JPH06116771A - Production of ethanol - Google Patents
Production of ethanolInfo
- Publication number
- JPH06116771A JPH06116771A JP4263841A JP26384192A JPH06116771A JP H06116771 A JPH06116771 A JP H06116771A JP 4263841 A JP4263841 A JP 4263841A JP 26384192 A JP26384192 A JP 26384192A JP H06116771 A JPH06116771 A JP H06116771A
- Authority
- JP
- Japan
- Prior art keywords
- ethanol
- electrode
- soln
- cuo
- zno
- 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.)
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Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、二酸化炭素を還元する
ことによりエタノールを製造する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing ethanol by reducing carbon dioxide.
【０００２】[0002]
【従来の技術】発電用ボイラ、産業用ボイラ、等化石燃
料の燃焼に対し、発生する排ガス中の二酸化炭素は、従
来、ほとんど無処理のままで大気中に放出されていた
が、昨今、地球環境保全の見地から、二酸化炭素を回収
・工業的利用することが要望されるようになってきた。2. Description of the Related Art Conventionally, carbon dioxide in exhaust gas generated by combustion of power generation boilers, industrial boilers, and fossil fuels has been released into the atmosphere without any treatment. From the viewpoint of environmental protection, there has been a demand for carbon dioxide recovery and industrial use.
【０００３】そして例えば、化石燃料から発生する二酸
化炭素を回収して、電気化学的手法により、有機化合物
に変換しリサイクル利用する技術が種々提案されている
（「地球温暖下の対策技術」オーム社発行、公害資源研
究所地球環境特別研究室編、２４５〜２４９頁参照）。For example, various technologies have been proposed for recovering carbon dioxide generated from fossil fuels, converting them into organic compounds by an electrochemical method and recycling them (“Countermeasures against global warming”, Ohmsha Co., Ltd.). Published, Special Research Laboratory for Global Environment, Institute for Pollution Resources, pp. 245-249).
【０００４】[0004]
【発明が解決しようとする課題】しかし、これら技術
は、製造物の利用価値及び／又は反応選択性（回収効
率）が低いものがほとんどである。反応選択性が高く、
利用価値があるものとして、メタノールに変換する技術
があるのみである。However, most of these techniques have low utility value and / or reaction selectivity (recovery efficiency) of products. High reaction selectivity,
The only technology that has utility is the technology for converting to methanol.
【０００５】そこで、電気化学的手法により、二酸化炭
素を有機化合物に変換しリサイクル利用するに際して、
メタノールより利用価値が高いエタノールに変換する技
術の出現が要請されている。Therefore, when converting carbon dioxide to an organic compound by an electrochemical method for recycling,
The emergence of a technology that converts methanol into ethanol, which has a higher utility value, is required.
【０００６】本発明は上記にかんがみて、電気化学的手
法により、二酸化炭素をエタノールに反応選択性良好に
変換可能な、エタノールの製造方法を提供することを目
的とする。In view of the above, it is an object of the present invention to provide a method for producing ethanol capable of converting carbon dioxide into ethanol with good reaction selectivity by an electrochemical method.
【０００７】[0007]
【課題を解決するための手段】本発明は、上記課題を解
決するために、鋭意開発に努力をした結果、下記構成の
エタノールの製造方法に想到した。In order to solve the above-mentioned problems, the present invention has devised an intensive development effort, and as a result, has conceived an ethanol production method having the following constitution.
【０００８】二酸化炭素を電気化学的に還元することに
よりエタノールを製造するに際して、酸化亜鉛（Ｚｎ
Ｏ）と酸化銅（ＣｕＯ）との複合酸化物電極を還元電極
に用いて、電解液水溶液中で、二酸化炭素を電気化学的
に還元してエタノールを製造することを特徴とする。In producing ethanol by electrochemically reducing carbon dioxide, zinc oxide (Zn oxide) is used.
