JP2022143968A - 二酸化炭素電解装置 - Google Patents
二酸化炭素電解装置 Download PDFInfo
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- JP2022143968A JP2022143968A JP2021044778A JP2021044778A JP2022143968A JP 2022143968 A JP2022143968 A JP 2022143968A JP 2021044778 A JP2021044778 A JP 2021044778A JP 2021044778 A JP2021044778 A JP 2021044778A JP 2022143968 A JP2022143968 A JP 2022143968A
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- Prior art keywords
- electrode
- carbon dioxide
- water
- gas
- reduction electrode
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- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 65
- 230000009467 reduction Effects 0.000 claims abstract description 118
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 67
- 230000003647 oxidation Effects 0.000 claims abstract description 61
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- 206010016803 Fluid overload Diseases 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 120
- 239000007789 gas Substances 0.000 description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 55
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- 229940087646 methanolamine Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 150000003457 sulfones Chemical class 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
第1の実施形態の二酸化炭素電解装置1(1A)について、図1を参照して説明する。図1に示す二酸化炭素電解装置1Aは、電解セル2と、電解セル2に二酸化炭素(CO2)を含むガス(以下、単にCO2ガスと記す場合もある)を供給する第1の供給経路3と、電解セル2でCO2の還元反応により生成された生成物を含むガスを排出する第1の排出経路4と、電解セル2に水(H2O)を含む電解液又は水蒸気を供給する第2の供給経路5と、電解セル2でH2Oの酸化反応により生成された生成物を電解液と共に排出する第2の排出経路6と、各部の動作等を制御する制御部7とを具備している。制御部7は、例えばPCやマイコン等のコンピュータで構成され、後述するように各部で出力されたデータ信号を演算処理し、必要な制御信号を構成部に出力する。
2H2O → 4H++O2+4e- …(1)
2CO2+4H++4e- → 2CO+2H2O …(2)
2H++2e- → H2 …(3)
2CO2+2H2O+4e- → 2CO+4OH-…(4)
2H2O+2e- → 2OH- …(5)
生成された水酸化物イオンは、隔膜10を介して酸化電極9に移動し、下記の式(6)に示すように、酸化電極9で水酸化物イオンが酸化されて酸素を生成する反応が生じる。
4OH- → 2H2O+O2+4e- …(6)
また、式(4)で生成した水酸化物イオンは、還元電極8付近に存在するCO2と反応し、重炭酸イオンや炭酸水素イオンを形成し、酸化電極9に移動する場合もある。さらに、副反応として水を還元して水素が生されることがある。
第2の実施形態の二酸化炭素電解装置1Bについて、図2を参照して説明する。図2に示す二酸化炭素電解装置1Bは、検知部として第1の排出経路4中に第1の水分量検知部19のみが設けられていると共に、水分量調整部として電解セル2の温調器23が設けられている。さらに、電解セル2に温度測定器24が設置されている。温度測定器24は還元電極8側及び酸化電極9側のいずれに設置してもよいが、酸化電極9側に設置することが好ましい。これら以外の構成について、第2の実施形態の二酸化炭素電解装置1Bは第1の実施形態と同様な構成を有している。
第3の実施形態の二酸化炭素電解装置について、図3を参照して説明する。図3に示す二酸化炭素電解装置1Cは、第1の水分量検知部19及び第2の水分量検知部20を有し、水分量調整部として第1の供給経路3に湿度調整器(調湿器)25が設けられている。湿度調整器25はガスを加湿又は除湿し、ガス中の水分量(露点温度)を調整する機能を有する。湿度調整器25は、加湿機能のみを有するものであってもよいが、加湿及び除湿の両機能を有するものが好ましい。これら以外の構成について、第3の実施形態の二酸化炭素電解装置1Cは第1の実施形態と同様な構成を有している。図3に示すよう、第1の水分量検知部19及び第2の水分量検知部20で検知された検知信号は制御部7に送られ、これにより水分量調整部である湿度調整器25の動作が制御される。すなわち、第1の供給流路3を流れるCO2ガス中の水分量が調整される。
