Carbon Dioxide to Methane via Electrolytic Hydrogen Generation for Intermittent Renewable Energy Supply

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1 Carbon Dioxide to Methane via Electrolytic Hydrogen Generation for Intermittent Renewable Energy Supply Koji Hashimoto, Naokazu Kumagai, Koichi Izumiya, Hiroyuki Takano, Shunsuke Sasaki, Zenta Kato Tohoku Institute of Technology, Sendai Hitachi Zosen Corporation, Kashiwa

2 Ratio to Developing Countries in 2011 Energy Consumption per Capita /10 9 J nd energy crisis Economic bubble burst US Global recession Lehman brothers bankruptcy Developed Germany Japan Eurasia 100 World China 1 0 Developing Year EIA, USA

3 Energy Consumption per Capita / 10 9 J World energy consumption will increase continuously. x x 42.5% x World x 10 9 J 49.0% Population / Billion % 79.9% EIA, USA

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5 World Energy Consumption / J fold increase every year since 1990 Natural Gas % 100 Petroleum 1.92% 0 Hydro 6.66% Year Coal Nuclear Electric % 4.63% 23.63% Other Renewable Electric EIA, USA BP Statistics

6 Fold Increase Every Year Since 1990 World Energy Consumption / J Uranium Consumption 66.0kt 4.63% 2012 Natural Gas Consumption Tft % Petroleum Consumption Gbbl 34.28% 2012 Hydro Electric 6.66% 2012 Coal Consumption G short t 28.88% 2012 Other Renewable Electric 1.92% World energy consumption per capita in 2050 Renewable 2057 is only Natural 54.5 % Gas Coal Energy of that in developed countries in 2011 Year Petroleum Uranium Coal Renewable Electric 2046 Petroleum Exhaustion Exhaustion Tbbl ( bbl Reserves) 2048 Exhaustion G short t (2011 Reserves) 2048 Natural Gas Exhaustion 6, Tft 3 (2013 Reserves) 2053 Uranium Exhaustion Mt (2014 Reserves) EIA, USA BP Statistics

7 Desert Area for Electricity Supply to the World Hours of Sunlight at 1000W/m 2 :8 hours/day Energy Efficiency:20% World Energy Consumption in x J/year Desert area necessary for this amount of power generation x 10 6 km 2 = Mha 1.17% of the Main Desert Area on the Earth 7.87% of the Main Desert Area in Australia The main desert area on the Earth:22.69x10 6 km 2

8 Direct Acceptance of Fluctuating Power by Power Company Frequency Fluctuation of Output Automobile industry Fluctuation of annealing condition : fluctuation of weld strength and appearance Chemical textile industry & Papermaking industry Fluctuation of reeling rate : partially thick and/or broken textile and paper Steelmaking industry & Aluminum making industry Fluctuation of rolling condition : fluctuation of thickness Oil industry Fluctuation of pressure for desulfurization : impure products Date Time Frequency/Hz Inquiry call for Frequency Fluctuations in 60 Hz Region February : March : March : April : May :

9 Target of Frequency Deviation in Japan Hokkaido Eastern region Central and Western regions 50 ± 0.3 Hz 50 ± 0.2 Hz 60 ± 0.2 Hz Hokkaido Electric Power Company Acceptance of 0.25 Gw of wind power origin electricity (4.8 % of the maximum output 5.11 Gw) Frequency deviation > 0.3 Hz For steady operation of industry The maximum of fluctuating and intermittent electricity acceptable by electric power company Less than 5 % of the maximum outputs Fluctuating electric energy storage: Conversion to Fuel

10 Hydrogen Produced by seawater electrolysis Using electricity generated from renewable energy No Transportation Methods No Combustion Systems Fuel that can be used over the world is only the currently used fuel for which efficient infrastructures of transportation and combustion exist

