JPH0610143B2 - Method for synthesizing lower hydrocarbon from carbon dioxide using water as reducing agent - Google Patents
Method for synthesizing lower hydrocarbon from carbon dioxide using water as reducing agentInfo
- Publication number
- JPH0610143B2 JPH0610143B2 JP63045472A JP4547288A JPH0610143B2 JP H0610143 B2 JPH0610143 B2 JP H0610143B2 JP 63045472 A JP63045472 A JP 63045472A JP 4547288 A JP4547288 A JP 4547288A JP H0610143 B2 JPH0610143 B2 JP H0610143B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- water
- reducing agent
- lower hydrocarbon
- methane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 17
- 239000001569 carbon dioxide Substances 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 5
- 229930195733 hydrocarbon Natural products 0.000 title claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 3
- 230000002194 synthesizing effect Effects 0.000 title claims 2
- 239000003638 chemical reducing agent Substances 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002803 fossil fuel Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 235000003332 Ilex aquifolium Nutrition 0.000 description 1
- 241000209027 Ilex aquifolium Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas 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
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［技術分野］ 本発明は白金担持二酸化チタン触媒を水に懸濁させ、３
１０ｎｍ以上の光を照射することによって、二酸化炭素
を常温で水によって還元し、低級炭化水素（メタン、エ
タンなど）を得る方法に関するものである。TECHNICAL FIELD The present invention involves suspending a platinum-supported titanium dioxide catalyst in water.
The present invention relates to a method of reducing carbon dioxide with water at room temperature by irradiation with light having a wavelength of 10 nm or more to obtain lower hydrocarbons (methane, ethane, etc.).
［従来技術］ 化石燃料の消費量の増加に伴って、大気中の二酸化炭素
濃度が年々増加し、その温室効果によって気温の上昇あ
るいは気候の温暖化が引き起こされる地球的規模での環
境問題が懸念されている。また、化石燃料資源の有限性
から、化石燃料の有効利用技術の開発が望まれている。
二酸化炭素を還元し、炭化水素あるいは有用な化学物質
として再利用するために、従来、比較的高温度（３００
℃前後）で水素を用いて、触媒的に還元することは広く
知られており、多くの論文が発表されている。一方、二
酸化チタンなどの光半導性をもつ物質を用いて、二酸化
炭素を水で光還元する方法については、本多らの報告
（Ｎａｔｕｒｅ，２７７，６３７ １９７９）後、いく
つかあるが主生成物はホルムアデヒドである。Ｓｏｍｏ
ｒｏｊａｉらはチタン酸ストロンチウム−白金箔によ
り、二酸化炭素と水蒸気からメタン生成を報告している
（Ｃｈｅｍ．Ｐｈｙｓ．Ｌｅｔｔｅｒｓ，５７，１００
１９７８）． ［発明が解決しようとする問題点］ しかし、これらの光を利用し、水あるいは水蒸気により
二酸化炭素を還元する方法には活性の再現性が得られな
い、活性の持続しないなどの問題点があり、触媒反応し
ての確認がなされていない。[Prior Art] As the consumption of fossil fuels increases, the concentration of carbon dioxide in the atmosphere increases year by year, and the greenhouse effect thereof causes a rise in temperature and global warming, which may cause environmental problems on a global scale. Has been done. Also, due to the finite nature of fossil fuel resources, the development of effective utilization technology for fossil fuels is desired.
In order to reduce carbon dioxide and reuse it as a hydrocarbon or a useful chemical substance, it has been conventionally performed at a relatively high temperature (300
Catalytic reduction with hydrogen at around (° C) is widely known, and many papers have been published. On the other hand, as for the method of photoreducing carbon dioxide with water using a substance having photoconductivity such as titanium dioxide, there are some main generations after the report by Honda et al. (Nature, 277, 637 1979). The object is Holm Adehyd. Somo
Rojai et al. reported methane production from carbon dioxide and water vapor by strontium titanate-platinum foil (Chem. Phys. Letters, 57, 100.
1978). [Problems to be Solved by the Invention] However, the method of reducing carbon dioxide with water or water vapor by using these lights has problems such as lack of reproducibility of activity and persistence of activity. , Catalytic reaction has not been confirmed.