第4の実施形態の二酸化炭素電解装置1Dについて、図4を参照して説明する。図4に示す二酸化炭素電解装置1Dは、2つの電解セル2A、2Bが積層されたスタックセルを備えている。すなわち、スタックセルは、第1の流路板16A、還元電極8A、隔膜10A、酸化電極9A、第2の流路板17A、第1の流路板16B、還元電極8B、隔膜10B、酸化電極9B、及び第2の流路板17Bが順に積層された構造を有している。第1の流路板16A、16Bは、それぞれ多孔質導電材で構成されている。第1の流路板16A、16Bの還元電極8A、8Bと接する面とは反対側の面に冷却水流路26となる溝が形成されている。冷却水流路26に冷却水を供給するように冷却水ポンプ27が設けられている。なお、電解セル2A、2B(スタックセル)の冷却効率を考慮して、第2の流路板17Bにも冷却水流路26を設けてもよい。これら以外の構成について、第4の実施形態の二酸化炭素電解装置1Dは第1の実施形態と同様な構成を有している。
図2に示したように、第1の排出経路中に第1の水分量検知部を設けた二酸化炭素電化装置を作製した。ただし、検証実験のために、第1の供給経路中に第2の水分量検知部を設けた。第1及び第2の水分量検知部には露点計及び流量計を用いて、電解セルから排出される気体中及び電解セルから排出される気体中の水分量を計測した。
水分量(還元電極)=水分量(第1の排出経路)―水分量(第1の供給経路)
この際、水分量の単位としては、単位電極面積当たりの水分の移動速度(ml/min/cm2)を用いた。
実施例2では、図3に構成を示した二酸化炭素電解装置において、水分量調整部として調湿器を用いて、電解セルに供給するCO2ガスの加湿温度を制御することで、還元電極における水分量が制御可能かどうかの検証を行った。加湿器では、水が収容された容器中でCO2ガスをバブリングすることでCO2ガスを加湿した。ここで、加湿温度とは容器中の水の温度を指し、加湿温度が高いほどガス中の水分量が多い。また、図示しないがCO2ガス中の水分が配管中で結露しないよう、配管をヒーターで加熱して評価を行った。なお、実施例1と同様に、この検証実験においても制御部を作動させず、検知部の読み取り及び調整部の動作を人為的に操作した。
Claims (10)
- 還元電極と、酸化電極と、前記還元電極に二酸化炭素を含むガスを供給するためのガス流路と、前記酸化電極に水を含む電解液又は水蒸気を供給するための液流路と、前記還元電極と前記酸化電極とを分離する隔膜とを備える第1の電解セルと、
前記還元電極に前記ガスを供給するように、前記ガス流路に接続された第1の供給経路と、
前記還元電極で生成された生成物を少なくとも排出するように、前記ガス流路に接続された第1の排出経路と、
前記第1の排出経路中を流れるガス中の水分量を検知するように、前記第1の排出経路に設置された第1の水分量検知部と、
前記還元電極に供給する水分量を調整するように構成された水分量調整部と、
前記第1の水分量検知部の検知信号に基づいて前記水分量調整部を制御するように構成された制御部と
を具備する二酸化炭素電解装置。 - さらに、前記第1の供給経路中を流れるガス中の水分量を検知するように、前記第1の供給経路に設置された第2の水分量検知部を具備する、請求項1に記載の二酸化炭素電解装置。
- 前記水分量調整部は、前記酸化電極に供給する前記電解液の量を調節する流量調整部を備える、請求項1又は請求項2に記載の二酸化炭素電解装置。
- さらに、前記酸化電極に前記電解液を供給するように、前記液供給路に接続された第2の供給経路と、
前記酸化電極で生成された生成物を前記電解液と共に排出するように、前記液供給路に接続された第2の排出経路と、
前記第2の供給経路、前記液供給路、及び前記第2の排出経路を介して前記電解液を循環させるポンプとを具備し、
前記水分量調整部は、前記ポンプを備え、
前記制御部は、前記第1の水分量検知部の検知信号に基づいて前記ポンプの流量を調整するように構成される、請求項1又は請求項2に記載の二酸化炭素電解装置。 - 前記水分量調整部は、前記第1の供給経路を流れる前記カス中の湿度を調整する湿度調節器を備える、請求項1又は請求項2に記載の二酸化炭素電解装置。
- 前記水分量調整部は、前記第1の電解セルの温度を調整する温度調節器を備える、請求項1又は請求項2に記載の二酸化炭素電解装置。
- さらに、前記第1の電解セルの温度を調整するように、前記還元電極と多孔質導電材を介して配置された冷却水流路と、前記冷却水流路に冷却水を導入する冷却水ポンプを具備し、
前記水分量調整部は、前記冷却水ポンプを備え、
前記制御部は、前記第1の水分量検知部の検知信号に基づいて前記冷却水ポンプの流量を調整するように構成される、請求項1又は請求項2に記載の二酸化炭素電解装置。 - 前記水分量検知部は、露点計を備える、請求項1ないし請求項7のいずれか1項に記載の二酸化炭素電解装置。
- 前記水分量検知部は、湿度計及び温度計を備える、請求項1ないし請求項7のいずれか1項に記載の二酸化炭素電解装置。
- さらに、還元電極と、酸化電極と、前記還元電極に二酸化炭素を含むガスを供給するためのガス供給路と、前記酸化電極に水を含む電解液又は水蒸気を供給するための液供給路と、前記還元電極と前記酸化電極とを分離する隔膜とを備える第2の電解セルを具備し、
前記第2の電解セルの前記ガス流路は、前記第1の供給経路及び前記第1の排出経路と接続されている、請求項1ないし請求項9のいずれか1項に記載の二酸化炭素電解装置。
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