JP2002211909A - Carbon manufacturing apparatus and manufacturing method using the same - Google Patents
Carbon manufacturing apparatus and manufacturing method using the sameInfo
- Publication number
- JP2002211909A JP2002211909A JP2001004392A JP2001004392A JP2002211909A JP 2002211909 A JP2002211909 A JP 2002211909A JP 2001004392 A JP2001004392 A JP 2001004392A JP 2001004392 A JP2001004392 A JP 2001004392A JP 2002211909 A JP2002211909 A JP 2002211909A
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- Prior art keywords
- carbon
- reactor
- gas
- catalyst
- methane
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えば二酸化炭
素、排水素、バイオガス（二酸化炭素とメタンの混合ガ
ス）などの排出ガスを有効利用して、炭素、水素を生成
活用する化学工場、食品工場、排水処理施設、環境・エ
ネルギー分野に適用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical factory and a foodstuff for producing and utilizing carbon and hydrogen by effectively utilizing exhaust gas such as carbon dioxide, exhaust gas and biogas (mixed gas of carbon dioxide and methane). Applies to factories, wastewater treatment facilities, environment and energy fields.
【０００２】[0002]
【従来の技術】１９９７年１２月 地球温暖化防止京都
会議でＣＯ2をはじめとした温室効果ガスの排出量を我
国が２０１０年頃までに１９９０年ベースで６％削減す
るという京都議定書が策定された。２０００年１１月オ
ランダ/ハーグでの地球温暖化防止条約締約国会議で、
排出権取引や森林、草地の吸収量などについて協議され
たが、妥結には至らず２００１年の次回に持ち越しと成
った。いずれにせよ、我が国に課せられるＣＯ2排出削
減量が決まり、今後、企業にかかる負担が増すことは確
かである。各企業のＣＯ2排出削減は急務であり、ＣＯ2
排出抑制、回収方法が検討されている。2. Description of the Related Art In December 1997, the Kyoto Protocol was formulated at the Kyoto Conference on Global Warming Prevention to reduce Japan's greenhouse gas emissions, including CO 2 , by 6% by around 2010 on a 1990 basis. . At the Conference of the Parties to the Convention on Climate Change in the Netherlands / The Hague in November 2000,
Discussions on emissions trading and the amount of forest and grassland removals were not reached, but they were carried over to the next 2001 in 2001. In any case, the amount of CO 2 emission reduction imposed on Japan is determined, and it is certain that the burden on companies will increase in the future. CO 2 emission reduction for each company is urgent, CO 2
Emission control and recovery methods are being studied.
【０００３】ＣＯ2排出抑制はＣＯ2を生み出す石化原料
を使わないでＣＯ2排出量の少ない天然ガスの利用す
る。太陽電池、風力発電、有機廃棄物からバイオガスを
発生させ燃料としての利用など化石燃料のでないエネル
ギーの利用拡大などの対策が行われている。また、一方
排出したＣＯ2回収方法としては、植林や砂漠緑化など
の自然のメカニズムを利用する物と、化学反応などを用
いて有効資源に再利用するものとが存在し、二酸化炭素
と水素を用いてメタノールなどの有効化学物質を取り出
す技術が検討されているが、水素生成コストがかかりす
ぎるなどの課題が有り、実用化には至っていない。[0003] CO 2 emissions is to use less natural gas CO 2 emissions without petrochemical feedstock produce CO 2. Measures are being taken to expand the use of non-fossil fuels, such as solar cells, wind power generation, biogas generation from organic waste, and use as fuel. On the other hand, there are two methods of recovering the emitted CO 2 : those that use natural mechanisms such as tree planting and desert greening, and those that re-use them as effective resources using chemical reactions. A technology for extracting an effective chemical substance such as methanol by using the same has been studied, but there are problems such as an excessive cost of hydrogen generation, and it has not been put to practical use.
【０００４】ＣＯ2の低減としては水素を利用した燃料
電池が有効であるが、この方法では水素の取り出し方法
としてメタノールの水蒸気改質等が利用されているの
で、ＣＯ 2も生成するためＣＯ2削減の抜本的解決策には
ならない。ＣＯ2の発生しない方法が待ち望まれてい
る。[0004] COTwoTo reduce fuel consumption using hydrogen
Batteries are effective, but this method uses hydrogen
Is used for steam reforming of methanol, etc.
And CO TwoAlso produces COTwoFundamental solutions for reduction
No. COTwoLong-awaited
You.
【０００５】ＣＯ2の発生しない方法として、本件出願
人の一人はＣＯ2をメタン、バイオガス（ＣＯ2とＣＨ4
の混合ガス）等と反応させ、炭素として固定化し、生成
する炭素、水素を商品として取り出すことを提案してい
る（特開平−１１−３２２３１５号）。本発明は、さら
に改良を加え、実用化装置として展開させるために、炭
素を要求される純度以上で安定的に生成し、商品として
取り出す方法および装置、生成水素を選択分離し、燃料
電池等に活用出来る様取り出す方法および装置を提供す
ることを目的とする。As a method of generating no CO 2 , one of the present applicants has proposed that CO 2 be converted into methane, biogas (CO 2 and CH 4).
