JP4044990B2 - Carbon dioxide organic treatment method - Google Patents
Carbon dioxide organic treatment method Download PDFInfo
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- JP4044990B2 JP4044990B2 JP27861597A JP27861597A JP4044990B2 JP 4044990 B2 JP4044990 B2 JP 4044990B2 JP 27861597 A JP27861597 A JP 27861597A JP 27861597 A JP27861597 A JP 27861597A JP 4044990 B2 JP4044990 B2 JP 4044990B2
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- carbon dioxide
- hydrogen
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- treatment method
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Description
【０００１】
【発明の属する技術分野】
本発明は、火力発電等の化石燃料を燃焼することにより発生する二酸化炭素（ＣＯ2 ）を有機物化する方法に関するもので、とくにＣＯ2 を、燃料として再資源化する方法に関する。
【０００２】
【従来の技術】
従来、地球温暖化防止の手法として、ＣＯ2 を回収し、これを固定化もしくは再利用する研究が行なわれている。
その代表例として、回収したＣＯ2 をクラスレート化して海中に固定する方法、あるいは藻類や微生物を利用したバイオマスによってＣＯ2 を固定して再資源化を図ることが提案されている。
また、ＣＯ2 を原料とし、触媒を用いてこれからメタンや水素を生成する方法なども提案されている。
【０００３】
しかし、これらは研究の緒についたばかりであり、クラスレート化による固定については、海中環境の問題が新たにクローズアップされており、クラスレート化するためのエネルギー消費等、経済性に対する問題が指摘されている。また、バイオマスによる処理については、大量生産（処理）に難点があるとの指摘もある。
さらに、触媒水素化法により、ＣＯ2 からメタンや水素を生成させる方法は、現在、最も期待されているが、ＣＯ2 の化学転換に要するエネルギーが高くなる可能性があり、これら何れの方法も経済的に懸念があり、産業ベースに乗る具体案がないのが現状である。
【０００４】
【発明が解決しようとする課題】
本発明は産業的に成り立つ手法で、ＣＯ2 を有機物化し、これを資源として再利用を図り得る方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明は、上記課題を解決しようとするもので、鉄成分としてＦｅ 0 ，ＦｅＯ，Ｆｅ 3 Ｏ 4 の少なくとも１種を用い、これを触媒もしくは反応材として、二酸化炭素を１００〜４００気圧、２５０〜４００℃の反応条件で水を水素源とした飽和水蒸気圧下で水熱反応により水素還元を行い、メタノール、アセトアルデヒド、プロパノールを得ることを特徴とする二酸化炭素の有機物化処理方法を提供するものである。
【０００６】
【発明の実施の形態】
本発明は、ＣＯ2 を水素還元して有機物化し、ＣＯ2 を資源化する。このため、水を水素源とした飽和水蒸気圧下で、ＣＯ2 を、鉄成分を触媒もしくは吸着材として水素反応させる。
鉄成分としては、Ｆｅ0 ，ＦｅＯ，Ｆｅ3 Ｏ4 を用いることができる。本実施例では例えば鉱滓を用いた。鉱滓はＦｅＯ，Ｆｅ3 Ｏ4 を主成分としているが、上記反応によってヘマタイト（Ｆｅ2 Ｏ3 ）化する。ヘマタイト化した鉱滓は、これを高炉へ戻してやれば、そのまま製鉄する上での原材料となり、資源的にロスとはならない。
鉱滓は、そのＦｅ成分が触媒として働く。
水素還元を行うに当っては、水をそのまま水素源とするため、水素等を用いるものに比べ遙に安価な溶媒となる。
【０００７】