It is characterized in that a compound oxide electrode of O) and copper oxide (CuO) is used as a reduction electrode to electrochemically reduce carbon dioxide in an aqueous electrolytic solution to produce ethanol.
【０００９】[0009]
Ａ．以下、本発明のエタノールの製造方法を、図例に基
づいて説明する。A. Hereinafter, the method for producing ethanol of the present invention will be described with reference to the drawings.
【００１０】(1) 本発明の方法に使用する還元電極は、
酸化亜鉛と酸化銅との複合酸化物からなるものを使用す
る。この複合酸化物における、酸化亜鉛と酸化銅のモル
比は、酸化亜鉛／酸化銅＝８／２〜４／６、望ましく
は、略７／３とする。(1) The reducing electrode used in the method of the present invention is
A composite oxide of zinc oxide and copper oxide is used. In this composite oxide, the molar ratio of zinc oxide and copper oxide is zinc oxide / copper oxide = 8/2 to 4/6, and preferably about 7/3.
【００１１】酸化銅の比率が過少では、エタノールの反
応選択性（触媒作用）が低く、酸化銅が過多では、エタ
ノールのファラデー効率（電流効率）が低く実際的でな
い。If the proportion of copper oxide is too small, the reaction selectivity (catalysis) of ethanol is low, and if the proportion of copper oxide is too large, the faradaic efficiency (current efficiency) of ethanol is low and not practical.
【００１２】なお、該複合酸化物は上記の如く触媒作用
を奏するもので、還元電極全体を当該複合酸化物で形成
する必要はなく、カーボン（活性炭等）、アルミナ、シ
リカ、チタニア、ジルコニア、ゼオライト等の無機物
を、還元電極における触媒担体の材料とすることもでき
る。Since the complex oxide exhibits the catalytic action as described above, it is not necessary to form the entire reduction electrode with the complex oxide, and carbon (activated carbon etc.), alumina, silica, titania, zirconia, zeolite. Inorganic substances such as can be used as the material of the catalyst carrier in the reduction electrode.
【００１３】(2) そして、この複合酸化物の製造方法
は、例えば、下記の如く行う。(2) Then, the method for producing the composite oxide is performed as follows, for example.
【００１４】硝酸亜鉛及び硝酸銅（II）の混合水溶液に
アンモニア水等を滴下して各金属の水酸化物を共沈させ
る。そして、当該共沈物を濾過・乾燥後（例えば、１１
０℃一昼夜）、仮焼（例えば、３６０℃×２４ｈ）し
て、ＺｎＯ／ＣｕＯ粉末を調製する。当該ＺｎＯ／Ｃｕ
Ｏ粉末を加圧成形（例えば、プレス圧：147 MPa ）後、
焼成（例えば、９００℃×４ｈ）して還元電極用のＺｎ
Ｏ／ＣｕＯ複合酸化物（例えば、板状：1.2 cm2×1.5
mmｔ）を得る。Ammonia water or the like is dropped into a mixed aqueous solution of zinc nitrate and copper (II) nitrate to coprecipitate hydroxides of the respective metals. Then, the coprecipitate is filtered and dried (for example, 11
A ZnO / CuO powder is prepared by calcining (for example, 360 ° C. × 24 h) at 0 ° C. overnight. ZnO / Cu
After pressure molding of O powder (for example, pressing pressure: 147 MPa),
Zn for reduction electrode after firing (eg, 900 ° C x 4h)
O / CuO composite oxide (for example, plate-shaped: 1.2 cm 2 × 1.5
mmt) is obtained.
【００１５】(3) そして、エタノール製造用の電解槽
は、下記の如く構成とする。(3) The electrolytic cell for ethanol production is constructed as follows.