［問題点を解決するための手段］ 本発明者は、二酸化炭素を水で還元する触媒として、二
酸化チタンに白金金属を１〜５重量パーセント担持した
ものを合成し、その活性を検討したところ、３１０ｎｍ
以上の光の照射によって室温で二酸化炭素と水からメタ
ン及びエタンが生成すること及びこの反応が触媒反応と
して進行することが確認できた。種々の排ガス中の二酸
化炭素をメタン、エタンとして再利用することで、化石
燃料資源の有効利用及び大気二酸化炭素濃度の増加を防
ぐために、これを利用できる点に着目して本発明をなす
に至った。 本発明における二酸化チタンは光半導性の
高いアナターゼ形で、比表面積の大きなものが望まし
い。本反応の機構の詳細は明らかでないが、白金担持二
酸化チタンの光触媒作用によって水が分解されて生じる
水素が、二酸化炭素を還元しメタン、エタンが生成する
と考えられる。[Means for Solving the Problems] As a catalyst for reducing carbon dioxide with water, the present inventor synthesized titanium dioxide carrying 1 to 5 weight percent of platinum metal, and studied its activity. 310 nm
It was confirmed that the above irradiation of light produced methane and ethane from carbon dioxide and water at room temperature and that this reaction proceeded as a catalytic reaction. By reusing carbon dioxide in various exhaust gases as methane and ethane, in order to effectively utilize fossil fuel resources and prevent an increase in atmospheric carbon dioxide concentration, the present invention can be made by focusing on the fact that they can be used. It was Titanium dioxide in the present invention is preferably an anatase type having high photoconductivity and a large specific surface area. Although the details of the mechanism of this reaction are not clear, it is considered that hydrogen generated by the decomposition of water by the photocatalytic action of platinum-supported titanium dioxide reduces carbon dioxide to produce methane and ethane.
［発明の効果・用途］ 本発明により得られる白金を担持した二酸化チタンは、
化石燃料の燃焼やセメントの培焼によって生成する二酸
化炭素を光（人工光でも太陽光でもよい）と水という安
価なエネルギーと資源によってメタン、エタンとして再
利用するための触媒として好適である。[Advantages and Uses of the Invention] Platinum-supported titanium dioxide obtained by the present invention is
It is suitable as a catalyst for reusing carbon dioxide generated by burning fossil fuels and culturing cement as methane and ethane by inexpensive energy and resources such as light (artificial light or sunlight) and water.
次に実施例によって本発明を更に詳細に説明する。Next, the present invention will be described in more detail with reference to Examples.
［実施例］ 実施例 １ 市販の試薬特級品である二酸化チタン粉末をヘリウム雰
囲気とした水中に懸濁させ、重量比で１〜５％となるよ
う秤量した塩化白金酸を加える。還元試薬としてのメタ
ノールを少量加えた後、キセノンランプによって光照射
をし、白金金属を二酸化チタン表面に析出、担持した。
この白金担持二酸化チタン粉末−水混合物を濾過、水洗
し、室温で乾燥した。この触媒を２５０ｍｇ秤量し、石
英製の反応器内で水１〜２ｍｌ中に懸濁させた。この反
応器を閉鎖型循環式反応装置に接続し、反応装置を真空
排気した後に、二酸化炭素約６００Ｔｏｒｒを供給し、
ポンプで循環しながら、反応器の底面より５００Ｗキセ
ノンランプからの光（３１０ｎｍ以下の光はフイルター
でカットした）を照射した。反応ガスを適宜、採取し分
析したところ、別紙第１図のごとき結果を得た。二酸化
炭素と水から常温でメタン及びエタンが得られることが
明らかである。なお、実験中、光照射を止めるとメタ
ン、エタンの生成が止まることが確認されている。[Examples] Example 1 Titanium dioxide powder, which is a commercially available special grade reagent, is suspended in water in a helium atmosphere, and chloroplatinic acid weighed so as to have a weight ratio of 1 to 5% is added. After adding a small amount of methanol as a reducing reagent, light was irradiated with a xenon lamp to deposit and carry platinum metal on the surface of titanium dioxide.