(Japanese Unexamined Patent Publication (Kokai) No. 11-322315). The present invention is a method and an apparatus for stably generating carbon with a purity higher than a required purity and extracting it as a commercial product in order to further improve and develop it as a practical application device, selectively separating generated hydrogen, and producing a fuel cell or the like. It is an object of the present invention to provide a method and a device for taking out the product so that it can be utilized.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を解
決するため、少なくともメタンを含むガスより炭素を製
造する装置であって、炭素を造粒成長させるプレ反応器
と、該プレ反応器にて成長させた炭素を更に成長させる
主反応器とを備えたことを特徴とする炭素製造装置を提
供する。ここで、プレ反応器は、例えば逆円錐形、逆角
錐形、円筒形のいずれかの形状からなり、下部からガス
と触媒を入れ、炭素/触媒を噴流層、流動層を形成させ
ながら造粒成長させるものが好ましいが、特に限定され
ない。なお、「プレ反応」とは、生成炭素を固化させ
ず、粒状で取り出す反応で、反応温度は４００〜７００
℃、好ましくは５５０〜６５０℃である。また、反応器
に入れる触媒は、ニッケル、コバルト、鉄などの金属触
媒が好ましい。このプレ反応では、炭素を例えば３〜３
０ｇ炭素／ｇ触媒、好ましくは１５〜２５ｇ炭素／ｇ触
媒まで成長させる。SUMMARY OF THE INVENTION In order to solve the above problems, the present invention is an apparatus for producing carbon from a gas containing at least methane, comprising: a prereactor for granulating and growing carbon; And a main reactor for further growing the carbon grown in the step (a). Here, the pre-reactor has, for example, an inverted conical shape, an inverted pyramid shape, or a cylindrical shape, in which a gas and a catalyst are charged from below, and the carbon / catalyst is granulated while forming a spouted bed and a fluidized bed. It is preferable to grow the material, but there is no particular limitation. The "pre-reaction" is a reaction in which the produced carbon is not solidified but is taken out in a granular form, and the reaction temperature is 400 to 700.
° C, preferably 550-650 ° C. Further, the catalyst to be put into the reactor is preferably a metal catalyst such as nickel, cobalt and iron. In this pre-reaction, for example, 3 to 3 carbon atoms are used.
Grow to 0 g carbon / g catalyst, preferably 15-25 g carbon / g catalyst.
【０００７】また、主反応器は、例えば逆円錐形、逆角
錐形、円筒形のいずれかの形状からなり、ガスを下部よ
りフイードし、成長した炭素を下部スクリュウコンベア
ーにて定期的に排出し、反応器内にマスフロー移動床を
形成してなるものが好ましいが、特に限定されない。な
お、「主反応」とは、プレ反応で粒状に成長させた炭素
を固化させずにさらに成長させる反応で、反応温度は４
００〜７００℃、好ましくは５５０〜６５０℃である。
また、反応器に入れる触媒は、ニッケル、コバルト、鉄
などの金属触媒が好ましい。この主反応では、炭素を例
えば１００ｇ炭素／ｇ触媒以上、もしくは要求ｇ炭素／
ｇ触媒 濃度まで成長させる。また、主反応器は、炭素
生産量に応じて器数を増減できる。The main reactor has, for example, an inverted conical shape, an inverted pyramid shape, or a cylindrical shape, feeds gas from the lower part, and periodically discharges the grown carbon by a lower screw conveyor. A reactor in which a mass flow moving bed is formed in a reactor is preferable, but is not particularly limited. The “main reaction” is a reaction in which carbon that has been grown in a granular form in the pre-reaction is further grown without solidifying, and the reaction temperature is 4 ° C.
It is 00-700 ° C, preferably 550-650 ° C.
Further, the catalyst to be put into the reactor is preferably a metal catalyst such as nickel, cobalt and iron. In this main reaction, carbon is reduced to, for example, 100 g carbon / g catalyst or more, or required g carbon / g
g Grow to catalyst concentration. Also, the number of main reactors can be increased or decreased according to the amount of carbon production.
【０００８】また、本発明では、プレ反応器及び／又は
主反応器を出たガスの微粉捕獲手段を設け、微粉捕獲
後、微粉を前記反応器に戻してもよい。ここで、微紛捕
獲手段としては、例えば、サイクロン、高温セラミック
バグを用いることができるが、これらには限定されな
い。さらに、ガスをサーモコンプレッサを用いてプレ反
応器及び／又は主反応器に循環させてもよい。サーモコ
ンプレッサを用いるのは、循環ガス系を降温熱ロスする
こと無く昇圧するためで、駆動圧力は、０．１５〜０．
８ＭＰａ、好ましくは０．２〜０．３ＭＰａである。In the present invention, a means for capturing fine powder of gas exiting the pre-reactor and / or the main reactor may be provided, and after capturing the fine powder, the fine powder may be returned to the reactor. Here, as the fine powder capturing means, for example, a cyclone and a high-temperature ceramic bug can be used, but the present invention is not limited to these. Further, the gas may be circulated to the pre-reactor and / or main reactor using a thermocompressor. The reason for using a thermocompressor is to increase the pressure of the circulating gas system without losing temperature and heat.
It is 8 MPa, preferably 0.2 to 0.3 MPa.
【０００９】なお、少なくともメタンを含むガスとは、
例えば、二酸化炭素にメタンまたはバイオガス（ＣＯ2
とＣＨ4の混合ガス）を混合したガスを挙げることがで
きるが、これに限定されない。二酸化炭素とメタンを含
む混合ガスの場合、二酸化炭素とメタンが等モルでない
場合、等モル調節手段を設けてもよい。ここで、等モル
調節手段は、例えば、混合ガスに二酸化炭素又はメタン
を導入する手段である。また、少なくともメタンを含む
ガスが、二酸化炭素がほとんど含まれていない場合、本
発明の装置はメタン分解装置として用いることができ
る。The gas containing at least methane is
For example, methane or biogas (CO 2
And it can be exemplified mixed gas) mixed gas of CH 4, but is not limited thereto. In the case of a mixed gas containing carbon dioxide and methane, if the carbon dioxide and methane are not equimolar, an equimolar adjusting means may be provided. Here, the equimolar adjusting means is, for example, means for introducing carbon dioxide or methane into the mixed gas. When the gas containing at least methane contains little carbon dioxide, the apparatus of the present invention can be used as a methane decomposition apparatus.
【００１０】また、本発明は、少なくともメタンを含む
ガスより炭素を製造する方法であって、炭素を触媒存在
下粒状に成長させることを特徴とする炭素製造法も提供
する。ここで、触媒は、ニッケル、コバルト、鉄などの
金属触媒が好ましく、反応温度は４００〜７００℃、好
ましくは５５０〜６５０℃、圧力は０．００１〜０．２
ＭＰａ、好ましくは０．００３〜０．０２ＭＰａであ
る。このような反応条件下で反応させると炭素を粒状に
成長させることが可能である。なお、本発明により製造
される炭素は、中空繊維状の炭素で（カーボンナノチュ
ーブ）直径１０〜２００ｎｍ、長さが５０nm〜０．１μ
ｍのサイズを有する。[0010] The present invention also provides a method for producing carbon from a gas containing at least methane, wherein the carbon is grown in the presence of a catalyst in the form of particles. Here, the catalyst is preferably a metal catalyst such as nickel, cobalt, and iron. The reaction temperature is 400 to 700 ° C, preferably 550 to 650 ° C, and the pressure is 0.001 to 0.2.
MPa, preferably 0.003 to 0.02 MPa. When reacted under such reaction conditions, carbon can be grown in a granular form. The carbon produced according to the present invention is hollow fiber carbon (carbon nanotube) having a diameter of 10 to 200 nm and a length of 50 nm to 0.1 μm.
m.
【発明の実施の形態】以下本発明のＣＯ2固定化設備を
図１に示すプロセスフローに基づいて詳細に説明する。
原料のメタン、バイオガス（メタン、炭酸ガスの混合ガ
ス）等のガスは例えば３kpa以上（系内加圧、加熱炉内
加圧を保持する圧力）で図示の原料ガスポートより受け
入れ、一部（原料組成により異なるが５〜１０％以下程
度）は循環ガス加熱用に消費され、残りは循環戻りガス
とミキサ−１にて混合して循環ガスブロワー２にて例え
ば０．２Mpa（サーモコンプレッサー駆動圧力以上）ま
で昇圧する。昇圧したガスは加圧ガスレシーバー３にて
蓄圧（触媒投入用駆動ガス、バグフイルター逆洗浄ガス
としてのアキュームレート）し、加熱されている循環戻
りガスと熱回収熱交換器４にて昇温熱交換され、更に循
環ガス加熱炉５にて反応温度４００から７００度（ただ
し原料ガスにより異なる）まで昇温する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the CO 2 fixing equipment of the present invention will be described in detail based on the process flow shown in FIG.
The raw material gas such as methane and biogas (mixed gas of methane and carbon dioxide) is received from the raw material gas port shown in the figure at a pressure of, for example, 3 kpa or more (pressurizing in the system and pressurizing in the heating furnace). About 5 to 10% or less, depending on the raw material composition, is consumed for heating the circulating gas, and the remainder is mixed with the circulating return gas in the mixer -1 and in the circulating gas blower 2, for example, 0.2 Mpa (thermo-compressor driving pressure) Above). The pressurized gas is stored in the pressurized gas receiver 3 (accumulation rate as a driving gas for catalyst input and an accumulation rate as a bag filter backwashing gas), and is heated and heat-exchanged with the heated circulation return gas and the heat recovery heat exchanger 4. The temperature is further raised in the circulating gas heating furnace 5 from the reaction temperature of 400 to 700 ° C. (however, it varies depending on the source gas).
【００１１】昇温したガスは循環用サーモコンプレッサ
ー９の駆動ガスとして送られる。循環ガス量は原料ガス
組成にて決まる反応転化率と滞留触媒量にて決定される
が、反応器内での生成炭素、触媒の流動化ガス速度を考
慮して通常原料ガス供給量の３〜２０倍にて設定する。
サーモコンプレッサー９の採用は熱ロスを生じる事無く
（循環ブロワーの場合はガス温度を下げる必要があ
る。）循環昇圧昇温ガス系を形成する事にある。The heated gas is sent as a driving gas for the circulating thermocompressor 9. The amount of circulating gas is determined by the reaction conversion rate and the amount of retained catalyst determined by the raw material gas composition, and is usually 3 to 3 times the raw material gas supply amount in consideration of the generated carbon in the reactor and the fluidizing gas velocity of the catalyst. Set at 20 times.
The use of the thermo-compressor 9 is to form a circulating pressure-raising gas system without heat loss (in the case of a circulating blower, the gas temperature must be reduced).