エネルギーの面からみると、水熱反応するために飽和水蒸気圧の環境を維持するだけで済み、かつＣＯ2 とＦｅＯ／Ｆｅ3 Ｏ4 との反応が発熱反応であることから、この点においても有利である。
本発明によれば、エネルギー的ロス、資源的ロスを少くして、ＣＯ2 を容易にエネルギー源として再利用することができる。従来のＣＯ2 の処理方法に対し、より経済性の高い方法を提供することができる。
【０００８】
図１を参照しながら、本発明を詳細に説明すると、ホッパ１の中へＣＯ2 供給ライン２からＣＯ2 を、水供給ライン３から水を供給し、混合ライン４でＣＯ2を水溶液化した状態にしてホッパ１に送り込む。次いでホッパ１の中へ、さらにＦｅＯ及びＦｅ 3 Ｏ 4 を主成分とする粉砕された鉱滓を送り、攪拌機９で混練しスラリー化する。
ＣＯ2 ，水，鉱滓よりなるスラリー状物は、バルブ１０を通ってスラリーポンプ５により加圧され、ヒータ６で温度保持された反応管７に入り、ここで３００℃〜４００℃程度の飽和水蒸気圧下で、水熱反応が行われる。
【０００９】
そのさい、ＣＯ2 のモル数に対し、水は２倍以上のモル数となるように加え、１００〜４００気圧に加圧する。このように、２５０℃〜４００℃程度の飽和水蒸気圧下の水中にＦｅＯ，Ｆｅ3 Ｏ4 を主成分とする鉱滓を混入し、その中へＣＯ2 を送り込むと、Ｆｅの触媒作用及びヘマタイト化への化合反応を促進する作用により、ＣＯ2 は水素還元され、メタノール（ＣＨ3 ＯＨ）やプロパン（ＣＨ3 ＣＨ2 ＣＨ3 ）等の有機物に転化される。
【００１０】
上記水素還元は例えば、下式によって行なわれる。
ＣＯ2 ＋Ｈ2 Ｏ＋Ｆｅｘ（ ）ｙ → ＣＨ3 ＯＨ，ＣＨ3 ＯＣＨ3 等
式中( ）内は、Ｆｅ0 ，ＦｅＯ，Ｆｅ3 Ｏ4 ，Ｆｅ2 Ｏ3 の混合物である。Ｆｅ0 はＦｅ3+となって、水素３個分、Ｆｅ2+Ｏは水素２個分、Ｆｅ3 Ｏ4 は水素１個分が各々ＣＯ2 を還元するように関与する。
【００１１】
このように、鉱滓は触媒としての機能を持つと共に、ヘマタイト化して化合反応を促進する作用をし、これにより、水中の水素でＣＯ2 を還元する。このときのＧＣ／ＭＳ解析（マス分析）の結果を図２に示す。ａのピークはメタノールで、ｂはアセトアルデヒド，ｃはプロパノールであり、有機化合物を生成していることが分る。
この他、３００℃〜４００℃の範囲内で飽和水蒸気圧を変えると、メタン等の生成もできる。有機物の生成にあたって、特にメタノールを合成したいとする場合は、３５０℃近傍が有効な反応領域となる。
【００１２】
このように反応した有機物を含む水溶液は、フィルタ８で鉱滓と分離され、次の蒸留塔等への反応ラインへ導かれ、所定の有機物と水に分離される。
分離された鉱滓は殆どがヘマタイト化されているため、溶鉱炉で鉱材として用いるか、あるいは、Ｈ2 もしくはＣＯ等の水性ガスにより、２００℃前後の水熱反応により、マグネタイト化して再利用することができる。この場合、反応管７をカートリッジ化して取り替え可能とし、置き替えることもできる。
【００１３】
【実施例】
水ホッパ１中へＣＯ2 のモル数に対して２倍以上のモル数となる水を混合ラインで水溶液化して供給し、これに２００メッシュ以下に粉砕された鉱滓を加え、２５０〜４００℃で１００〜４００気圧で反応を行ったところ、ＣＯ2 をメタノール、アセトアルデヒド、プロパノールにすることができた。
【００１４】
【発明の効果】
本発明によればエネルギー的ロス、資源的ロスを少くしてＣＯ2 を容易にエネルギー源として再利用することができる。
【図面の簡単な説明】
【図１】 本発明に係る処理方法のフロー図である。
【図２】 本発明に基づくＧＣ／ＭＣ解析の結果を示す図である。
【符号の説明】
１ ホッパ
２ ＣＯ2 供給ライン
３ 水供給ライン
４ 混合ライン
５ スラリーポンプ
６ ヒータ
７ 反応管
８ フィルタ
９ 攪拌機
１０ バルブ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for converting carbon dioxide (CO 2 ) generated by burning fossil fuel such as thermal power generation into an organic material, and more particularly to a method for recycling CO 2 as fuel.