11 Methane can be formed by the Reaction of Carbon Dioxide and Hydrogen Carbon Dioxide + Hydrogen M ethane + Water CO 2 + 4H 2 CH 4 + 2H 2 O The Same Fuel as Currently Used Natural Gas Methane

12 Global Carbon Dioxide Recycling Power Generation by Solar Cell Methane Production from Carbon Dioxide and Hydrogen Hydrogen Production by Seawater Electrolysis Methane Energy Consumer Carbon Dioxide Capture Carbon Dioxide

13 Key Materials for Global CO 2 Recycling H 2 Production Cathode for Water Electrolysis Anode Direct seawater electrolysis Alkali water electrolysis Methane Production Catalyst for CO 2 Conversion by the Reaction with H 2

14 Cathode Electrodeposited Ni-Fe-Co-C alloys 49.6Ni-3.1Co-43.3Fe-4.0C 53.9Ni-2.9Co-40.0Fe-3.2C 26.7Ni- 16.4Co -56.9Fe 144 mv/dec 33.3Ni- 20.9Co -45.8Fe 47.8Ni- 28.6Co 4.5 M KOH 90 C -23.6Fe 52.5Ni- 0.4Co-41.5Fe-5.6C 59.2Ni- 2.7Co-32.0Fe-6.1C 36 mv/dec 2H + + 2e - H 2 H + + e - H ads 2H ads H 2 (1) (2) H + + e - + H ads H 2 (3) Rate-determining step H + + e - H ads (1) Slow proton discharge i/f = k 1 [H + ]exp(- FE/2RT) E/ (log i) = 2.3x2RT/F ~ 144 mv/decade Remarkably fast discharge Rate-determining step 2H ads H 2 (2) Essentially fast recombination i/f = k 2 [H + ] 2 exp(- 2FE/RT) E/ (log i) = 2.3xRT/2F ~ 36mV/decade Rate-determining step H + + e - + H ads H 2 (3) E/ (log i) = 2.3x2RT/3F ~ 48mV/decade

15 With Diaphragm: 1.8 V at 6000Am kwh / Nm 3 H kwh / Nm 3 CH 4 Cathodes H 2 O V Anodes 4.5 M KOH 90 C Electrodeposited Cathodes Anodes

16 Carbon monoxide Hydrogen Methane Carbon dioxide Catalyst Necessary reaction Reaction should not occur CO 2 + 4H 2 CH 4 + 2H 2 O CO 2 + H 2 CO + H 2 O Poison

17 4H 2 + CO 2 CH 4 + 2H 2 O

18 CO 2 methanation catalyst CO 2 + 4H 2 CH 4 + 2H 2 O Precursor: Amorphous Ni-Zr alloys Catalyst: Ni supported on tetragonal ZrO 2 type oxide Stable ZrO 2 : monoclinic Ni/monoclinic ZrO 2 catalyst: Low activity Tetragonal ZrO 2 : Zr 4+ 1-x Ni 2+ xo 2-2-x V Ox stabilized by inclusion of Ni 2+ V o : Oxygen vacancy Inclusion of Ni 2+ with lower valence than Zr 4+ : Oxygen vacancy in ZrO 2 lattice V O in Zr 4+ 1-x Ni 2+ xo 2-2-x V ox attracts O in CO 2 CO 2 + 2H 2 C* + 2H 2 O The rate-determining reaction of the total reactions C* + 2H 2 CH 4 spontaneous reaction Inclusion of M n+ with lower valence than Zr 4+ stabilizes Zr 4+ 1-x M n+ xo 2-2-(2-n/2)x V o (2-n/2) x (n<4). M n+ : Ca 2+, Mg 2+, Ni 2+, Sm 3+

19 Mass production of catalysts Aqueous ZrO 2 sol with nickel salt and RE, Ca or Mg salt Heating in air Mixture of NiO and tetragonal ZrO 2 stabilized by inclusion of Ni 2+ and RE ion, Ca 2+ or Mg 2+ Reduction by H 2 Metallic Ni-supported on tetragonal ZrO 2 stabilized by inclusion of Ni 2+ and RE ion, Ca 2+ or Mg 2+