【００１２】反応器６、７、８をでた循環ガスはサーモ
コンプレッサー９にて吸引圧縮され再び反応器６、７、
８へ戻されるが、循環ガスの一部はサーモコンプレッサ
ー９を通さず、反応生成水を除去するために４０度まで
降温して冷却分離させる。この冷却器行き循環ガスは熱
回収熱交換器４にて循環ガス加熱炉５行きガスと熱交換
により熱回収されるが、炭素微粉除去のため高温バグフ
イルター１２（例えば８００度耐熱用特殊セラミックフ
イルター）にて除塵し、集塵した炭素微粉、飛散触媒は
反応器６に戻す。熱回収熱交換器４を出たガスは冷却器
（生成水凝縮器）１４にて生成水を冷却分離除去する。
分離された生成水は生成水分離受器１５、生成水送りポ
ンプ１６にて排出される。生成水分離後のガスは循環戻
りガスとして循環ガスブロワー２吸入側に戻るThe circulating gas flowing out of the reactors 6, 7, 8 is suction-compressed by a thermo-compressor 9 and is returned to the reactors 6, 7, 8 again.
8, a part of the circulating gas does not pass through the thermo-compressor 9 and is cooled to 40 ° C. in order to remove the reaction product water. The circulating gas going to the cooler is heat-recovered by heat exchange with the gas going to the circulating gas heating furnace 5 in the heat recovery heat exchanger 4. However, the high-temperature bag filter 12 (for example, a special ceramic filter for heat resistance of 800 degrees) is used to remove carbon fines. ), And the collected carbon fine powder and scattering catalyst are returned to the reactor 6. The gas that has exited the heat recovery heat exchanger 4 is cooled and separated and removed by a cooler (generated water condenser) 14.
The separated product water is discharged by a product water separation receiver 15 and a product water feed pump 16. The gas after generated water separation returns to the circulation gas blower 2 suction side as circulation return gas.
【００１３】なお、原料組成にメタンが多い場合は循環
ガス内に生成水素が余剰となるので、余剰水素を水素分
離装置３０で分離する。分離した水素は燃料電池等に活
用される。If the raw material composition contains a large amount of methane, the generated hydrogen becomes excessive in the circulating gas, so the excess hydrogen is separated by the hydrogen separator 30. The separated hydrogen is used for fuel cells and the like.
【００１４】反応器６は触媒表面の生成炭素を粒状状態
で取り出すためのプレ反応を行わせる物で、噴流層、流
動層を形成させながら炭素量を例えば３〜３０ｇ−炭素
/g−触媒まで成長させる。これが上手く形成されないと
次工程の反応器７で炭素が固化し、排出が困難になる。
この反応器６は、例えば図２に示す様に逆円錐形状をし
ている。図２（ａ）は全体概略図、図２（ｂ）はＡ−Ａ
葬f面図である。図２中、６１が触媒入口、６２が循環
ガス入口、６３が炭素／触媒出口、６４が循環ガス出
口、６５が炭素／触媒回転掻き取り翼、６６は回転攪拌
棒である。原料循環ガスは循環ガス入口６２からフイー
ドされ、触媒/炭素層へ噴流、流動層を形成し、更に反
応器６の中でインジェクター１７にて触媒入口６１に定
期定量フイードされる触媒と噴流混合される。注入され
る触媒は数回/ｈｒ定期的に生産量に応じてバッチ投入
する。触媒は反応器６下部から、炭素を生成させながら
反応器上部に移動していく。生成した炭素/触媒は上部
棚の開口部より回転掻き取り翼６５にて数回/ｈｒ定期
的に掻き取り炭素／触媒出口６３から反応器７へ排出さ
れる。The reactor 6 is used to carry out a pre-reaction for removing carbon formed on the surface of the catalyst in a granular state, and to form a spouted bed and a fluidized bed while reducing the carbon amount to, for example, 3 to 30 g-carbon.
g / g-catalyst. If this is not formed well, the carbon will solidify in the reactor 7 in the next step, making it difficult to discharge.
This reactor 6 has, for example, an inverted conical shape as shown in FIG. FIG. 2A is an overall schematic diagram, and FIG.
It is a funeral f side view. In FIG. 2, 61 is a catalyst inlet, 62 is a circulating gas inlet, 63 is a carbon / catalyst outlet, 64 is a circulating gas outlet, 65 is a carbon / catalyst rotary scraping blade, and 66 is a rotary stirring rod. The raw material circulating gas is fed from the circulating gas inlet 62, spouts into the catalyst / carbon layer to form a fluidized bed, and is further jet-mixed with the catalyst periodically fed to the catalyst inlet 61 by the injector 17 in the reactor 6. You. The catalyst to be injected is charged several times / hr periodically according to the production amount. The catalyst moves from the lower part of the reactor 6 to the upper part of the reactor while generating carbon. The produced carbon / catalyst is scraped several times / hr by a rotary scraping blade 65 from the opening of the upper shelf, and is discharged to the reactor 7 from the carbon / catalyst outlet 63 at regular intervals.
【００１５】反応器６へフィードされる循環ガス量は原
料組成、滞留触媒量により異なるが、例えば１０〜５０
L/ｇ−触媒を目安とする。循環ガスは反応器６内で炭
素、一酸化炭素、水素、水に一部転化され、混合ガス組
成として循環ガス出口６４から反応器６を出てサイクロ
ン１３に送られ微粉/触媒を分離除去し、高温バグフイ
ルター１２に送られる。このガスを高温バグフイルター
１２に直接通さず、サイクロン１３にて分離除去するの
は活性触媒がセラミックフイルターの濾材内に極力入ら
ない様にするためである。The amount of circulating gas fed to the reactor 6 varies depending on the raw material composition and the amount of retained catalyst.
