JP5144755B2 - メタノール製造のための水媒体中の二酸化炭素の一酸化炭素及び水素への電気分解 - Google Patents
メタノール製造のための水媒体中の二酸化炭素の一酸化炭素及び水素への電気分解 Download PDFInfo
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- JP5144755B2 JP5144755B2 JP2010516272A JP2010516272A JP5144755B2 JP 5144755 B2 JP5144755 B2 JP 5144755B2 JP 2010516272 A JP2010516272 A JP 2010516272A JP 2010516272 A JP2010516272 A JP 2010516272A JP 5144755 B2 JP5144755 B2 JP 5144755B2
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- methanol
- carbon dioxide
- hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
理想的には、Sは2に等しい、或いは若干2を超えなければならない。2を超える値は水素過剰を示す一方、2を下回る値は相対的な水素欠乏を示す。プロパン、ブタン又はナフサ等のより高いH/C比を有する原料の改質は、S値をメタノールへの変換に適した2近辺に導く。しかしながら、石炭又はメタンを用いた場合、最適なS値を得るのに追加的処理を要する。石炭からの合成ガスは、望ましくない副生成物の形成を回避するための処理が必要である。メタンの蒸気改質は、2.8〜3.0の化学量論数を有する合成ガスを生産し、CO2を添加することによって、或いはアンモニア合成等の一部の他の工程で過剰の水素を使用することによって、S値を2に近似した値に低めることを要する。しかしながら、天然ガスは、高水素含量に加えて、最も低いエネルギー消費、資本投資及び操業コストをもたらすので、依然としてメタノール生成用原料として好適である。また、天然ガスは、工程で使用する触媒を毒するおそれのある硫黄、ハロゲン化化合物及び金属等の成分をより少量で含有する。
本発明の利益は、以下の実施態様の詳細な説明及び図面を精査することでより明らかになるであろう。
テトラブチルアンモニウムハロゲン化物、優先的にテトラブチルアンモニウムブロミドを、Ag/AgCl参照電極に対して-1.5Vかまたは-4Vで、メタノール水溶液媒体中での金電極(カソード)上の電解質として用いた分離した電気化学セルにおいて、CO2が還元され、水はカソードでCOとH2とが1:2の最適混合物に電気分解される。多少の臭素だけでなく、純酸素がアノードで生産される。
0.1MのKHCO3水溶液を電解質として用いた分離した電気化学セルにおいて、Ag/AgCl参照電極に対して-3.2Vの金カソードでCO2が還元され、水はメタノール合成に適したCOとH2とが1:2の最適混合物に電気分解される。COとH2生産のための総ファラデー効率は、最高100%に達する。純酸素は、アノードで生産される。
Claims (12)
- 入手可能な二酸化炭素源の再利用および還元的変換によってメタノールを製造する環境的に有益な方法であって、
第一のセル部にアノードを、第二のセル部に金属カソード電極を具え、かつアルキルアンモニウムハロゲン化物、アルカリ炭酸塩若しくはそれらの組み合わせの一つ以上の電解質である、水溶液又はメタノール水溶液をも含有する分割された電気化学セルを設ける工程と、
第二のセル部内に既存の資源から二酸化炭素を再利用する工程と、
第二のセル部内で再利用された二酸化炭素、および第二のセル部内の溶液を電気化学的に還元して、そこで一酸化炭素および水素ガスを1:2〜1:2.1の比で含む反応混合物を生産する工程と、
第二のセル部から反応混合物の一酸化炭素および水素ガスを得て、触媒存在下で反応混合物を直接反応させてメタノールを生成し、かつアノードで第一のセル部中に酸素を生成して大気の二酸化炭素を減少させることによって環境に利益を与える工程とを含む方法。 - 前記電解質が、一つ以上の多価アルキルアンモニウムハロゲン化物、一つ以上のアルカリ炭酸塩或いは重炭酸塩と、メタノール又は水とを含む請求項1に記載の方法。
- 前記一つ以上の多価アルキルアンモニウムハロゲン化物が、テトラブチルアンモニウムハロゲン化物である請求項2に記載の方法。
- 前記テトラブチルアンモニウムハロゲン化物が、テトラブチルアンモニウムブロミド、テトラブチルアンモニウムクロリド、テトラブチルアンモニウムヨージド又はこれらの混合物からなる群より選ばれる請求項3に記載の方法。
- 前記アルカリ炭酸塩が、ナトリウム重炭酸塩又はカリウム重炭酸塩を含む請求項1に記載の方法。
- 前記金属カソード電極が、Cu、Au、Ag、Zn、Pd、Ga、Ni、Hg、In、Sn、Cd、Tl、Pb又はPt電極である請求項1に記載の方法。
- 前記金属カソード電極が、金電極である請求項6に記載の方法。
- 前記電気化学的還元が、Ag/AgCl参照電極に対して−1.5〜−4Vの電圧の適用することを含む請求項1に記載の方法。
- 前記既存の資源が、化石燃料火力発電所又は工場、天然ガス付随の資源、或いは地熱井からの排出蒸気であり、二酸化炭素を前記既存の資源から得ることを含む請求項1に記載の方法。
- 前記既存の資源が大気中にあり、さらに、適切な吸着剤上に既存の資源の二酸化炭素を吸着させ、次いで吸着剤を処理してそこから吸着された二酸化炭素を放出させることによって、前記既存の資源からの二酸化炭素を得る工程を含む請求項1に記載の方法。
- 前記吸着剤が、充分な加熱によって又は吸着剤を充分な減圧にさらすことによって処理されて、吸着された二酸化炭素を放出する請求項10に記載の方法。
- 二酸化炭素の電気化学的還元用電気エネルギーが、原子力発電、水力発電、風、地熱又は太陽熱に基づくエネルギー源から供給される請求項1に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US94972307P | 2007-07-13 | 2007-07-13 | |
US60/949,723 | 2007-07-13 | ||
PCT/US2008/069803 WO2009012154A2 (en) | 2007-07-13 | 2008-07-11 | Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol |
Publications (3)
Publication Number | Publication Date |
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JP2010533784A JP2010533784A (ja) | 2010-10-28 |
JP2010533784A5 JP2010533784A5 (ja) | 2012-02-09 |
JP5144755B2 true JP5144755B2 (ja) | 2013-02-13 |
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Application Number | Title | Priority Date | Filing Date |
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JP2010516272A Expired - Fee Related JP5144755B2 (ja) | 2007-07-13 | 2008-07-11 | メタノール製造のための水媒体中の二酸化炭素の一酸化炭素及び水素への電気分解 |
Country Status (9)
Country | Link |
---|---|
US (1) | US7704369B2 (ja) |
EP (1) | EP2167706B1 (ja) |
JP (1) | JP5144755B2 (ja) |
KR (1) | KR20100036317A (ja) |
CN (1) | CN101743343B (ja) |
AU (1) | AU2008276180B2 (ja) |
CA (1) | CA2690980C (ja) |
ES (1) | ES2659978T3 (ja) |
WO (1) | WO2009012154A2 (ja) |
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