GasTech2017 Technical Session Stream 1 Alternate Energy Transportation & Storage. Large-Scale Hydrogen Storage and Transportation System

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1 GasTech2017 Technical Session Stream 1 Alternate Energy Transportation & Storage Large-Scale Hydrogen Storage and Transportation System 5 th April, 2017 Yoshimi Okada, Dr. Principal Researcher Chiyoda Corporation Technology Development Unit Hydrogen Supply Chain Development Unit All Rights Reserved. CHIYODA

2 Recent Events on Hydrogen Energy April 2014 Cabinet Decision on the New Strategic Energy Plan June 2014 The Strategic Roadmap for Hydrogen and Fuel Cells Dec COP21 Paris Agreement by all 196 countries Mar The Revised Version The Strategic Roadmap for Hydrogen and Fuel Cells April 2016 National Energy and Environmental Strategy June 2016 Hydrogen thermal power generation is launched in technology road map for Next-generation thermal power generation Jan Hydrogen Council was initiated at the World Economic Forum in Davos by 13 companies. All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 2 March 1 st 2017

3 Target of The Strategic Road Map for Hydrogen and Fuel Cells Cabinet decision of New Strategic Energy Plan in April, The strategic road map of H 2 and Fuel Cells also issued in June 2014 and revised in April Target 1. Stationary Fuel Cells (Ene-Farm etc.) 2020 :1.4 million unit, 2030 : 5.3 million units 2. Fuel Cell Vehicle (FCV) FCV : 40,000 (2020), 200,000 (2025), 800,000 (2030) H 2 station : 160 (2020), 320 (2025) 3. Hydrogen for thermal power generation 2025 : Fuel for thermal power generation 2030 : Japan aims introduce to import H 2 from abroad All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 3 March 1 st 2017

4 National Energy and Environment Strategy for Technological Innovation towards 2050 Source : Cabinet office, Government of Japan HP All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-74 March 1 st 2017

5 Technology Road Map for Next-Generation Thermal Power Generation CCUS: Carbon dioxide Capture, Utilization and Storage Technical demonstration Technical demonstration CH 4 /H 2 mixture fuel for gas turbine H 2 gas turbine Source : METI HP All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 5 March 1 st 2017

6 Hydrogen Supply Chain Concept All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 6 March 1 st 2017

7 SPERA Hydrogen System (Liquid Organic Hydrogen Carrier) H 2 Production Site H 2 Utilization Site MCH H 2 Toluene H 2 Resources CH 3 Hydrogenation CH 3 Storage Transportation Storage Utilization Dehydrogenation CH 3 CH 3 + 3H2 + 3H2 Toluene MCH : Methylcyclohexane MCH Toluene Liquid state storage and transportation Under the ambient temperature and pressure Hydrogen energy can be treated as easy as potential risk of gasoline. Conventional infrastructure can be utilized. (storage tanks, chemical tanker and chemical tracks has been well commercialized.) High Energy efficiency All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 7 March 1 st 2017

8 Tankers for Overseas shipment Present MR: Middle range Class MCH: 44,000ton/ship (H 2 : 2,700ton/ship= 56,000m 3 -MCH/ship) 14kn (26km/hr) : 21 days from Middle east to Japan Crew : Fuel : Heavy oil 36ton/day Commercialized Future VLCC: Very large Crude oil carrier MCH: 190,000 ton/ship (H 2 : 11,500ton/ship= 240,000m 3 - MCH/ship) Crew : Fuel : Heavy oil 100ton/day Not commercialized License by IMO is necessary IMO (Inter national Maritime Organization) Chemical Tanker (Middle range class) Very large crude oil Carrier: VLCC All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-78 March 1 st 2017

9 Typical Organic Chemical Hydride System CH 3 CH 3-3H 2 + 3H 2 Methylcyclohexane (MCH) Toluene H=205kJ/mol (1) Cyclohexane Decalin - 3H 2 + 3H 2-5H 2 + 5H 2 Benzene Naphthalene H=206kJ/mol H=332kJ/mol (2) (3) All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-79 March 1 st 2017

10 Equilibrium Conversion (%) Chemical Equilibrium of MCH Dehydrogenation Decalin Methyl cyclohexane Cyclohexane Pressure : 1atm Temperature (K) All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 10 March 1 st 2017

11 Toluene/MCH System (1) CH 3 CH 3 Methylcyclohexane (MCH) MCH-Toluene - 3H 2 + 3H 2 Toluene Cyclohexane-Benzene ΔH=205kJ/mol Decalin-Naphthalene Methylcyclohexane Toluene Cyclohexane Benzene Decalin Naphthalene Fomula M.W. State at room temp. C 7 H 14 C 7 H 8 C 6 H 12 C 6 H 6 C 10 H 18 C 10 H Liquid Liquid Liquid Liquid Liquid Solid Density (g/cm 3 ) mp. ( ) cis : trans : bp. ( ) cis : trans : Hydrogen storage density (wt%) (kg-h 2 /m 3 ) Amount for 5kg-H 2 storage (kg) (L) All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 11 March 1 st 2017

12 Conventional Dehydrogenation Catalyst Performance in 1980 s 100 Activity, % 500, 1atm LHSV=0.11 h -1 H 2 +N 2 +MCH in molar ratio=9/9/ Time on Stream, Hours University of Connecticut, AICh Journal of Catalysis, vol.88, 150 (1985) 50 Time on Stream, Hours Indian Institute of Technology, AICh Journal, vol.31, No.12, 1997 (1985) All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 12 March 1 st 2017

13 MCH Conversion (%) Developed Dehydrogenation Catalyst Performance in Laboratory-Scale (2009) 100 MCH 転化率 (%) 90 Reaction Condition : , LHSV=2.0h -1 反応条件 : , LHSV=2.0h 80 Feed : Industrial grade MCH, -1 原料 : 工業用 MCH, co-feed H 2 : 無 Co-feed H 2 : Nothing 70 Performance 触媒性能 60 MCH MCH Conversion 転化率 : >95%, トルエン選択率 Toluene Selectivity : >99.9% : >99.9% H 水素発生速度 >1,000 2 generation rate : > 1,000Nm 3 -H 2 /m 3 -cat/h /h Time 反応時間 on stream (h) All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 13 March 1 st 2017

14 Development of SPERA H 2 System (Note) MCH: Methylcyclohexane TOL: Toluene Dehydrogenation Section Product TOL Feed MCH H 2 50Nm 3 /h Hydrogenation Section Product MCH Feed TOL O S = O = o o Pt 1nm Pt アルミナ担体 Al 2 O 3 Carrier S 原子 O S = O = o o Estimated catalyst surface model S MCH Tank MCH Tank TOL Tank TOL Tank Process Section (50Nm 3 -H 2 /h) Tank Area Demonstration plant at Chiyoda R&D Center, Yokohama, Japan All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 14 March 1 st 2017

15 Demonstration plant (Reaction Section) Dehydrogenation (H 2 Utilization Site) Hydrogenation (H 2 Production Site) Dehydrogenator Hydrogenator All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 15 March 1 st 2017

16 Demonstration Plant [Tank yard] MCH Tank Toluene Tank Tanks for hydrogenation unit Tanks for dehydrogenation unit All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 16 March 1 st 2017

17 Demonstration Performance (April, 2013 Nov. 2014) Demonstration operation All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 17 March 1 st 2017

18 Demonstration Performance Capacity:50Nm 3 /h (H 2 storage & generation) Hydrogenation(H 2 storage reaction) Conversion :> 99 % Selectivity:> 99% Yield(H 2 storage ratio): > 99% Dehydrogenation(H 2 generation) Conversion :>95% Selectivity :> 99% Yield(H 2 generation ratio): > 95% H 2 storage & generation ratio: > 95% All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 18 March 1 st 2017