Use L / g-catalyst as a guide. The circulating gas is partially converted into carbon, carbon monoxide, hydrogen, and water in the reactor 6 and exits the reactor 6 from the circulating gas outlet 64 as a mixed gas composition and is sent to the cyclone 13 to separate and remove fine powder / catalyst. Is sent to the high temperature bag filter 12. This gas is not directly passed through the high-temperature bag filter 12 but is separated and removed by the cyclone 13 in order to prevent the active catalyst from entering the filter medium of the ceramic filter as much as possible.
【００１６】反応器７は図３に示す様に例えば、逆円錐
形状をしており、内部にマスフローを形成させるための
円錐型内装物７２と炭素粒子固化防止の為の回転撹拌棒
７４、更に循環ガスを下部より吹き込むノズル７１を保
有している。また、７３は循環ガス入口、７５は炭素抜
き出し口、７６は循環ガス出口、７７は炭素／触媒入口
である。反応器６から排出された炭素は、反応器７の炭
素／触媒入口７７上部より投入され、循環ガス入口７３
からの循環ガスと交流接触しながら、炭素量を例えば５
０〜７０ｇ−炭素/g−触媒まで成長させる。反応器７で
は、炭素は成長しながら凝集固化しないマスフロー移動
床を形成する必要があり、炭素は成長度、炭素滞留量、
幾何形状が重要な要素となる。従って炭素生産量に応じ
て反応器７の基数は増減する。The reactor 7 has, for example, an inverted conical shape as shown in FIG. 3, and has a conical interior 72 for forming a mass flow therein, a rotary stirring rod 74 for preventing solidification of carbon particles, and It has a nozzle 71 for blowing circulating gas from below. Reference numeral 73 denotes a circulating gas inlet, 75 denotes a carbon outlet, 76 denotes a circulating gas outlet, and 77 denotes a carbon / catalyst inlet. The carbon discharged from the reactor 6 is introduced from the upper portion of the carbon / catalyst inlet 77 of the reactor 7 and the circulating gas inlet 73
Carbon contact with the circulating gas from
Grow to 0-70 g-carbon / g-catalyst. In the reactor 7, it is necessary to form a mass flow moving bed in which carbon does not coagulate and solidify while growing.
Geometry is an important factor. Therefore, the number of reactors 7 increases or decreases according to the amount of carbon production.
【００１７】また、排出口（炭素抜き出し口７５）には
凝集破砕、マスフロー排出目的の粉砕排出スクリュウコ
ンベヤー１０が設置される。スクリュウコンベヤー１０
から生成炭素は定期定量排出され、反応器８にフィード
される。循環ガスは、循環ガス出口７６から反応器７を
出て高温バグフイルター１２を通って熱回収熱交換器４
及びサーモコンプレッサー９行ラインへ送られる。Further, a pulverizing and discharging screw conveyor 10 for coagulation and crushing and mass flow discharging is provided at the discharging port (carbon extracting port 75). Screw conveyor 10
, And the generated carbon is periodically discharged and fed to the reactor 8. The circulating gas exits the reactor 7 through the circulating gas outlet 76 and passes through the high-temperature bag filter 12 through the heat recovery heat exchanger 4.
And sent to the thermocompressor 9 line.
【００１８】反応器８は反応器７と同様の形状で炭素量
を例えば１００〜１２０ｇ−炭素/g−触媒まで成長させ
る。生成炭素は定期定量、抜き出しスクリュウコンベヤ
ー１１にて排出され、気力輸送用ブロアー１８にて一酸
化炭素除去槽１９に送られる。この気力輸送ブロアー１
８は一酸化炭素をＣＯ2にて置換する事、炭素温度を１
００℃以下（空気着火防止温度以下）にする事を目的と
する。炭素温度の冷却は炭素輸送集塵機２０、循環冷却
器２１を通した二酸化炭素循環系にておこなわれる。冷
却された炭素は貯槽２２に送られる。なお、図１中、２
３〜２７はシール用ロータリーバルブ、３１は流量コン
トローラ、３２は温度コントローラ、３３は液面コント
ローラ、３４は圧力コントローラである。The reactor 8 has the same shape as that of the reactor 7 and has a carbon content of, for example, 100 to 120 g-carbon / g-catalyst. The generated carbon is discharged at a fixed amount and withdrawn from the screw conveyor 11 at regular intervals, and sent to a carbon monoxide removal tank 19 by a blower 18 for pneumatic transportation. This energy transport blower 1
8 is replacing carbon monoxide with CO 2, and setting carbon temperature to 1
The purpose is to reduce the temperature to 00 ° C or less (below the air ignition prevention temperature). Cooling of the carbon temperature is performed in a carbon dioxide circulation system through a carbon transport dust collector 20 and a circulation cooler 21. The cooled carbon is sent to the storage tank 22. In FIG. 1, 2
Reference numerals 3 to 27 denote rotary valves for sealing, 31 denotes a flow rate controller, 32 denotes a temperature controller, 33 denotes a liquid level controller, and 34 denotes a pressure controller.
