JP6096129B2 - 電気化学還元装置および、芳香族炭化水素化合物の水素化体の製造方法 - Google Patents
電気化学還元装置および、芳香族炭化水素化合物の水素化体の製造方法 Download PDFInfo
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 130
- 239000002184 metal Substances 0.000 claims description 130
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
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- 239000001301 oxygen Substances 0.000 claims description 27
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- 238000000034 method Methods 0.000 claims description 10
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- 150000002739 metals Chemical class 0.000 claims description 9
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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Description
<酸素発生用電極での電極反応>
3H2O→1.5O2+6H++6e−:E0=1.23V
<還元電極での電極反応>
トルエン+6H++6e−→メチルシクロヘキサン:E0=0.153V(vs RHE)
すなわち、酸素発生用電極での電極反応と、還元電極での電極反応とが並行して進行し、酸素発生用電極での電極反応によって、水の電気分解により生じたプロトンが電解質膜110を介して還元電極に供給され、還元電極での電極反応において、芳香族化合物の核水素化に利用される。
より詳しくは、還元電極120での電極電位を原料として用いる芳香族化合物の標準酸化還元電位E0以下にし、酸素発生用電極130の電極電位を酸素発生電位より高くすることで、電気化学反応を両極で進行させる。従って、本反応を進行させるのに必要な外部電場の電圧は、この電位差に、反応に要する過電圧、物質移動拡散の過電圧、電解質膜110の抵抗により生じる抵抗損失(オーミックロス)を足した電圧である。外部電場の電圧は、1.2〜2.4Vが好ましく、1.3〜2.0Vがより好ましく、1.35〜1.6Vが最も好ましい。外部電場の電圧が1.2Vより低いと、理論上、電極反応が進行しないため、芳香族化合物の核水素化を工業的に実施することが困難になる。また、外部電場の電圧が2.4Vより高い場合には、外部電場から与える電気エネルギーが過剰に必要になるため、エネルギー効率の観点から好ましくない。また、還元電極120側の電位が低下し過ぎることにより、芳香族化合物の核水素化以外の副反応(たとえば、水素発生)が進行する。一方、酸素発生用電極130側の電位が高くなり過ぎることにより、酸素発生用電極130に用いられる触媒の腐食が進行しやすくなる。
実施例1〜7および比較例1〜4の電解セルを用いて、トルエンの核水素化反応を行った場合の電流密度評価を行った。表1に実施例1〜7および比較例1〜4の電解セルに用いた構成および成分を示す。
還元触媒金属の全質量:0.5mg/cm2
還元電極の電位:0mV(vs RHE)
イオノマー比(質量比I/C):1
表1に各電解セルに流れる電流密度を示す。また、図3に、各電解セルと電流密度の関係、すなわち、還元電極に用いられる触媒金属と電流密度の関係を示す。
第1の触媒金属のみを用いた場合を基準として、第2の触媒金属の含有率を変えたときの相対電流密度を評価した。表2は、第1の触媒金属と第2の触媒金属との組み合わせと、第2の触媒金属の含有率を変えたときの相対電流密度を示す。1種の第1の触媒金属に対して1種の第2の触媒金属からなる組成物を用いて評価を行ったため、表2および図4は便宜的に「第2の触媒金属の含有率(wt%)」と記載しているが、100から第2の触媒金属の含有率を減じた値が第1の触媒金属の含有率に相当する。図4は、第2の触媒金属の含有率と相対電流密度との関係を示すグラフである。なお、還元触媒金属の成分を除いて、電解セルの構成は電流密度評価で用いた電解セルと同様である。
イオノマー比が1の場合を基準として、イオノマー比を変えたときの相対電流密度を評価した。評価に用いた電解セルの構成は、表1の電流密度評価で用いた電解セルと同様である。表3にイオノマー比(質量比I/C)と相対電流密度との関係を示す。図5は、イオノマー比と相対電流密度との関係を示すグラフである。図5に示すように、質量比I/Cが0.1〜2の範囲で良好な電極活性が得られ、0.2〜1.5の範囲、0.3〜1.1の範囲の順で電極活性が顕著に向上することが確認された。ここでは、表1に記載の実施例3の金属触媒を用いて評価を行ったが、反応物質である芳香族化合物の触媒金属の活性点への接触性や電子伝導性への相対的影響度としては、他の金属触媒を用いても同様の傾向にあると言える。
Claims (6)
- プロトン伝導性を有する電解質膜と、
前記電解質膜の一方の側に設けられ、アルキルベンゼンを核水素化するための還元触媒を含む還元電極と、
前記電解質膜の他方の側に設けられた酸素発生用電極と、
を備え、
前記還元触媒は、Pt、Pdの少なくとも一方を含む第1の触媒金属と、
Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Ru、Sn、W、Re、Pb、Biから選択される1種または2種以上の第2の触媒金属と、を含む組成物であり、
前記第1の触媒金属と前記第2の触媒金属の総質量に対する第1の触媒金属の割合は、10wt%以上、95wt%以下であり、
前記第1の触媒金属および前記第2の触媒金属が多孔性カーボン、多孔性金属、多孔性金属酸化物のいずれかを含有する導電性材料に担持されており、
前記導電性材料が1.0×10−2S/cm以上の電気伝導度を有することを特徴とする電気化学還元装置。 - 前記還元電極がプロトン伝導体を含む請求項1に記載の電気化学還元装置。
- 前記プロトン伝導体がイオン伝導性ポリマーである請求項2に記載の電気化学還元装置。
- 前記還元触媒が、前記プロトン伝導体で部分的に被覆されている請求項2または3に記載の電気化学還元装置。
- 請求項1乃至4のいずれか1項に記載の電気化学還元装置の還元電極側に、アルキルベンゼンを導入し、酸素発生用電極側に水または加湿したガスを流通させ、還元電極が卑な電位、酸素発生用電極が貴な電位となるよう外部から電場を印加することで、還元電極側に導入されたアルキルベンゼンを核水素化することを特徴とする芳香族炭化水素化合物の水素化体の製造方法。
- 請求項5に記載の芳香族炭化水素化合物の水素化体の製造方法において、還元電極側へ導入する前記アルキルベンゼンを反応温度において液体の状態で導入する芳香族炭化水素化合物の水素化体の製造方法。
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