hydrogen economy and hydrogen treatment of materials

Hydrogen Economy and Hydrogen Treatment of Materials

Fifth International Conference

HTM-2007

Donetsk, Ukraine May 21-25, 2007

Conference Report

Conference overview

◼ 134 participants, 18 countries – mainly Europe, Asia

◼ 70 oral , 95 poster presentations◼ Hydrogen economy-scenario,viability

◼ Hydrogen production

◼ Platinum and rare metals in fuel cells

◼ Technologies of Hydrogen Storage, transportation and use

◼ Hydrogen Treatment of Metals

◼ Hydrogen degradation of materials and accompanying phenomena

Inauguration and Plenary Talks

Sorensen, Denmark- Scenarios for Renewable Hydrogen

Marty, France-GENHSTOK H2 Prodn with CO2 Capture

Skripnyuk, Israel- Hydrogen storage properties by ECAP

Equal Channel Angular Processing (Plastic Deformation process)

Mg alloy ZK60

Analysed morphology and microstructure

Rougier, France-Tuned catalysts H2 sorption MgH2

Commercial MgH2

ball milled- addition of Ni, Nb205, NbF5 catalyst

Ball milled sample 100 to desorb 80%

Correlated to surface area

Of catalyst

Tamaura, Japan-Economic Solar Hybrid Hydrogen

Solar Steam Reforming

Methanol and Hydrogen

Beam down solar conc system

Tronstad Norway Ultra Clean Shipping

FellowShip project

330 kW Fuel cell

Hybrid Diesel system

Molten Carbonate Fuel Cell

Operation by 2008

Technoeconomic Assessment of Hydrogen Fuel Chain

Manish S, Rangan BanerjeeIndian Institute of Technology Bombay

Keynote talk at HTM 5, Donetsk, 22nd May 2007

Motivation

◼ Fossil fuel scarcity, adverse environmental effects (local and global)

◼ Indian transport sector◼ 22% of total commercial energy

◼ Share in total pollutant load; 70% in New Delhi, 52% in Bombay

◼ Need for alternative transport fuels.

◼ Indian government’s emphasis on biodiesel, hydrogen ..

Hydrogen vehicles - Issues

◼ Is hydrogen fuel chain economically viable?

◼ Can hydrogen vehicles reduce the fossil fuel consumption for transportation?

◼ Can hydrogen vehicles reduce emissions (especially greenhouse gas emissions)?

◼ Is hydrogen a sustainable future vehicle fuel?

Fuel chains

Refinery

Vehicle (Utilization)

Filling stations (Petrol storage and delivery)

Crude oil production centre

Intercontinental crude oil transport

Petrol transport (via Rail/Truck)

Primary energy source

Vehicle (On-board storage and utilization)

Hydrogen production centre (Production and compression)

Filling stations (Hydrogen storage and delivery)

Pipeline transport

Hydrogen fuel chainFossil fuel chain

Base case Fossil fuel based fuel chain

◼ Small-size passenger car (Maruti 800) manufactured by Maruti Udyog Limited

◼ Petrol fuelled,

◼ 37 bhp (27 kW) IC engine

50% share in Indian passenger vehicle-market

560,000 units sold 2005-6

Hydrogen fuel chain – different routes

Hydrogen Production

Storage

Utilization

Steam methane reforming (SMR), Coal gasification, Water electrolysis, Renewable hydrogen (Photovoltaic-electrolysis, Wind power-electrolysis, Biomass gasification, Biological methods)

Compressed hydrogen storage, Metal hydrides, Liquid hydrogen storage, Complex chemical hydrides

Fuel cells (PEMFC), IC engine

Transmission Pipeline transport, transport via truck and rail

Comparison criteria

◼ Non-renewable energy consumption per km travel (MJ/km)

◼ Greenhouse gas emissions per km travel (g CO2-eq/km)

◼ Cost per km travel (Rs./km) (1 UAH = 8.2 Rs)

◼ Annualised life cycle costing (ALCC) method

◼ Existing Indian prices.

◼ If technology is not available commercially in India, international prices are used

◼ Resource constraints

Methodology

◼ Life cycle assessment (LCA) ◼ All material and energy inputs to the process

are identified

◼ Total input energy required to extract, produce, and deliver a given energy output or end use

◼ Energy use and corresponding emissions during fabrication of PV, electrolyzer, wind machine etc. are also taken into account.

