Development of large scale H 2 storage and transportation technology with Liquid Organic Hydrogen Carrier (LOHC)

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1 Development of large scale H 2 storage and transportation technology with Liquid Organic Hydrogen Carrier (LOHC) Abroad See Japan CO2 [H2 Plant] H2 CHIYODA H 2 Storage and Transportation Technology Metyhylcyclohexane Metyhylcyclohexane Hydrogenation Dehydrogenation Plant Storage Plant Tank Plant Tank Plant Toluene Toluene H2 Thermal Power Plant (CH 4 /H 2 Fuel) FC System City Gas Blend (Hythane) CCS CCS EOR EOR CO CO 2 Separation 2 Separation Reforming [H2 Plant] H2 H2 Electrolysis etc. Natural Gas CO2 CO CO 2 Separation 2 Separation CCS CCS ( ECBM ECBM ) Gasification Wind Energy Solar Energy Hydraulic Energy Renewable Energy Coal February 5,

2 Organic Chemical Hydride Method The Methylcyclrohexene(MCH) is considered one of the safety and economical hydrogen carriers because of the storage and transportation in the liquid phase under the ambient temperature and pressure. Methylcycrohexene (MCH) H 2 H 2 Toluene Hydrogenation Storage Transportation Storage Dehydrogenation CH 3 CH 3 + 3H 2 Δ H= + 205kJ/mol Toluene Methylcycrohexane Hydrogenation CH 3 CH 3 + 3H 2 ΔH= - 205kJ/mol Methylcycrohexane Toluene Dehydrogenation 2

3 Idea for Global Hydrogen Supply Chain CHIYODA H 2 Storage and Transportation System by Organic Chemical hydride Method Abroad Sea Japan Hydrogenation Plant Storage Dehydrogenation H Tank Unit 2 Thermal Power Plant (CH 4 /H 2 Fuel) etc. FC System City Gas Blend (Hythane) H 2 H 2 CO 2 Separation Sift reaction Reforming CCS CO 2 CO 2 Separation Sift reaction Gasification Electrolysis Renewable Energy Wind Energy Natural Gas Heavy Oil Coal Solar Energy Fossil Fuel Hydraulic Energy 3

4 200 Hydrogen Storage Density Liquid hydrogen and compressed hydrogen system have been proposed for the hydrogen transport and storage method. But in these systems, the very low temperature of around minus 250 or the high pressure of about 35MPa are required respectively. Volumetric density (kg-h 2 /m 3 ) wt% Methylcyclohexane (MCH) Metal hydride Organic chemical hydride 3wt% Decalin Cyclohexane Liquefied H 2 70MPa Compressed H 2 35MPa Gravimetric density (wt%) Note: In the calculation of the gravimetric density, weight of container to storage liquid and compressed hydrogen is considered. 4

5 Comparison of Organic Chemical Hydride System CH 3 CH 3-3H 2 + 3H 2 Methylcyclohexane (MCH) Toluene H=205kJ/mol Cyclohexane - 3H 2 + 3H 2 Benzene H=206kJ/mol Decalin - 5H 2 + 5H 2 Naphthalene H=332kJ/mol Property Organic Chemical Hydride System MHC and Toluene System Cyclohexane and Benzene System Decaline and Naphthalene System MHC Toluene Cyclohexane Benzene Decaline Naphthalene Chemical Formula CH 3 CH 3 Molecular Weight State at room temperature liquid liquid liquid liquid liquid Solid Density (g/cm 3 ) Melting Point ( ) , Boiling Point ( ) , Hydrogen Storage Density (wt%) (kg-h 2 /m 3 )

6 Reaction Equilibrium for Dehydrogenation To get 100% conversion of MCH, the reaction temperature should be set higher than 300. And the external heat supply for endothermic dehydrogenation reaction is required. Equilibrium Conversion (%) Decalin Methyl cyclohexane Pressure:1atm Cyclohexane Temperature ( ) 6

7 Characteristics of Dehydrogenation Catalyst 1.STEM Image 2.EPMA Observation 1)Ordinary egg shell type Pt/Al 2 O 3 cat. 2)Developed Pt/Al 2 O 3 cat. is uniform type Sulfur Sulfur Platinum Platinum From the STEM image, it is observed that platinum clusters which have the size around 1nm are highly dispersed on alumina carrier. Small amount of sulfur compound is intentionally added in the alumina support for our catalyst preparation. As shown in EPMA analysis the sulfur compound is uniformly distributed with platinum. 7

8 Results of Catalyst Life Test MHC Conversion (%) Reaction Conditions Temperature: Pressurea : 0.3MPa LHSV: 2.0h -1 Feed:Methylcycrohexane(Purity=99.85%) Time on Stream (HR) Catalyst performance MCH Conversion: >95% Toluene Selectivity : >99.9% Catalyst life : > 8,000 (1year) 8

9 Idea of Hydrogen and Natural Gas Co-firing System for Power Generation The external heat supply for dehydrogenation reaction is required to get hydrogen from MCH, MCH Dehydrogenation Unit Gas Turbine combined Cycle with H2 & NG Co-firing Unit (Heat-exchanger type Dehydrogenation Reactor) Heat Utilization for Dehydrogenation Reaction Natural gas HRSG Electric Generator Exhaust Gas Steam turbine Gas turbine Around 50% reduction of CO2 can be expected by using the hydrogen mixed natural gas. (Hydrogen content:75vol%) Hydrogen HRGS: Heat Recovery Steam Generator System 9

10 Image of Demonstration Plant Hydrogenation Reactor Dehydrogenation Reactor MHC Tank ToleneTank Operation of demonstration plant which has hydrogen production capacity is 50 Nm3/hr will be started at the end of this February. Through this demonstration test the performance of our chemical hydoride system will be confirmed. 10

11 Conclusion Chiyoda have been proposed the H2 supply Chain by Organic Chemical hydride (OCH ) method as liquid organic hydrogen Carrier (LOHC) technology since The system can be applied to the storage and transportation of H2 produced from both fossil fuel and renewable energy. In this technology, Toluene and Methylcyclohexane (MCH) system is employed, because this system can keep the liquid state in wide temperature range without any solvents. Novel dehydrogenation catalyst which is the key technology for the OCH method has been developed. Chiyoda will commence the demonstration test of total system of hydrogenation and dehydrogenation to established the technology for a large scale system in this February. Large scale H2 storage and transportation technology will be established and ready for commercialization at the end of

12 Thank you for your kind attention! 12