し１時間保持する処理を施した。 This reaction apparatus was subjected to a pre-reaction treatment A in which the temperature was raised to 600 ° C. and kept for 1 hour while circulating hydrogen.
そして、この反応前処理Ａ後の反応装置を用い、グリセリン（キシダ化学（株）製、特級）３６．２ｇ及び蒸留水（和光純薬工業（株）製）６３．８ｇを予め混合調製した溶液を反応流体（比重１．０９６）として、マイクロフィードポンプにより１．３０ｍＬ／ｈで連続的に予熱部に供給し、２０℃から６００℃に昇温した。反応流体の反応部への供給時の流速は０．０２５ｍ/ｓであった。反応部での反応流体の温度は６００℃とした。反応部での反応流体の滞留時間（反応時間）は２秒であった。反応部に供給するグリセリンと水とのモル比率は、グリセリンの炭素原子数に対して水９モル倍であった。冷却部では、反応流体を６００℃から２０℃に冷却した。 Then, using the reaction apparatus after the pretreatment A, a solution prepared by previously mixing and preparing 36.2 g of glycerin (made by Kishida Chemical Co., Ltd., special grade) and 63.8 g of distilled water (made by Wako Pure Chemical Industries, Ltd.) As a reaction fluid (specific gravity 1.096) was continuously supplied to the preheating section at 1.30 mL / h by a microfeed pump, and the temperature was raised from 20 ° C to 600 ° C. The flow rate when supplying the reaction fluid to the reaction section was 0.025 m / s. The temperature of the reaction fluid in the reaction part was 600 ° C. The residence time (reaction time) of the reaction fluid in the reaction part was 2 seconds. The molar ratio of glycerin and water supplied to the reaction part was 9 moles of water with respect to the number of carbon atoms of glycerin. In the cooling section, the reaction fluid was cooled from 600 ° C. to 20 ° C.
１００時間の運転後、反応部を解体し、内部に生長した黒色堆積物を４９３ｍｇ回収することができた。また、黒色堆積物はＳＥＭにて確認を行い、図５に示すように繊維状炭素の形状を有し、６９ｎｍの平均繊維径、３９６ｎｍ以上の平均繊維長であることが観察された。尚、運転終了時点における触媒総表面積に対するグリセリンの総供給量は１０．９ｋｇ−グリセリン／ｍ２−触媒表面積にあった。 After 100 hours of operation, the reaction part was disassembled, and 493 mg of black deposit grown inside could be recovered. Further, the black deposit was confirmed by SEM, and as shown in FIG. 5, it was observed that it had a fibrous carbon shape and an average fiber diameter of 69 nm and an average fiber length of 396 nm or more. In addition, the total supply amount of glycerin relative to the total surface area of the catalyst at the end of the operation was 10.9 kg-glycerin / m 2 -catalyst surface area.
冷却部から得られた気液混合状態の反応流体をテドラーバックに捕集し、ガス量、ガス組成をそれぞれ分析した。 The reaction fluid in a gas-liquid mixed state obtained from the cooling part was collected in a Tedlar bag, and the gas amount and gas composition were analyzed.
その結果、回収ガス量は２４．１Ｌであり、終了直前で捕集されたガスは水素６８％、一酸化炭素９％を含む組成であった。 As a result, the amount of recovered gas was 24.1 L, and the gas collected immediately before the end had a composition containing 68% hydrogen and 9% carbon monoxide.
（比較例１）
図３に示すのと同一構成であって、流体供給ポンプがマイクロフィーダーであり、予熱部が内径１．０ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製のものであり、反応部が内径１．８ｍｍ及び長さ２００ｍｍの円管流路を有するＳＵＳ３１６材製のものにＮｉ粉末（純度９９．０％以上、粒径１５０μｍ以下、触媒総表面積０．０００５３２ｍ２）１１８ｍｇを充填したものであり、冷却部が内径１．８ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製で空冷方式のものであり、加熱部として輻射伝熱形式で６００℃に昇温及び恒温する電気炉を配置した反応装置を構成した。
(Comparative Example 1)
3, the fluid supply pump is a microfeeder, the preheating part is made of SUS316 material having an inner diameter of 1.0 mm and a length of 1000 mm, and the reaction part is It is made of SUS316 material having a circular pipe flow path with an inner diameter of 1.8 mm and a length of 200 mm, filled with 118 mg of Ni powder (purity 99.0% or more, particle size 150 μm or less, total catalyst surface area 0.000532 m 2 ). There is an electric furnace that is made of SUS316 and has an air cooling method with a cooling part having a circular pipe flow path with an inner diameter of 1.8 mm and a length of 1000 mm. The arranged reactor was configured.
この反応装置に、反応前処理Ａとして、水素を流通させつつ６００℃に昇温し１時間保持する処理を施した。 This reaction apparatus was subjected to a pre-reaction treatment A in which the temperature was raised to 600 ° C. and kept for 1 hour while circulating hydrogen.
