JP2003213472A - Electrode for electrochemical conversion of carbon dioxide into hydrocarbon gas - Google Patents
Electrode for electrochemical conversion of carbon dioxide into hydrocarbon gasInfo
- Publication number
- JP2003213472A JP2003213472A JP2002007655A JP2002007655A JP2003213472A JP 2003213472 A JP2003213472 A JP 2003213472A JP 2002007655 A JP2002007655 A JP 2002007655A JP 2002007655 A JP2002007655 A JP 2002007655A JP 2003213472 A JP2003213472 A JP 2003213472A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- methane
- carbon dioxide
- ethylene
- current efficiency
- 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.)
- Pending
Links
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は二酸化炭素の電気化
学的固定化に関するものである。TECHNICAL FIELD The present invention relates to electrochemical immobilization of carbon dioxide.
【0002】[0002]
【従来の技術】従来、電解還元による二酸化炭素の変換
で炭化水素ガスを製造するためには、純度の良い銅を電
極としていた。しかも、メタンとエチレンそれぞれの電
流生成率の和は63.1%で、また、電解液から分離が
容易な二酸化炭素の電解還元によるガス類の全生成電流
効率は67%が限度であった。また、この時の水素の生
成を含めた時は82%で、その他は蟻酸やエタノ−ルな
ど水に溶けるものであった。2. Description of the Related Art Conventionally, in order to produce a hydrocarbon gas by converting carbon dioxide by electrolytic reduction, copper of good purity has been used as an electrode. Moreover, the sum of the current generation rates of methane and ethylene was 63.1%, and the total current generation efficiency of gases by electrolytic reduction of carbon dioxide, which was easy to separate from the electrolytic solution, was 67%. In addition, the production of hydrogen at this time was 82%, and the others were soluble in water such as formic acid and ethanol.
【0003】[0003]
【発明が解決しようとする課題】銅電極により二酸化炭
素を電解還元して炭化水素に変換する時は、二酸化炭素
の還元中間生成物として一酸化炭素(CO)が生成し、銅
電極上に吸着する。その吸着量が重要であり、従って、
その量を制御することが必要である。そのためには、銅
と異種金属と合金化してCOの吸着を多くする必要があ
った。When carbon dioxide is electrolytically reduced by a copper electrode to be converted into hydrocarbon, carbon monoxide (CO) is produced as a reduction intermediate product of carbon dioxide and is adsorbed on the copper electrode. To do. The amount of adsorption is important and therefore
It is necessary to control that amount. For that purpose, it was necessary to alloy with copper and a dissimilar metal to increase the adsorption of CO.
【0004】[0004]
【課題を解決するための手段】COの吸着量を多くする
ためにはCOと金属表面エネルギ−の関係が重要であ
る。そのために、銅と異種原子とを合金化することによ
り、COと金属電極間の吸着問題を解決をしようとし
た。The relationship between CO and metal surface energy is important in order to increase the amount of CO adsorbed. Therefore, an attempt was made to solve the adsorption problem between CO and the metal electrode by alloying copper and a heteroatom.
【0005】[0005]
【発明の実施の形態】二酸化炭素の電解還元により、炭
化水素に変換するためには水素が必要である。この場
合、COが銅電極に吸着する電位と、水の電解による水素
発生電位が近いことが望ましい。また、COが電極に吸着
する量と、水素が発生する量のバランスが必要であると
言える。これらの関係を最適化することが二酸化炭素を
炭化水素ガス類へ固定化するためには重要である。DETAILED DESCRIPTION OF THE INVENTION Hydrogen is required to convert carbon dioxide into hydrocarbons by electrolytic reduction of carbon dioxide. In this case, it is desirable that the potential at which CO is adsorbed on the copper electrode is close to the hydrogen generation potential due to the electrolysis of water. It can also be said that a balance between the amount of CO adsorbed on the electrode and the amount of hydrogen generated is necessary. Optimizing these relationships is important for immobilizing carbon dioxide to hydrocarbon gases.