【００１９】以上の固定化装置において、原料ガスがＣ
Ｈ4：ＣＯ2＝１：１の等モルの場合には、 ＣＨ4→Ｃ＋２Ｈ2 ２Ｈ4＋ＣＯ2→ＣＯ＋Ｈ2＋Ｈ2Ｏ ＣＯ＋Ｈ2＋Ｈ2Ｏ→Ｃ＋２Ｈ2０ となるが、実際の反応は複雑で、循環ガス系ではＣ
Ｈ4、ＣＯ2、ＣＯ、Ｈ2、Ｈ2Ｏが各々組成の転化率での
ガス平衡組成となり、ある気相組成を形成する。また炭
素は分解され触媒に生成付着させる。原料ガス組成が等
モルでなくメタンが過剰の場合水素が蓄積される事にな
る。蓄積される余剰水素は選択的に分離し、系外で排出
利用する。水素分離は既存技術（吸着分離、水素分離
膜、水素吸蔵合金）にて実現可能であり水素組成要求純
度に依り選定される。例えば水素吸蔵合金を用いる場
合、ミッシュメタル−ニッケル系水素吸蔵合金（MmNｉ
4.5Al0.5）に0.8Mpaで水素を吸蔵させ、２塔サーマルス
イング方式で水素を分離放出させる方法では純度の高い
水素が得られる。In the above fixing apparatus, the raw material gas is C
When H 4 : CO 2 = 1: 1 equimolar, CH 4 → C + 2H 2 2H 4 + CO 2 → CO + H 2 + H 2 O CO + H 2 + H 2 O → C + 2H 20 , but the actual reaction is complicated. In the circulating gas system, C
H 4 , CO 2 , CO, H 2 , and H 2 O each have a gas equilibrium composition at a conversion of the composition, and form a certain gas phase composition. Also, carbon is decomposed and formed and adhered to the catalyst. If the raw material gas composition is not equimolar and methane is excessive, hydrogen will be accumulated. The accumulated excess hydrogen is selectively separated and discharged and used outside the system. Hydrogen separation can be realized by existing technologies (adsorption separation, hydrogen separation membrane, hydrogen storage alloy) and is selected according to the required purity of the hydrogen composition. For example, when a hydrogen storage alloy is used, a misch metal-nickel-based hydrogen storage alloy (MmNi
4.5Al0.5) absorbs hydrogen at 0.8 Mpa and separates and releases hydrogen by a two-column thermal swing method to obtain high-purity hydrogen.
【００２０】また、反応熱収支は等モルの場合、吸熱反
応、発熱反応がほぼバランスし、放熱見合いで熱供給を
行えば良いが、メタンが過剰の場合は分解反応が多く、
吸熱反応が支配するので加熱が必要である。In addition, when the reaction heat balance is equimolar, the endothermic reaction and the exothermic reaction are almost balanced, and heat may be supplied in proportion to heat release.
Heating is necessary because the endothermic reaction is dominant.
【００２１】[0021]
【発明の効果】本発明は上記の構成であるから下記の利
点を有する。 （１）ＣＯ2、排Ｈ2、バイオガス（ＣＯ2とＣＨ4の混合
ガス）を固定化して炭素を連続的に生成する。 （２）要求される純度の炭素を安定的に生成する。 （３）ＣＯ2とＣＨ4の混合ガスが等モルの場合加熱熱量
は初期加熱、冷却ガス再加熱、放熱補充のみとエネルギ
ーが非常に小さい。 （４）バイオガス（ＣＯ2とＣＨ4の混合ガス）でのＣＨ
4の余剰はメタン分解により水素を生成し、水素分離に
より水素の利用が可能。The present invention has the following advantages since it has the above configuration. (1) CO 2 , waste H 2 , and biogas (mixed gas of CO 2 and CH 4 ) are immobilized to continuously generate carbon. (2) stably produce carbon of required purity. (3) When the mixed gas of CO 2 and CH 4 is equimolar, the energy of heating is very small as only the initial heating, cooling gas reheating, and replenishment of heat radiation. (4) CH in biogas (mixed gas of CO 2 and CH 4 )
The surplus of 4 generates hydrogen by decomposition of methane, and hydrogen can be used by hydrogen separation.
【図１】本発明ＣＯ2固定化装置での炭素生成プロセス
フロー図FIG. 1 is a flowchart of a carbon generation process in the CO 2 immobilization apparatus of the present invention.
【図２】プレ反応器の構造の概略を示す図FIG. 2 is a diagram schematically showing the structure of a pre-reactor.
【図３】主反応器の構造の概略を示す図FIG. 3 is a diagram schematically showing the structure of a main reactor.