19 How to prevent global warming by H 2 energy H 2 Electricity City Gas Industry Traffic Home H 2 fuel for Power generation (CH 4 /H 2, Coal/H 2, H 2 Turbine) MW Class Fuel Cell (Air port, Station, Buildings etc.) Synthetic Methane (Sabatier reaction : CO 2 + 4H 2 CH 4 + 2H 2 O) CH 4 /H 2 : Hytan (Hydrogen methane) Chemical Utilization of Recovered CO 2 H 2 + CO 2 Chemistry (Reverse shift reaction : CO 2 +H 2 CO+H 2 O ) H 2 Station (FCV, FC Ship etc. ) Residential Fuel Cell All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 19 March 1 st 2017

20 1.H 2 Supply Chain Demonstration Project (NEDO) The project aims to demonstrate a Hydrogen Supply Chain by Organic Chemical Hydride Method by utilizing not utilized resource for H2 production. The project consist of phase 1 (2years) and phase 2 (4years). Phase 1 : Investigation of Scale-up, catalyst durability, supply chain operation etc. Phase 2 : It will be decided after evaluation of the results of phase 1. H 2 Supply Chain by Organic Chemical Hydride Method Institution for execution Chiyoda Corporation Co-execution company Mitsubishi Corporation Mitsui & Co., LTD Schedule Co-operation company Nippon Yusen (NYK LINE) MITSUBISHI HITACH POWER SYSTEMS Development Bank of Japan All Rights Reserved. CHIYODA 2016 Resource : By Chiyoda based on the material of METI All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 20 March 1 st 2017

21 2. H 2 from Renewable Energy Storage Project (NEDO) H 2 production (Electrolyzer) Fluctuated Electricity (Pseudo signal) Rectifier Electricity Electrolyzer Resource : By Chiyoda based on the material of METI 4 years R&D from 2015 H 2 Production (Alkaline water electrolysis) Absorb fluctuation of grid electricity by electrolyzer H 2 purification from electrolyzer SPERA Hydrogen System (Demo plant) Efficient hydrogenation with a load change H 2 Storage as MCH SOFC (Laboratory investigation) Purification of H 2 from SPERA Hydrogen Heat integration between SOFC and dehydrogenation H 2 Utilization (SOFC) Electrical grid Electricity Heat SOFC H 2 purification H 2 purification Hydrogeantion MCH MCH Dehydrogeantion Toluene Toluene H 2 Storage (SPERA Hydrogen) All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 21 March 1 st 2017

22 3. H 2 Refueling Station Development (NEDO) Key : Down sizing and cost down of dehydrogenation unit 1. Use : FCV, Falk Lift MCH Chemical Track Tank Purification Dehydrogenation Compressor Cylinder Dispenser Unit 2. R&D Items Down sizing and cost down of dehydrogenation unit Purifiction system :ISO Hot oil unit for dehydrogenation reaction heat supply Heat management Resource : By Chiyoda based on the material of METI All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 22 March 1 st 2017

23 4. Membrane Reactor Development (NEDO) Collaboration project with RITE (RITE : Research Institute of Innovative Technology for the Earth) Development of a Membrane Reactor (MR) for the dehydrogenation unit Fundamental study (Phase 1: 3years) and evaluation for Phase 2 Target image is for a compact dehydrogenation unit for H 2 refueling station etc. MCH Toluene Resource : By Chioyda based on the material of METI All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 23 March 1 st 2017

24 Acknowledgement Above four R&D projects are funded by NEDO (New Energy and Industrial Technology Development Organization) We express wards of gratitude for NEDO. All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 24 March 1 st 2017

25 Thank you for your attention. All Rights Reserved. CHIYODA 2016 All Rights Reserved. CHIYODA 2017 FC EXPO 2017 Technical conference FC-7 26 March 1 st 2017

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