Methodology contd..

Inventory (process energy and material) to produce one unit of output

Classification of total primary energy into non-renewable and renewable energy

Non-renewable energy useGHG emissions

Total primary energy required to produce required process energy and materials

Cost of different equipment and material required, discount rate, life of the equipment

Life cycle cost

Materials and other resources such as water, land etc required to produce 1 kg of hydrogen

Resource constraint

Amount of material and other resources required to meet the current demand

Process flow chartsSizing of different equipment required

Total GHG emissions in producing process energy and materials (using emission factors)

Resource constraint

Resource constraint

Material supply constraint

Area

Material constraint

Other constraint

Annual requirement/Reserve

Area required/Available land area

Annual requirement/Reserve

No constraint

Technical constraint, water for biomass based systems etc.

Source: Manish S, Indu R Pillai, and Rangan Banerjee, "Sustainability analysis of renewables for climate change mitigation," Energy for Sustainable Development, vol. 10, no. 4, pp. 25-36, 2006.

Energy analysis

Power required at wheels

Transmission and IC engine efficiency

Fuel requirement from fuel tank

Input (Drive cycle,Vehicle weight,Front area, Air density, Cd, Cr)

IC engine vehicle


Transmission, Fuel cell and Electric motor efficiency

Fuel requirement from fuel tank

Input (Drive cycle,Vehicle weight,Front area, Air density, Cd, Cr)

Fuel cell vehicle

Source: Manish S and Rangan Banerjee, "Techno-economic assessment of fuel cell vehicles for India," 16th World hydrogen energy conference, Lyon (France), 2006.

Indian urban drive cycle

Indian urban drive cycle :-

Low average speed (23.4 km/h) and rapid accelerations (1.73 to -2.1 m/s2)

European urban drive cycle :-

Average speed (62.4 km/h) and accelerations from 0.83 to -1.4 m/s2

0

2

4

6

8

10

12

14

16

18

20

0 500 1000 1500 2000 2500 3000

Time (s)

Spee

d (m

/s)

Avg. speed - EUDC

Avg. speed IUDC


◼ Three forces acts on the vehicle (Assumption:-vehicle is running on a straight road with a zero gradient). These are

◼ Aerodynamic drag {FDrag(t)} = 0.5ρAv(t)2Cd

◼ Frictional resistance {FFriction(t)} = mgCr

◼ Inertial force {FInertia(t)} = mf {f=dv(t)/dt}

◼ FTotal(t)=FDrag(t)+FFriction(t)+FInertia(t)

◼ PWheel(t)=FTotal(t)×v(t)

Data used for base case vehicleParameter Value

Air density (kg/m3) 1.2

Coefficient of drag resistance 0.4

Coefficient of rolling resistance 0.01

Cargo weight (kg) 250

Frontal area (m2) 2

Transmission efficiency 0.7

Transmission weight (kg) 114

IC engine weight (kg) 90

Fuel tank weight (kg) 40

Fuel capacity (kg) 24

Vehicle body weight (kg) 406

Total weight (kg) 900

Result for base case vehicle

Parameter Value

Driving range (km) 434

Cost (Rs/km) 2.8 (0.34)

Non-renewable energy use during operation (MJ/km) 2.6

GHG emissions (g/km) 180

Driving range of hydrogen vehicles should be at least half (~217 kms) for their public acceptance.

•Average daily travel Indian urban 100 kms.

•Vehicle to run for 2-3 days.