【００１６】作用電極（カソード）１は、電極となる
上記ＺｎＯ／ＣｕＯ複合酸化物３の裏面に、導電性低融
点金属（Ｉｎ−Ｇａ合金）５及び銀ペースト７を介して
リード線（銅線）９を接続し、ＺｎＯ／ＣｕＯ複合酸化
物３の不要部分（周囲）を絶縁体（エポキシ樹脂等）１
１で囲繞する（図１参照）。なお、リード線９は、耐熱
性ガラス１２で途中まで被覆されている 対極１３は、慣用の白金電極を、参照電極１５は、慣
用の、塩化カリウム飽和・銀／塩化銀電極を用いる。The working electrode (cathode) 1 is provided with a lead wire (copper wire) on the back surface of the ZnO / CuO composite oxide 3 serving as an electrode via a conductive low melting point metal (In-Ga alloy) 5 and a silver paste 7. ) 9 is connected, and an unnecessary portion (around) of the ZnO / CuO composite oxide 3 is made into an insulator (epoxy resin etc.) 1
Surround with 1 (see FIG. 1). The lead wire 9 is partially covered with the heat-resistant glass 12, the counter electrode 13 is a conventional platinum electrode, and the reference electrode 15 is a conventional potassium chloride saturated / silver / silver chloride electrode.
【００１７】そして、上記各電極を図２に示す如く、
作用極１がセットされる第一槽（負極側）１７、対応電
極１３がセットされる第二槽（正極側）１９とが、中間
に陽イオン交換膜２１が組み込まれた導管２１で接続さ
れている。なお、参照電極は第一槽１７の側面にセット
される。この図例中、２３はガス入口、２５はガス出口
である。Then, as shown in FIG.
The first tank (negative electrode side) 17 in which the working electrode 1 is set and the second tank (positive electrode side) 19 in which the corresponding electrode 13 is set are connected by a conduit 21 in which a cation exchange membrane 21 is incorporated. ing. The reference electrode is set on the side surface of the first tank 17. In this example, 23 is a gas inlet and 25 is a gas outlet.
【００１８】(4) 電解に使用する溶液は、電解質水溶液
であれば特に限定されないが、リン酸塩水溶液、炭酸塩
水溶液、等電離度の高いもの、特に電離度が安定してい
るリン酸塩水溶液が望ましい。(4) The solution used for electrolysis is not particularly limited as long as it is an electrolyte aqueous solution. However, a phosphate aqueous solution, a carbonate aqueous solution, a solution having a high degree of ionization, particularly a phosphate having a stable ionization degree. Aqueous solution is preferred.
【００１９】リン酸塩としては、オルトリン酸カリウ
ム、リン酸二水素カリウム、リン酸一水素カリウム、等
を挙げることができる。Examples of the phosphate include potassium orthophosphate, potassium dihydrogen phosphate, potassium monohydrogen phosphate and the like.
【００２０】４．上記電解槽は、慣用の方法で配管・配
線して、エタノールを製造するために、二酸化炭素を電
気化学的に還元する。このとき電流密度は、通常、０．
２〜１０００ｍＡ／ cm2とし、望ましくは、０．３〜５
０ｍＡ、特に、０．５ｍＡ／cm2前後が望ましい。4. The electrolyzer is plumbed and wired in a conventional manner to electrochemically reduce carbon dioxide to produce ethanol. At this time, the current density is usually 0.
2 to 1000 mA / cm 2 , preferably 0.3 to 5
0 mA, especially around 0.5 mA / cm 2 is desirable.
【００２１】[0021]
【試験例】以下、本発明の効果を確認するために行った
試験例について説明をする。[Test Example] A test example conducted to confirm the effects of the present invention will be described below.
【００２２】(1) 試験例１ 前述の態様において、作用電極をＺｎＯ／ＣｕＯ（モル
比）＝７／３とし、濃度０．１ mol／dm3 各種カリウム
塩水溶液中、電流密度０．５ｍＡ／ cm2で二酸化炭素の
定電流電気化学的還元（通電電気量４０Ｃ）を行った。(1) Test Example 1 In the above embodiment, the working electrode was ZnO / CuO (molar ratio) = 7/3, and the concentration was 0.1 mol / dm 3 in various potassium salt aqueous solutions, and the current density was 0.5 mA / A constant-current electrochemical reduction of carbon dioxide was carried out at a cm 2 (current of electricity of 40 C).
【００２３】試験結果を表１に示すが、リン酸二水素カ
リウム水溶液の場合が、エタノールの電流効率が１１．
７％と良好で、且つ、反応選択性も約８９％と良好であ
ることが分かる。The test results are shown in Table 1. When the aqueous potassium dihydrogen phosphate solution was used, the current efficiency of ethanol was 11.
It can be seen that it is as good as 7% and the reaction selectivity is as good as about 89%.
【００２４】(2) 試験例２ 前述の態様において、作用電極としてＺｎＯ／ＣｕＯ
（モル比）を種々変えたものを使用し、濃度０．１ mol
／dm3 のリン酸二水素カリウム水溶液中、窒素雰囲気下
で電流密度０．３ mA ／ cm2で２Ｃを流し電極を還元処
理した後、試験例１同様、電流密度０．５ｍＡ／ cm2で
二酸化炭素の定電流電気化学的還元（通電電気量４０
Ｃ）を行った。(2) Test Example 2 In the above-mentioned embodiment, ZnO / CuO was used as the working electrode.
(Mol ratio) variously used, concentration 0.1 mol
/ Dm 3 aqueous solution of potassium dihydrogen phosphate under a nitrogen atmosphere at a current density of 0.3 mA / cm 2 to reduce the electrode by flowing 2C, the same as in Test Example 1 at a current density of 0.5 mA / cm 2 Constant current electrochemical reduction of carbon dioxide
C) was performed.
【００２５】試験結果を表２に示すが、二酸化炭素の電
解前に予め作用電極を還元させると、エタノールの電流
効率が１７．３％と増大し、また、ＺｎＯ／ＣｕＯ（モ
ル比）が、３／７及び５／５の場合、選択性が９９％以
上と増大していることが分かる。The test results are shown in Table 2. When the working electrode is reduced in advance before electrolysis of carbon dioxide, the current efficiency of ethanol increases to 17.3%, and ZnO / CuO (molar ratio) It can be seen that in the cases of 3/7 and 5/5, the selectivity increased to 99% or more.
【００２６】(3) 試験例３ 試験例２のＺｎＯ／ＣｕＯ（モル比）＝７／３のものに
ついて、電流密度を種々に変えて試験をした例である。(3) Test Example 3 This is an example in which the ZnO / CuO (molar ratio) = 7/3 of Test Example 2 was tested with various current densities.
【００２７】試験結果を表３に示すが、どの電流密度に
おいても、二酸化炭素からの還元生成物としては、エタ
ノールが主生成物であることが分かる。電流密度０．５
ｍＡ／ cm2のとき電流効率が最大となった。The test results are shown in Table 3, and it can be seen that ethanol is the main product as the reduction product from carbon dioxide at any current density. Current density 0.5
The maximum current efficiency was obtained at mA / cm 2 .
【００２８】酸化亜鉛（ＺｎＯ）と酸化銅（ＣｕＯ）と
からなる複合酸化物焼結体電極を用いて、リン酸塩水溶
液中で、二酸化炭素を電気化学的に還元してエタノール
を製造することTo produce ethanol by electrochemically reducing carbon dioxide in a phosphate aqueous solution using a composite oxide sintered body electrode composed of zinc oxide (ZnO) and copper oxide (CuO).
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【発明の作用・効果】本発明の方法は、ＺｎＯとＣｕＯ
との複合酸化物電極を用いて、電解質水溶液中で、二酸
化炭素を電気化学的に還元してエタノールを製造するこ
とにより、二酸化炭素をエタノールに反応選択性良好に
変換可能となる。The operation and effect of the present invention are as follows: ZnO and CuO
By using the composite oxide electrode of and to electrochemically reduce carbon dioxide in an aqueous electrolyte solution to produce ethanol, carbon dioxide can be converted into ethanol with good reaction selectivity.
【００３３】従って、化石燃料から発生する二酸化炭素
を、回収効率・エネルギー効率良好にエタノールに変換
可能となる。Therefore, it is possible to convert carbon dioxide generated from fossil fuel into ethanol with good recovery efficiency and energy efficiency.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の方法に還元電極として使用する複合酸
化物電極の一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of a composite oxide electrode used as a reduction electrode in the method of the present invention.
【図２】本発明のエタノールの製造方法に使用する電解
槽の分解斜視図である。FIG. 2 is an exploded perspective view of an electrolytic cell used in the method for producing ethanol of the present invention.
１ 作用電極 ３ ＺｎＯ／ＣｕＯ複合酸化物 １３ 対極 １５ 参照電極 1 Working electrode 3 ZnO / CuO complex oxide 13 Counter electrode 15 Reference electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堺 松成 愛知県名古屋市緑区大高町字北関山20番地 の１ 中部電力株式会社技術開発本部電力 技術研究所内 (72)発明者 野田 英智 愛知県名古屋市緑区大高町字北関山20番地 の１ 中部電力株式会社技術開発本部電力 技術研究所内 (72)発明者 伊藤 要 愛知県知多市佐布里字東金久曽23番地19 (72)発明者 池田 章一郎 愛知県名古屋市名東区藤巻町３丁目２番地 の334 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Sakai Matsunari Aichi No. 20 Kitakanzan, Otaka-cho, Midori-ku, Nagoya-shi, Aichi Prefecture Chubu Electric Power Co., Inc. Technology Development Headquarters Electric Power Research Laboratory (72) Inventor Hidetomo Noda Aichi Aichi 1 20-20 Kitakousanyama, Odaka-cho, Midori-ku, Nagoya-shi, Chuo Electric Power Co., Ltd. Technology Development Headquarters (72) Inventor Kaname Ito 23, Tougane-Kusa, Tozaguri, Chita-shi, Aichi Prefecture 19 (72) Invention Ikeda Shoichiro 334, 3-2, Fujimaki-cho, Meito-ku, Nagoya, Aichi
Claims (1)
ールを製造するに際して、 酸化亜鉛（ＺｎＯ）と酸化銅（ＣｕＯ）との複合酸化物
電極を用いて、電解質水溶液中で、二酸化炭素を電気化
学的に還元してエタノールを製造することを特徴とする
エタノールの製造方法。1. When ethanol is produced by reducing carbon dioxide, carbon dioxide is electrochemically converted in an aqueous electrolyte solution by using a composite oxide electrode of zinc oxide (ZnO) and copper oxide (CuO). A method for producing ethanol, which comprises reducing ethanol to produce ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4263841A JPH06116771A (en) | 1992-10-01 | 1992-10-01 | Production of ethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4263841A JPH06116771A (en) | 1992-10-01 | 1992-10-01 | Production of ethanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06116771A true JPH06116771A (en) | 1994-04-26 |
Family
ID=17394971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4263841A Withdrawn JPH06116771A (en) | 1992-10-01 | 1992-10-01 | Production of ethanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06116771A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009138270A (en) * | 1997-05-07 | 2009-06-25 | George A Olah | Recycling of carbon dioxide into methyl alcohol and related oxygenates or hydrocarbons |
| JP2018031034A (en) * | 2016-08-23 | 2018-03-01 | 古河電気工業株式会社 | Electrode carrying metal-containing nanoparticles and carbon dioxide reduction apparatus |
-
1992
- 1992-10-01 JP JP4263841A patent/JPH06116771A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009138270A (en) * | 1997-05-07 | 2009-06-25 | George A Olah | Recycling of carbon dioxide into methyl alcohol and related oxygenates or hydrocarbons |
| JP2018031034A (en) * | 2016-08-23 | 2018-03-01 | 古河電気工業株式会社 | Electrode carrying metal-containing nanoparticles and carbon dioxide reduction apparatus |
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