[0002]
[Prior art]
Conventionally, as a technique for preventing global warming, research has been conducted to collect CO 2 and fix or reuse it.
As a representative example, a method of clathrating recovered CO 2 and fixing it in the sea, or fixing CO 2 with biomass using algae or microorganisms to recycle is proposed.
Also proposed is a method of producing methane and hydrogen from CO 2 using a catalyst as a raw material.
[0003]
However, these are just the beginning of research. Regarding the fixation by clathrate, the problem of the underwater environment has been newly highlighted, and problems with economics such as energy consumption for the clathrate are pointed out. ing. In addition, it has been pointed out that there is a difficulty in mass production (processing) for biomass processing.
Furthermore, a method of generating methane and hydrogen from CO 2 by catalytic hydrogenation is currently most expected, but the energy required for chemical conversion of CO 2 may be high. At present, there are concerns about the economy and there is no specific plan to get on the industrial base.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method that can be reused by converting CO 2 into an organic material and using it as a resource, using an industrially effective method.
[0005]
[Means for Solving the Problems]
The present invention is intended to solve the above-mentioned problems, and at least one of Fe 0 , FeO, and Fe 3 O 4 is used as an iron component , and this is used as a catalyst or a reaction material, and carbon dioxide is 100 to 400 atm, 250 Provided is a method for organically converting carbon dioxide, characterized in that hydrogen reduction is performed by hydrothermal reaction under saturated steam pressure using water as a hydrogen source under a reaction condition of ˜400 ° C. to obtain methanol, acetaldehyde, and propanol. is there.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, CO 2 is reduced to an organic material by hydrogen reduction, and CO 2 is recycled. For this reason, CO 2 is subjected to a hydrogen reaction under a saturated water vapor pressure using water as a hydrogen source, using an iron component as a catalyst or an adsorbent.
Fe 0 , FeO, and Fe 3 O 4 can be used as the iron component. In this embodiment, for example, iron ore was used. The iron ore is composed mainly of FeO and Fe 3 O 4 , and is converted into hematite (Fe 2 O 3 ) by the above reaction. If hematized slag is returned to the blast furnace, it becomes a raw material for iron making as it is, and there is no loss in resources.
In the iron ore, the Fe component acts as a catalyst.
In performing the hydrogen reduction, water is used as it is as a hydrogen source, so that the solvent is much cheaper than those using hydrogen or the like.
[0007]
From the energy point of view, it is only necessary to maintain a saturated water vapor pressure environment for the hydrothermal reaction, and the reaction between CO 2 and FeO / Fe 3 O 4 is an exothermic reaction. It is advantageous.
According to the present invention, energy loss and resource loss can be reduced, and CO 2 can be easily reused as an energy source. It is possible to provide a more economical method than the conventional CO 2 treatment method.
[0008]
With reference to FIG. 1, when describing the present invention in detail, the CO 2 from the CO 2 supply line 2 into the hopper 1, to supply water from the water supply line 3 and an aqueous solution of CO 2 at a mixing line 4 The state is sent to the hopper 1. Next, the pulverized slag containing FeO and Fe 3 O 4 as main components is further fed into the hopper 1 and kneaded with a
The slurry-like material composed of CO 2 , water, and ore is pressurized by the slurry pump 5 through the valve 10 and enters the reaction tube 7 maintained at the temperature by the heater 6, where the saturated steam at about 300 ° C. to 400 ° C. Under pressure, a hydrothermal reaction takes place.
[0009]
At that time, water is added so that the number of moles is twice or more the number of moles of CO 2 and pressurized to 100 to 400 atm. In this way, when iron ore containing FeO and Fe 3 O 4 as main components is mixed in water under saturated water vapor pressure of about 250 ° C. to 400 ° C., and CO 2 is fed into it, the catalytic action of Fe and the formation of hematite are achieved. By the action of promoting the compounding reaction, CO 2 is reduced by hydrogen and converted into an organic substance such as methanol (CH 3 OH) or propane (CH 3 CH 2 CH 3 ).