【0006】[0006]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
【0007】実施例1
パルス電解を適用し、0.1MKHCO3を電解質とし
てCu/Sn/P(リン青銅)においてカソ−ド電位
(Ec)=−2100mVvs.Ag/AgClで、ア
ノ−ド電位(Ea)を変えてメタン、エチレン等のガス
類の生成電流効率を測定した。その結果を図1に示す。
図1からわかるようにEa=−900mVvs.Ag/
AgClにおいてこの両者の最大値、68.7%を示し
た。この時、メタンの電流生成効率は61.6%、エチ
レンの電流生成効率は7.1%であった。この場合、ア
ノ−ド電位が−500mVから−900mVまであれば
従来の値、メタンとエチレンの生成効率の和63.1%
より高い値を示している。Example 1 Pulsed electrolysis was applied, and cathode potential (Ec) =-2100 mV vs. Cu / Sn / P (phosphor bronze) using 0.1 MKHCO 3 as an electrolyte. The anodic potential (Ea) was changed with Ag / AgCl, and the production current efficiency of gases such as methane and ethylene was measured. The result is shown in FIG.
As can be seen from FIG. 1, Ea = −900 mV vs. Ag /
In AgCl, the maximum value of both was 68.7%. At this time, the current generation efficiency of methane was 61.6% and the current generation efficiency of ethylene was 7.1%. In this case, if the anode potential is from -500 mV to -900 mV, the conventional value, the sum of methane and ethylene production efficiency is 63.1%.
It shows a higher value.
【0008】実施例2
パルス電解を適用し、0.1MKHCO3を電解質とし
てCu/Sn/P(リン青銅)を使用してカソ−ド電位
(Ec)=−2100mVvs.Ag/AgClで、ア
ノ−ド電位(Ea)を変えてメタン、エチレンと共に、
水素、一酸化炭素を測定した。このように、メタン、エ
チレンとCOの全生成電流効率は75%以上になった。従
来は上記3種ガス類の生成電流効率は67%であり、ま
た、水素を含むガス類の全生成電流効率は95%以上に
なった。その他は蟻酸やエタノ−ルなど水に可溶なもの
が得られる。このことは、ガス類は容易に電解液より分
離が可能であるため、電解液を長時間取り替えることな
く使用することが出来る。Example 2 Pulse electrolysis was applied, using 0.1 MKHCO 3 as an electrolyte and Cu / Sn / P (phosphor bronze) as the cathode potential (Ec) =-2100 mVvs. By changing the anode potential (Ea) with Ag / AgCl, together with methane and ethylene,
Hydrogen and carbon monoxide were measured. In this way, the total efficiency of methane, ethylene and CO generated current was 75% or more. Conventionally, the production current efficiency of the above-mentioned three kinds of gases was 67%, and the total production current efficiency of gases containing hydrogen was 95% or more. Others, such as formic acid and ethanol, are soluble in water. This means that the gases can be easily separated from the electrolytic solution, so that the electrolytic solution can be used for a long time without replacement.
【0009】実施例3
同じく、パルス電解を適用し、0.1MKHCO3にお
いて3種のCuの濃度の異なるCu/Ag、およびCu
/Ni、Cu/Zn、Cu/Beにおいてカソ−ド電位
(Ec)を−1650mVvs.Ag/AgClから−
2200mVvs.Ag/AgClまで,アノ−ド電位
(Ea)を−50mVから−700mVvs.Ag/A
gClまで変えてメタン、エチレン等の炭化水素の生成
効率を測定した。それぞれの合金においてメタン及びエ
チレンの最大生成電流効率を銅の含有率に対するプロッ
ト図を図2に示す。しかし、メタン、エチレンの最大生
成効率電位は異なるため、同一電位ではメタンとエチレ
ンの生成電流効率の和はこの図でのメタンとエチレの和
より小さくなるので、Cu/Sn/Pの図1での値であ
る68.7%より当然小さくなる。Example 3 Similarly, pulse electrolysis was applied to Cu / Ag and Cu having different concentrations of three kinds of Cu in 0.1 MKHCO 3 .