１：原料／循環ガスミキサ ２：循環ガスブロア ３：加圧ガスレシーバ ４：熱回収熱交換器 ５：循環ガス加熱炉 ６：プレ反応器 ７：反応器１ ８：反応器２ ９：循環用サーモコンプレッサー １０：破砕排出用スクリュウコンベアー １１：抜出しスクリュウコンベア- １２：高温バグフィルター １３：サイクロン １４：生成水凝縮器 １５：生成水分離受器 １６：生成水送りポンプ １７：触媒インジェクター １８：気力輸送用ブロアー １９：一酸化炭素除去槽 ２０：炭素輸送集塵機 ２１：循環冷却器 ２２：貯槽 ２３〜２７：シール用ロータリーバルブ ３０：水素分離装置 ３１：液量コントローラ ３２：温度コントローラ ３３：液面コントローラ ３４：圧力コントローラ 1: Raw material / circulating gas mixer 2: circulating gas blower 3: pressurized gas receiver 4: heat recovery heat exchanger 5: circulating gas heating furnace 6: pre-reactor 7: reactor 18: reactor 2 9: thermo-compressor for circulation 10: Screw conveyor for crushing and discharging 11: Extraction screw conveyor-12: High temperature bag filter 13: Cyclone 14: Generated water condenser 15: Generated water separation receiver 16: Generated water feed pump 17: Catalyst injector 18: Blower for power transfer 19: Carbon monoxide removal tank 20: Carbon transport dust collector 21: Circulating cooler 22: Storage tank 23-27: Rotary valve for sealing 30: Hydrogen separator 31: Liquid volume controller 32: Temperature controller 33: Liquid level controller 34: Pressure controller
フロントページの続き (72)発明者 吉村 修七 三重県四日市市東邦町１番地 三菱化学株 式会社四日市事業所内 (72)発明者 宗澤 潤一 三重県四日市市大字塩浜191番地の１ 三 菱化学エンジニアリング株式会社内 (72)発明者 加藤 三郎 京都市中京区西ノ京桑原町１番地 株式会 社島津製作所内 Ｆターム(参考） 4G004 KA01 KA06 4G046 CA01 CA02 CB02 CC03 CC06 CC08 4G075 AA04 AA23 AA27 AA45 AA61 AA63 BA01 BA05 BA06 BD14 CA02 CA03 CA05 CA54 CA65 CA66 EB01 ED03 FB04 Continued on the front page (72) Inventor Shuichi Yoshimura 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation Yokkaichi Office (72) Inventor Junichi Munezawa 191-1, Shiojihama, Yokkaichi-shi, Mie 1 Mitsubishi Chemical Engineering Co., Ltd. In-company (72) Inventor Saburo Kato 1 Nishinokyo Kuwabaracho, Nakagyo-ku, Kyoto F-term in Shimadzu Corporation (Reference) 4G004 KA01 KA06 4G046 CA01 CA02 CB02 CC03 CC06 CC08 4G075 AA04 AA23 AA27 AA45 AA61 AA63 BA01 BA02 BA06 BD06 CA03 CA05 CA54 CA65 CA66 EB01 ED03 FB04
Claims (10)
造する装置であって、炭素を造粒成長させるプレ反応器
と、該プレ反応器にて成長させた炭素を更に成長させる
主反応器とを備えたことを特徴とする炭素製造装置。1. An apparatus for producing carbon from a gas containing at least methane, comprising: a pre-reactor for granulating and growing carbon; and a main reactor for further growing the carbon grown in the pre-reactor. An apparatus for producing carbon, comprising:
形のいずれかの形状からなり、下部からガスと触媒を入
れ、炭素/触媒を噴流層、流動層を形成させながら造粒
成長させる請求項１記載の炭素製造装置。2. The pre-reactor has an inverted conical shape, an inverted pyramid shape, or a cylindrical shape. Gas and a catalyst are charged from the lower portion, and carbon / catalyst is formed while forming a spouted bed and a fluidized bed. The carbon production apparatus according to claim 1, wherein the carbon is grown.
のいずれかの形状からなり、ガスを下部よりフイード
し、成長した炭素を下部スクリュウコンベアーにて定期
的に排出し、反応器内にマスフロー移動床を形成してな
る請求項１記載の炭素製造装置。3. The main reactor has an inverted conical shape, an inverted pyramid shape, or a cylindrical shape, feeds gas from a lower portion, and periodically discharges grown carbon by a lower screw conveyor. The carbon production apparatus according to claim 1, wherein a mass flow moving bed is formed in the reactor.
反応器及び／又は主反応器を出たガスの微粉捕獲手段を
設け、微粉捕獲後、微粉を前記反応器に戻すことを特徴
とする請求項１乃至３記載の炭素製造装置。4. A carbon production apparatus according to claim 1, further comprising means for capturing fine powder of gas exiting the pre-reactor and / or the main reactor, and after capturing the fine powder, returning the fine powder to the reactor. 4. The carbon production apparatus according to claim 1, wherein:
応器及び／又は主反応器に循環させることを特徴とする
請求項１乃至４記載の炭素製造装置。5. The carbon production apparatus according to claim 1, wherein the gas is circulated to a pre-reactor and / or a main reactor using a thermocompressor.
とメタンを含む混合ガスであり、二酸化炭素とメタンが
等モルでない場合、等モル調節手段を設けてなる請求項
１乃至５記載の炭素製造装置。6. The carbon production apparatus according to claim 1, wherein the gas containing at least methane is a mixed gas containing carbon dioxide and methane, and when carbon dioxide and methane are not equimolar, equimolar adjusting means is provided. .
応器に二酸化炭素又はメタンを導入する手段である請求
項６記載の炭素製造装置。7. The carbon production apparatus according to claim 6, wherein the equimolar adjusting means is means for introducing carbon dioxide or methane into the pre-reactor and the main reactor.
造する方法であって、炭素を触媒存在下粒状に成長させ
ることを特徴とする炭素製造法。8. A method for producing carbon from a gas containing at least methane, wherein the carbon is grown in the form of particles in the presence of a catalyst.
製造法。9. The method according to claim 8, wherein the catalyst is a metal catalyst.
求項８乃至９記載の炭素製造法。10. The method for producing carbon according to claim 8, wherein the reaction temperature is 400 to 700 ° C.