そして、この反応前処理Ａ後の反応装置を用い、グリセリン（キシダ化学（株）製、特級）３６．２ｇ及び蒸留水（和光純薬工業（株）製）６３．８ｇを予め混合調製した溶液を反応流体（比重１．０９６）として、マイクロフィードポンプにより０．２８ｍＬ／ｈで連続的に予熱部に供給し、２０℃から６００℃に昇温した。反応流体の反応部への供給時の流速は０．０９７ｍ/ｓであった。反応部での反応流体の温度は６００℃とした。反応部での反応流体の滞留時間（反応時間）は２秒であった。反応部に供給するグリセリンと水とのモル比率は、グリセリンの炭素原子数に対して水９モル倍であった。冷却部では、反応流体を６００℃から２０℃に冷却した。 Then, using the reaction apparatus after the pretreatment A, a solution prepared by previously mixing and preparing 36.2 g of glycerin (made by Kishida Chemical Co., Ltd., special grade) and 63.8 g of distilled water (made by Wako Pure Chemical Industries, Ltd.) As a reaction fluid (specific gravity 1.096) was continuously supplied to the preheating portion at 0.28 mL / h by a microfeed pump, and the temperature was raised from 20 ° C to 600 ° C. The flow rate when supplying the reaction fluid to the reaction section was 0.097 m / s. The temperature of the reaction fluid in the reaction part was 600 ° C. The residence time (reaction time) of the reaction fluid in the reaction part was 2 seconds. The molar ratio of glycerin and water supplied to the reaction part was 9 moles of water with respect to the number of carbon atoms of glycerin. In the cooling section, the reaction fluid was cooled from 600 ° C. to 20 ° C.
１１時間の運転後、反応部には黒色堆積物が認められ、供給したグリセリン量から回収されていない炭素量を逆算して１９０ｍｇが在中していた。また、黒色堆積物はＳＥＭにて確認を行い、図６に示すように不定形な炭素粒子の形状を有することが観察された。尚、運転終了時点における触媒総表面積に対するグリセリンの総供給量は２．３ｋｇ−グリセリン／ｍ２−触媒表面積にあった。 After 11 hours of operation, black deposits were observed in the reaction part, and 190 mg was present by back-calculating the amount of carbon not recovered from the amount of glycerin supplied. Further, the black deposit was confirmed by SEM, and it was observed that it had an amorphous carbon particle shape as shown in FIG. In addition, the total supply amount of glycerin with respect to the total surface area of the catalyst at the end of the operation was 2.3 kg-glycerin / m 2 -catalyst surface area.
冷却部から得られた気液混合状態の反応流体をテドラーバックに捕集し、ガス量、ガス組成をそれぞれ分析した。 The reaction fluid in a gas-liquid mixed state obtained from the cooling part was collected in a Tedlar bag, and the gas amount and gas composition were analyzed.
その結果、回収ガス量は１．３Ｌであり、終了直前で捕集されたガスは水素６３％、一酸化炭素１０％を含む組成であった。 As a result, the amount of recovered gas was 1.3 L, and the gas collected just before the end had a composition containing 63% hydrogen and 10% carbon monoxide.
（比較例２）
図３に示すのと同一構成であって、流体供給ポンプがマイクロフィーダーであり、予熱部が内径１．０ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製のものであり、反応部が内径１．８ｍｍ及び長さ１００ｍｍの内壁が平滑面の円管流路を有するニッケル材製のもの（ニッケル純度＞９９．０％、中心線平均粗さＲａ０．４μｍ）であり、冷却部が内径１．８ｍｍ及び長さ１０００ｍｍの円管流路を有するＳＵＳ３１６材製で空冷方式のものであり、加熱部として輻射伝熱形式で６００℃に昇温及び恒温する電気炉を配置した反応装置を構成した。この反応装置では、反応部の内壁が金属触媒を構成する（触媒総表面積０．０００５５９ｍ２）。
(Comparative Example 2)
3, the fluid supply pump is a microfeeder, the preheating part is made of SUS316 material having an inner diameter of 1.0 mm and a length of 1000 mm, and the reaction part is It is made of nickel material (nickel purity> 99.0%, centerline average roughness Ra 0.4 μm) with an inner wall of 1.8 mm in inner diameter and 100 mm in length and having a smooth circular pipe channel, and the cooling part has an inner diameter It is made of SUS316 material having a circular pipe flow path of 1.8 mm and length of 1000 mm, and is an air-cooling type, and constitutes a reactor equipped with an electric furnace that raises and keeps the temperature up to 600 ° C. in a radiant heat transfer type as a heating part did. In this reactor, the inner wall of the reaction portion constitutes a metal catalyst (total catalyst surface area of 0.000559 m 2 ).