/ Ni, Cu / Zn, Cu / Be, the cathode potential (Ec) is -1650 mV vs. From Ag / AgCl-
2200 mV vs. The anodic potential (Ea) from -50 mV to -700 mV vs. Ag / AgCl. Ag / A
The production efficiency of hydrocarbons such as methane and ethylene was measured while changing to gCl. FIG. 2 shows a plot diagram of the maximum production current efficiency of methane and ethylene with respect to the copper content in each alloy. However, since the maximum production efficiency potentials of methane and ethylene are different, the sum of the production current efficiencies of methane and ethylene is smaller than the sum of methane and ethyl in this figure at the same potential. It is naturally smaller than the value of 68.7%.
【0010】[0010]
【発明の効果】二酸化炭素を高電流効率で炭化水素を固
定化することにより地球温暖化防止に貢献するとともに
石油代替物を提供する。文献によると、銅電極を使用し
た場合のメタンとエチレンの生成電流効率は63.1で
あり、本発明のCu/Sn/P電極を使用した時よりか
なり小さい。これら以外の生成物の中には水に可溶な成
分であるエタノ−ルや蟻酸がある。これらは電解時間と
共に増加し、ひいてはこれらのものが電極反応を受けた
り、電解液の抵抗の増加を引き起こし、炭化水素ガスの
電流効率を下がるため、電解液を頻繁に取り変える必要
である。これらのことを考えると、水に不溶性の物質を
多く製造する必要があり、本発明の効果は大きい。Industrial Applicability The present invention contributes to the prevention of global warming by fixing carbon dioxide to carbon dioxide with high current efficiency, and provides a petroleum substitute. According to the literature, the production current efficiency of methane and ethylene when the copper electrode is used is 63.1, which is considerably smaller than when the Cu / Sn / P electrode of the present invention is used. Among the products other than these, there are water-soluble components such as ethanol and formic acid. These increase with electrolysis time, and as a result, they undergo an electrode reaction or cause an increase in the resistance of the electrolytic solution, which lowers the current efficiency of the hydrocarbon gas, so that it is necessary to replace the electrolytic solution frequently. Considering these matters, it is necessary to produce a large amount of water-insoluble substances, and the effect of the present invention is great.
【図1】 Cu/Sn/P電極でのカソ−ド電位−21
00mV.Ag/AgClでのメタン及びエチレン、一
酸化炭素、水素の生成電流効率とアノ−ド電位との関係
をしめすグラフFIG. 1 Cathode potential-21 at Cu / Sn / P electrode
00 mV. Graph showing the relationship between the anodic potential and the generation current efficiency of methane, ethylene, carbon monoxide and hydrogen in Ag / AgCl.
【図2】 各種銅合金中での銅含有率とメタン及びエチ
レンの生成電流効率との関係を示すグラフFIG. 2 is a graph showing the relationship between the copper content rate in various copper alloys and the production current efficiency of methane and ethylene.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 川波 美幸 福岡市東区香住ケ丘1−1−1 福岡女子 大学内 (72)発明者 田中 筆子 福岡市東区香住ケ丘1−1−1 福岡女子 大学内 (72)発明者 合原 眞 福岡市東区香住ケ丘1−1−1 福岡女子 大学内 Fターム(参考) 4K011 AA68 DA10 4K021 AA09 AC02 BA17 BB03 DA13 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Miyuki Kawanami 1-1-1 Kazumigaoka, Higashi-ku, Fukuoka City Fukuoka Women Inside the university (72) Inventor, Brush Tanaka 1-1-1 Kazumigaoka, Higashi-ku, Fukuoka City Fukuoka Women Inside the university (72) Inventor Makoto Aihara 1-1-1 Kazumigaoka, Higashi-ku, Fukuoka City Fukuoka Women Inside the university F-term (reference) 4K011 AA68 DA10 4K021 AA09 AC02 BA17 BB03 DA13
Claims (2)
電流効率が75%以上である二酸化炭素変換用電極。2. A carbon dioxide conversion electrode having a production current efficiency including claim 1 and a CO production current efficiency of 75% or more.
Priority Applications (1)
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JP2002007655A JP2003213472A (en) | 2002-01-16 | 2002-01-16 | Electrode for electrochemical conversion of carbon dioxide into hydrocarbon gas |
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