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| JP2001004392A JP4852787B2 (en) | 2001-01-12 | 2001-01-12 | Carbon production equipment |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5829862A (en) * | 1981-08-14 | 1983-02-22 | Mitsubishi Chem Ind Ltd | Preparation of carbon black |
| JPS6351467A (en) * | 1986-08-21 | 1988-03-04 | Kawasaki Steel Corp | Production of high-purity carbon black |
| JPS63319045A (en) * | 1987-06-23 | 1988-12-27 | Masaki Sadakata | Production of fine particle by gaseous phase reaction |
| JPH01298214A (en) * | 1988-05-24 | 1989-12-01 | Asahi Chem Ind Co Ltd | Production of carbon fiber |
| JPH11322315A (en) * | 1998-03-13 | 1999-11-24 | Shimadzu Corp | Carbon production system utilizing biomass |
| JPH11350257A (en) * | 1998-06-05 | 1999-12-21 | Nikkiso Co Ltd | Gas phase growing carbon fiber production unit |
| JP2000086217A (en) * | 1998-09-05 | 2000-03-28 | Agency Of Ind Science & Technol | Production of carbon nanotube |
| JP2000181143A (en) * | 1998-12-11 | 2000-06-30 | Shimadzu Corp | Production of carbon for electrophotographic toner |
| JP2000264616A (en) * | 1999-03-15 | 2000-09-26 | Kawasaki Heavy Ind Ltd | Method and apparatus for producing activated carbonized material |
| JP2000271472A (en) * | 1999-03-24 | 2000-10-03 | Shimadzu Corp | Carbon dioxide immobilizing device by anaerobic fermentation gas |
-
2001
- 2001-01-12 JP JP2001004392A patent/JP4852787B2/en not_active Expired - Lifetime
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5829862A (en) * | 1981-08-14 | 1983-02-22 | Mitsubishi Chem Ind Ltd | Preparation of carbon black |
| JPS6351467A (en) * | 1986-08-21 | 1988-03-04 | Kawasaki Steel Corp | Production of high-purity carbon black |
| JPS63319045A (en) * | 1987-06-23 | 1988-12-27 | Masaki Sadakata | Production of fine particle by gaseous phase reaction |
| JPH01298214A (en) * | 1988-05-24 | 1989-12-01 | Asahi Chem Ind Co Ltd | Production of carbon fiber |
| JPH11322315A (en) * | 1998-03-13 | 1999-11-24 | Shimadzu Corp | Carbon production system utilizing biomass |
| JPH11350257A (en) * | 1998-06-05 | 1999-12-21 | Nikkiso Co Ltd | Gas phase growing carbon fiber production unit |
| JP2000086217A (en) * | 1998-09-05 | 2000-03-28 | Agency Of Ind Science & Technol | Production of carbon nanotube |
| JP2000181143A (en) * | 1998-12-11 | 2000-06-30 | Shimadzu Corp | Production of carbon for electrophotographic toner |
| JP2000264616A (en) * | 1999-03-15 | 2000-09-26 | Kawasaki Heavy Ind Ltd | Method and apparatus for producing activated carbonized material |
| JP2000271472A (en) * | 1999-03-24 | 2000-10-03 | Shimadzu Corp | Carbon dioxide immobilizing device by anaerobic fermentation gas |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002284513A (en) * | 2001-03-28 | 2002-10-03 | Shimadzu Corp | Method for manufacturing carbon |
| US7947245B2 (en) | 2005-04-12 | 2011-05-24 | National University Corporation Kitami Institute Of Technology | Method for producing nanocarbon and catalytic reaction device for producing nanocarbon |
| JP2006290682A (en) * | 2005-04-12 | 2006-10-26 | Kitami Institute Of Technology | Method and catalyst reactor for producing nano-carbon |
| US9403682B2 (en) | 2005-04-12 | 2016-08-02 | National University Corporation Kitami Institute Of Technology | Method for producing nanocarbon and catalytic reaction device for producing nanocarbon |
| JP2007290928A (en) * | 2006-04-26 | 2007-11-08 | Kyushu Institute Of Technology | String-like carbon, method of utilizing the same and method of manufacturing the same |
| JP2009046387A (en) * | 2007-08-21 | 2009-03-05 | Semes Co Ltd | Method and apparatus for synthesizing carbon nanotube |
| JP2009161426A (en) * | 2007-12-31 | 2009-07-23 | Semes Co Ltd | Fluidized bed carbon nanotube production apparatus, and carbon nanotube production apparatus and method using the same |
| JP2010030887A (en) * | 2008-06-30 | 2010-02-12 | Showa Denko Kk | Method of manufacturing carbon nanomaterial and manufacturing unit of carbon nanomaterial |
| JP2012106921A (en) * | 2010-11-16 | 2012-06-07 | Waseda Univ | Method for producing carbon nanotube |
| JP2013049599A (en) * | 2011-08-31 | 2013-03-14 | Hitachi Zosen Corp | Production apparatus of fibrous carbon material |
| JP2015518461A (en) * | 2012-04-16 | 2015-07-02 | シーアストーン リミテッド ライアビリティ カンパニー | Methods and reactors for producing solid carbon nanotubes, solid carbon clusters, and forests |
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| JP2015519280A (en) * | 2012-04-18 | 2015-07-09 | エクソンモービル アップストリーム リサーチ カンパニー | Removal of carbon nanotubes from aqueous systems |
| US9975793B2 (en) | 2012-04-18 | 2018-05-22 | Exxonmobil Upstream Research Company | Removing carbon nanotubes from a water system |
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| US11951428B2 (en) | 2016-07-28 | 2024-04-09 | Seerstone, Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
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| KR102308018B1 (en) | 2019-11-14 | 2021-09-30 | 주식회사 포스코 | Device for manufacturing cabon dust |
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