[0010]
The hydrogen reduction is performed by the following formula, for example.
CO 2 + H 2 O + Fex () y → CH 3 OH, CH 3 OCH 3 etc. In the formula (), a mixture of Fe 0 , FeO, Fe 3 O 4 , and Fe 2 O 3 is shown. Fe 0 becomes Fe 3+ , 3 hydrogens, Fe 2+ O is 2 hydrogens, and Fe 3 O 4 is 1 hydrogen so that CO 2 is reduced.
[0011]
As described above, the iron ore has a function as a catalyst and also acts to hematite to promote a chemical reaction, thereby reducing CO 2 with hydrogen in water. The result of GC / MS analysis (mass analysis) at this time is shown in FIG. The peak of a is methanol, b is acetaldehyde, c is propanol, and it turns out that the organic compound is produced | generated.
In addition, when the saturated water vapor pressure is changed within a range of 300 ° C. to 400 ° C., methane and the like can be generated. When it is desired to synthesize methanol in the production of organic matter, the reaction region around 350 ° C. is an effective reaction region.
[0012]
The aqueous solution containing the organic matter reacted in this manner is separated from the iron slag by the filter 8 and led to a reaction line to the next distillation column or the like, where it is separated into a predetermined organic matter and water.
Most of the separated slag is hematized, so it should be used as a mineral material in a blast furnace or reused by magnetizing it with water gas such as H 2 or CO by hydrothermal reaction at around 200 ° C. Can do. In this case, the reaction tube 7 can be replaced as a cartridge and can be replaced.
[0013]
【Example】
Into the water hopper 1, water having a number of moles more than twice the number of moles of CO 2 is supplied as an aqueous solution in a mixing line, and the iron powder crushed to 200 mesh or less is added thereto, and the temperature is 250 to 400 ° C. When the reaction was performed at 100 to 400 atmospheres, CO 2 could be converted to methanol, acetaldehyde, and propanol .
[0014]
【The invention's effect】
According to the present invention, CO 2 can be easily reused as an energy source with reduced energy loss and resource loss.
[Brief description of the drawings]
FIG. 1 is a flowchart of a processing method according to the present invention.
FIG. 2 is a diagram showing the results of GC / MC analysis based on the present invention.
[Explanation of symbols]
1 Hopper 2 CO 2 supply line 3 Water supply line 4 Mixing line 5 Slurry pump 6 Heater 7 Reaction tube 8
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27861597A JP4044990B2 (en) | 1997-10-13 | 1997-10-13 | Carbon dioxide organic treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27861597A JP4044990B2 (en) | 1997-10-13 | 1997-10-13 | Carbon dioxide organic treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11116508A JPH11116508A (en) | 1999-04-27 |
| JP4044990B2 true JP4044990B2 (en) | 2008-02-06 |
Family
ID=17599755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27861597A Expired - Fee Related JP4044990B2 (en) | 1997-10-13 | 1997-10-13 | Carbon dioxide organic treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4044990B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010099626A (en) * | 2008-10-27 | 2010-05-06 | Mitsui Eng & Shipbuild Co Ltd | Apparatus and method for reducing and fixing carbon dioxide |
| FR2973364B1 (en) * | 2011-03-31 | 2014-04-25 | Ifp Energies Now | METHOD FOR THE VALORISATION OF CO2 |
| JP6727949B2 (en) * | 2016-06-23 | 2020-07-22 | 学校法人 名城大学 | Hydrocarbon production method |
| CN109516892B (en) * | 2018-11-29 | 2020-08-04 | 上海交通大学 | Method for producing long-chain alkane by using iron powder and cobalt powder to hydrothermally reduce carbon dioxide |
| JP7370038B2 (en) * | 2019-06-28 | 2023-10-27 | 国立研究開発法人産業技術総合研究所 | Hydrocarbon production method |
| JP7449326B2 (en) * | 2022-03-25 | 2024-03-13 | 本田技研工業株式会社 | fuel production system |
-
1997
- 1997-10-13 JP JP27861597A patent/JP4044990B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH11116508A (en) | 1999-04-27 |
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