This platinum-supported titanium dioxide powder-water mixture was filtered, washed with water, and dried at room temperature. 250 mg of this catalyst was weighed and suspended in 1-2 ml of water in a quartz reactor. This reactor was connected to a closed circulation reactor, the reactor was evacuated, and then about 600 Torr of carbon dioxide was supplied,
While circulating with a pump, the bottom surface of the reactor was irradiated with light from a 500 W xenon lamp (light of 310 nm or less was cut with a filter). When the reaction gas was appropriately sampled and analyzed, the results shown in FIG. 1 of the attached sheet were obtained. It is clear that methane and ethane can be obtained from carbon dioxide and water at room temperature. During the experiment, it was confirmed that methane and ethane production stopped when light irradiation was stopped.
実施例 ２ 二酸化チタンの白金担持量を変化させ、二酸化炭素から
のメタン及びエタンの生成速度を検討したところ、別紙
第１表のごとき結果を得た。白金担持量の増加は、メタ
ン生成速度を大きくすることに効果があるが、エタン生
成速度はあまり変化しないことがわかる。Example 2 When the amount of platinum supported on titanium dioxide was changed and the production rates of methane and ethane from carbon dioxide were examined, the results shown in Table 1 of the attached sheet were obtained. It can be seen that the increase in the amount of platinum supported is effective in increasing the methane production rate, but the ethane production rate does not change much.
第１図は白金担持量２％の二酸化チタンを用いた場合の
反応時間（光照射時間）とメタン及びエタン生成量の関
係を示すグラフである。FIG. 1 is a graph showing the relationship between the reaction time (light irradiation time) and the production amounts of methane and ethane when titanium dioxide having a platinum loading of 2% was used.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 9/04 9280−4Ｈ 9/06 9280−4Ｈ // Ｃ０７Ｂ 61/00 ３００ Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location C07C 9/04 9280-4H 9/06 9280-4H // C07B 61/00 300
Claims (1)
に懸濁させ、この懸濁液に３１０ｎｍ以上の光を照射す
ることにより、常温で二酸化炭素から低級炭化水素を合
成する方法。1. A method of synthesizing a lower hydrocarbon from carbon dioxide at room temperature by suspending titanium dioxide carrying 1 to 5% of platinum in water and irradiating the suspension with light having a wavelength of 310 nm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63045472A JPH0610143B2 (en) | 1988-02-26 | 1988-02-26 | Method for synthesizing lower hydrocarbon from carbon dioxide using water as reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63045472A JPH0610143B2 (en) | 1988-02-26 | 1988-02-26 | Method for synthesizing lower hydrocarbon from carbon dioxide using water as reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01221332A JPH01221332A (en) | 1989-09-04 |
| JPH0610143B2 true JPH0610143B2 (en) | 1994-02-09 |
Family
ID=12720331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63045472A Expired - Lifetime JPH0610143B2 (en) | 1988-02-26 | 1988-02-26 | Method for synthesizing lower hydrocarbon from carbon dioxide using water as reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610143B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007190556A (en) * | 2007-04-06 | 2007-08-02 | Ishihara Sangyo Kaisha Ltd | Visible light-responsive photocatalyst, method for manufacturing the same and photocatalytic body using the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000004993A1 (en) * | 1998-07-23 | 2000-02-03 | Korea Research Institute Of Chemical Technology | Photocatalyst for methane conversion, method for preparing the same and method for preparing low carbohydrates using the same |
| JP2012219233A (en) * | 2011-04-13 | 2012-11-12 | Nippon Telegr & Teleph Corp <Ntt> | Apparatus for recycling carbon dioxide |
-
1988
- 1988-02-26 JP JP63045472A patent/JPH0610143B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007190556A (en) * | 2007-04-06 | 2007-08-02 | Ishihara Sangyo Kaisha Ltd | Visible light-responsive photocatalyst, method for manufacturing the same and photocatalytic body using the same |
| JP4570637B2 (en) * | 2007-04-06 | 2010-10-27 | 石原産業株式会社 | Visible light responsive photocatalyst, method for producing the same, and photocatalyst using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01221332A (en) | 1989-09-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |