“SPERA Hydrogen” System for Large Scale H2 Storage & Transportation and 

H2 Supply Chain ConceptH2 Supply Chain Concept

June 26th, 2014

Chi d C tiChiyoda Corporation

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014 1

Organic Chemical Hydride(OCH) MethodOrganic Chemical Hydride(OCH) Method

MCH

TolueneResourcesResources

HH22HH22

UtilizationUtilization

HH22HH22

HydrogenationHydrogenation

ResourcesResources UtilizationUtilizationStorageStorage StorageStorage

TransportationTransportation DehydrogenationDehydrogenation

CH 3CH 3CH 3CH 3

+ 3H2

CH 3CH 3 CH 3CH 3

+ 3H2

MCH : MethylcyclohexaneToluene MCH Toluene

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014 2

Hydrogen Supply Chain Concept

PVPV Wi dWi d+3H２

CH３CH３

Power Gen.Power Gen.

Renewable EnergyRenewable Energy

PVPV WindWind

CSPCSP

TOL MCHCity GasMobilityCity GasMobility

EnergyEnergy

HH HH

ElectrolysisTOLTOLTOLTOL

FutureFutureFutureFuture

HGNHH22 HH22

HGNHGN DHGDHG

StorageStorageStorageStorageStorageStorageStorageStorageSourcesSourcesSourcesSources UsersUsersUsersUsers

FeedstockFeedstockBy‐ProductReformingGasificationCO2 GasGas MCHMCHMCHMCH Petro Refining

ChemicalsPetro RefiningChemicals

CCSFossil FuelFossil Fuel

EOR

CoalCoalOilOil

Steel MillsCO2 Recycle(Reverse Shift)

Steel MillsCO2 Recycle(Reverse Shift)

HGN: hydrogenation, DHG: dehydrogenationTOL: toluene, MCH:  Methylcyclohexane

CurrentCurrentCurrentCurrent

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

(Reverse Shift)(Reverse Shift)CurrentCurrentCurrentCurrent

3

Dehydrogenation CatalystOrdinary egg shell type Pt/Al O cat Developed Uniform type S Pt/Al O cat

Dehydrogenation CatalystOrdinary egg shell type Pt/Al2O3 cat. Developed Uniform type S‐Pt/Al2O3 cat.

S Pt PtSS Pt PtS

SOO ≒ 1nm

SOO

Estimated Model

PtSo o So oS

Al2O3 Support

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

2 3 pp

4

Dehydrogenation CatalystDehydrogenation CatalystNew Catalyst Observation of Pt particle by STEMNew Catalyst Observation of Pt particle by STEM

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014 5

P f f D h d ti C t l tPerformance of Dehydrogenation Catalyst

100Lab. Test

90

100

 %

80

70onversion,

ConditionsFeed: Methylcyclohexane (99.85% Purity)

60

50

MCH

 Co

Catalyst: S‐Pt/Al2O3Press.: 0.3 MpaLHSV: 2.0h‐1

0 2000 4000 6000 8000 1000050

Time on Stream, h

Catalyst performance

MCH conversion: >95%, Toluene selectivity; >99.9%, H2 yield: >95%H2 generation rate: >1 000 Nm3‐H2/h/m3‐cat (1 000 Ncc‐H2/h/cc‐cat )

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

H2 generation rate: >1,000 Nm H2/h/m cat. (1,000 Ncc H2/h/cc cat.)Catalyst life: >8,000h (1year)

6

Demonstration PlantH2

50Nm3/h

Dehydrogenation Section

Dehydrogenation Section

Hydrogenation Section

Hydrogenation Section

FeedMCH

ProductTOL

d C

Feed TOL

MCHT kMCHT k

MCHTankMCHTank

Product MCH

TOLTankTOLTank

TankTank

TOLTankTOLTank

At Chiyoda R&D Center, Yokohama, Japan

Process Plants (50NmProcess Plants (50Nm33‐‐HH22/h)/h)Process Plants (50NmProcess Plants (50Nm33‐‐HH22/h)/h) Tank Tank Area (1 week capacity)Area (1 week capacity)Tank Tank Area (1 week capacity)Area (1 week capacity)

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

(Note) MCH: Methylcyclohexane TOL: Toluene

7

Hydrogenation ProcessHydrogenation ProcessH2

Charge Heater

C li

Hydrogenation Reactor

Exothermic reaction Cooling Medium

Exothermic reaction Heat exchanger type< 250deg.C temp.< 1.0 MPaG press.

MCHSeparator

TolueneVaporizer

Product Cooler

Vaporizer

Toluene MCH( )

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

(SPERA Hydrogen)

8

Dehydrogenation ProcessDehydrogenation Process

ChCharge Heater

Product

Heating

H2H2 Treatment

Endothermic reaction

Dehydrogenation Reactor

Heating MediumHeat exchanger type

350~400deg.C temp.<1.0 MPaG press.

TolueneSeparator

MCHVaporizer

Effluent Cooler

Vaporizer

MCH(SPERA H d )

Toluene

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

(SPERA Hydrogen)

9

Hydrogenation PerformanceHydrogenation Performance150

200 n

%

50

100

150

Ope

ratio

Load

, %

100

110 0

m

%

80

90

100

quili

briu

mle

ctiv

ity, %

60

70

80 Ratio to Equilibrium

MCH Selectivity

Rat

io to

E&

MC

H S

el

50 0 1000 2000 3000 4000

Operation hours h

R &

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

Operation hours, hNote) Ratio to Equilibrium = (Toluene Conversion ) / (Equilibrium Toluene Conversion)

10

Dehydrogenation PerformanceDehydrogenation Performance200

50

100

150

Ope

ratio

nLo

ad, %

110 0

50

m %

O

90

100

quili

briu

mel

ectiv

ity,

60

70

80 Ratio to Equilibrium

Toluene Selectivityatio

to E

qol

uene

Se

50

60

0 1000 2000 3000 4000

Toluene Selectivity

O ti h h

Ra

& T

o

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014

Operation hours, h

11

Jules Verne Award from IAHEChiyoda awarded at 20th world Hydrogen Energy Conference (WHEC2014) atChiyoda awarded at 20 world Hydrogen Energy Conference (WHEC2014) at  S.Korea from International Association of Hydrogen Energy (IAHE) on 18th June, 2014.  Jules Verne Award is a top award in the hydrogen energy field.

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014 12

Thank you for your attention.

IEA H2 Roadmap Asia Workshop, June 26‐27, 2014 13