20 4H 2 + CO 2 CH 4 + 2H 2 O

21 Desert CO 2 Recycling Plant Coast near by desert Electric Power Electricity generation by solar cell Energy consumer Hydrogen production by seawater electrolysis 4H 2 O 4H 2 + 2O 2 CO 2 Combustion & carbon dioxide capture CH 4 + 2O 2 CO 2 + 2H 2 O CH 4 Methane formation by the reaction of hydrogen and carbon dioxide 4H 2 + CO 2 CH 4 + 2H 2 O 1995 at Institute for Materials Research, Tohoku University

22 Hydrogen Production by Seawater Electrolysis 4H 2 O 4H 2 + 2O 2 Pilot Plant of Industrial Scale 2003 Methane Production by the reaction of Carbon Dioxide with Hydrogen CO 2 + 4H 2 CH 4 + 2H 2 O 2003 at Tohoku Institute of Technology

23 International Joint R & D Hitachi Zosen Corporation PTT Exploration and Production Public Co., Ltd. January 2012-March 2016 Construction of a methane producion plant with a rate of 1000 Nm 3 /h at natural gas field of high content of CO 2

24 High CO 2 source platform

25 Self support of energy at an isolated island Electrolysis O 2 Hydrogen O 2 Biomass Gas Digestion Gas Methanation CO 2 Synthesized Natural Gas Thermal Power Generation CO 2 Oxygen-methane power generation

26 Fluctuating Remote Renewable Green Energy (Solar energy, Wind energy Ocean energy, etc.) Hot Alkali Electrolysis of desalinated water Electricity Hydrogen Direct Seawater Electrolysis Methane Reaction with CO 2 Current & efficient infrastructures for transportation and combustion Sustainable Development of the World

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28 White Paper: Electrical Energy Storage December 2011

29 2011 Scenario A Reduction of Energy Consumption Electricity conversion Cogeneration Transportation Electric vehicles Plug- in hybrid 50% Efficiency improvement Heat Saving New construction Reconstruction Other losses Electricity conversion losses Non-energy consumption Transportation Industry Commercial & institutional Household By 2050 Scenario B: Hydrogen produced by Renewable will be converted to Methane. Scenario C: Only Electric (80%) and Plug- in hybrid vehicles

30 Production technology of a fuel, for which new combustion system is required, cannot spread. Technologies requiring a large amount of precious metals and/or rare elements cannot spread to the world. World Pt reserves 60,000-70,000 t World Pt supply in 2012 :183 t Number of cars in the world in 2012 Number of 4 wheel cars produced in billion million A fuel cell car 75-80kW, Pt required for electrodes: g Even if 20 t/y of Pt is supplied, the number of car with 50 g Pt is only 0.4 million. Fuel cell cars cannot spread. For spreading a new technology, the industrial development of the technology should begin after the basic research reaches no requirement of a large amount of noble and/or rare elements. Industrial development of the technology which cannot spread to the world is just like the hobby of rich people.

31 2 nd energy crisis Economic bubble burst Global recession Lehman brothers bankruptcy World energy consumption and CO 2 emissions increase continuously except economic depression. EIA, USA

32 Ratio to Developing Countries in CO 2 Emissions per Capita / t 20 US Developed Germany Japan Eurasia 5 World China 1 0 Developing Year EIA, USA

33 Overview of Our Future For Survival of the Whole World Avoiding Complete Exhaustion of Fossil Fuels and Intolerable Global Warming Koji Hashimoto, Naokazu Kumagai, Koichi Izumiya, Hiroyuki Takano, Shunsuke Sasaki, Zenta Kato Tohoku Institute of Technology, Sendai Hitachi Zosen Corporation, Kashiwa

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