この反応装置に、反応前処理Ａとして、水素を流通させつつ６００℃に昇温し１時間保持する処理を施した。 This reaction apparatus was subjected to a pre-reaction treatment A in which the temperature was raised to 600 ° C. and kept for 1 hour while circulating hydrogen.
そして、この反応前処理Ａ後の反応装置を用い、グリセリン（キシダ化学（株）製、特級）１００ｇを反応流体（比重１．２６６）として、マイクロフィードポンプにより０．０３４ｍＬ／ｈで連続的に予熱部に供給し、２０℃から６００℃に昇温した。反応流体の反応部への供給時の流速は０．００４ｍ/ｓであった。反応部での反応流体の温度は６００℃とした。反応部での反応流体の滞留時間（反応時間）は７．２４秒であった。反応部に供給するグリセリンと水とのモル比率は、グリセリンの炭素原子数に対して水０モル倍であった。冷却部では、反応流体を６００℃から２０℃に冷却した。 Then, using the reaction apparatus after the pre-reaction A, 100 g of glycerin (manufactured by Kishida Chemical Co., Ltd., special grade) is used as a reaction fluid (specific gravity 1.266) and continuously at 0.034 mL / h by a microfeed pump. The temperature was raised from 20 ° C. to 600 ° C. by supplying the preheated portion. The flow rate when the reaction fluid was supplied to the reaction section was 0.004 m / s. The temperature of the reaction fluid in the reaction part was 600 ° C. The residence time (reaction time) of the reaction fluid in the reaction part was 7.24 seconds. The molar ratio of glycerin and water supplied to the reaction part was 0 mole times water relative to the number of carbon atoms of glycerin. In the cooling section, the reaction fluid was cooled from 600 ° C. to 20 ° C.
１８．１時間の運転後、反応部には黒色堆積物が認められ、供給したグリセリン量から回収されていない炭素量を逆算して２０９ｍｇが在中していた。また、黒色堆積物はＳＥＭにて確認を行い、不定形な炭素粒子の形状を有することが観察された。尚、運転終了時点における触媒総表面積に対するグリセリンの総供給量は１．４ｋｇ−グリセリン／ｍ２−触媒表面積にあった。 After the operation for 18.1 hours, black deposits were observed in the reaction part, and 209 mg was present by calculating back the amount of carbon not recovered from the supplied amount of glycerin. Further, the black deposit was confirmed by SEM, and it was observed that it had an amorphous carbon particle shape. In addition, the total supply amount of glycerin relative to the total surface area of the catalyst at the end of the operation was 1.4 kg-glycerin / m 2 -catalyst surface area.
冷却部から得られた気液混合状態の反応流体をテドラーバックに捕集し、ガス量、ガス組成をそれぞれ分析した。 The reaction fluid in a gas-liquid mixed state obtained from the cooling part was collected in a Tedlar bag, and the gas amount and gas composition were analyzed.
その結果、回収ガス量は１．５Ｌであり、終了直前で捕集されたガスは水素４１％、一酸化炭素２５％を含む組成であった。 As a result, the amount of recovered gas was 1.5 L, and the gas collected just before the end had a composition containing 41% hydrogen and 25% carbon monoxide.
（まとめ）
表１は、実施例１、２及び比較例１、２それぞれで用いた反応装置の反応部の反応流路等の構成及び試験評価結果を示す。
(Summary)
Table 1 shows the configuration of the reaction flow path and the like of the reaction section of the reaction apparatus used in Examples 1 and 2 and Comparative Examples 1 and 2 and the test evaluation results.
実施例１と比較例１とを比較すると、触媒としての効果的な形状が分かる。 When Example 1 and Comparative Example 1 are compared, an effective shape as a catalyst can be seen.
実施例１と比較例２との比較においては、繊維状炭素の生長に効果的なグリセリンと水の反応比率が分かる。 In the comparison between Example 1 and Comparative Example 2, the reaction ratio of glycerin and water effective for the growth of fibrous carbon is known.
本発明は、繊維状炭素の製造方法として有用であり、例えばカーボンニュートラルな原料であるグリセリンの有効利用方法として高い有用性を有する。 The present invention is useful as a method for producing fibrous carbon. For example, it has high utility as an effective utilization method of glycerin, which is a carbon neutral raw material.
１０ 反応装置
１１ 原料流体供給部
１２ 流体供給ポンプ
１３ 反応部
１３ａ 反応流路
１４ 反応場
１５ 回収部
１６ 加熱部
１７ 触媒
１８ 予熱部
１９ 冷却部
DESCRIPTION OF SYMBOLS 10 Reaction apparatus 11 Raw material fluid supply part 12 Fluid supply pump 13 Reaction part 13a Reaction flow path 14 Reaction field 15 Recovery part 16 Heating part 17 Catalyst 18 Preheating part 19 Cooling part
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