Hydrogen fuel chain – Options considered

Hydrogen fuel chain

Production

Steam methane reforming (SMR)

PV-electrolysis (PV)

Wind-electrolysis (WE)

Biomass gasification (BG)

Transmission

Pipeline transport

(PL)

Storage

Compressed hydrogen (C)

Liquid hydrogen (L)

Metal hydride (M)

Utilization

PEM fuel cell

(FC)

IC engine

(IC)

Hydrogen production – Steam Methane Reforming (SMR)

◼ Feedstock - Natural Gas

◼ SMR: CH4 + 2H2O → 4H2 + CO2

◼ Life of plant 20 years

◼ Existing NG price Rs 8/Nm3, 1 UAH/ Nm3

Price of Hydrogen Rs 48/ kg 4.3 Rs/Nm3 or 400 Rs/GJ (5.9 UAH/kg 0.5UAH/Nm3,

49 UAH/GJ)

Variation of Hydrogen price with NG price

0

0.5

1

1.5

2

2.5

0 1 2 3 4 5 6

Natural Gas price (UAH/Nm3)

Hyd

rog

en

Pri

ce (

UA

H/N

m3)

PV-Electrolyzer System

• HYSOLAR (Saudi Arabia) 350 kW Alkaline electrolyser 65 m3/h peak (German-Saudi) ~5.8 kg/hr

PV arrayMPPT and DC-DC converter

Water

Oxygen

PEM Electrolyzer

Hydrogen

PV-Hydrogen

◼ 100 kg hydrogen/ day

◼ Electrolyzer efficiency 70%

◼ Annual capacity factor 20%

◼ Module area 8800 m2

◼ 1300 kWp PV, 1200 kW electrolyzer

Wind-ElectrolyzerUtsira Plant

10 Nm3/h (~0.9kg/h)

48 kW electrolyzer

Two wind turbines 600 kW (peak) each

Source: Norsk Hydro

WECSAC-DC converter

Water

Oxygen

PEM Electrolyzer

Hydrogen

Wind-Electrolyzer

◼ 100 kg hydrogen/ day

◼ Electrolyzer efficiency 70%

◼ Annual capacity factor 30%

◼ 880 kW (peak), 784 kW electrolyzer

Biomass gasifier-reformer

Many configurations possible – atmospheric, pressurised, air blown, oxygen blown

No large scale systems

Hydrogen

SyngasBiomass

Air

Steam

Gasifier Gas cleaning

Methane steam reforming

Water gas shift reaction

Pressure swing adsorption

Comparison of hydrogen production methods

Indicator Unit SMR PV-electrolysis

WECS-electrol.

BiomassGasification

Non-renewable energy use

MJ/kg 182 67.5 12.4 67.7

GHG emission kg/kg 12.8 3.75 0.98 5.4

Life cycle cost* Rs/kgUAH/kg

485.85

1220148.8

40048.8

44.75.45

*At 10% discount rateAverage load factors; PV-0.2, WECS-0.3, Biomass gasification-0.65

Hydrogen transmission

◼ Can be transported as a compressed gas, a cryogenic liquid (and organic liquid) or as a solid metal hydride.

◼ Via pipeline, trucks, rail etc.

◼ Compressed hydrogen via pipeline◼ US, Canada and Europe

◼ Typical operating pressures 1-2 MPa

◼ Flow rates 300-8900 kg/h

Hydrogen transmission-contd..

◼ 210 km long 0.25 m diameter pipeline in operation in Germany since 1939 carrying 8900 kg/h at 2 MPa

◼ The longest pipeline (400 km, from Northern France to Belgium) owned by Air Liquide.

◼ In US, total 720 km pipeline along Gulf coast and Great lakes.

Results for transmission process

For 1 million kg/day, transmission distance 100 km, supply pressure 10 bar

Parameter Value Unit

Optimum pipe diameter 1 m

Transmission cost 6.93 (0.85UAH/kg) Rs/kg

GHG emissions 0.99 kg/kg

0

2

4

6

8

10

12

14

16

18

20

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

Pipe dia (m)

Tra

nsm

issio

n c

ost

(Rs/k

g)

Transmission cost vs. pipe diameter

Hydrogen on-board storage and utilization

◼ Demo hydrogen vehicles : Daimler-Benz, Honda, Toyota, Ford, BMW, General Motors, Daimler-Chrysler, Mazda

◼ On-board storage: compressed gas, liquid hydrogen, metal hydride, organic liquid

◼ Energy conversion device: internal combustion engine, fuel cell

Vehicles with compressed hydrogen storage

Name of thevehicle/Company

Energy conversiondevice

Net poweroutput

Storage system Range ofVehicle(km)

NEBUS (bus)(Daimler-Benz)

Fuel cells10 stacks of 25kW

190 kW 150 litre cylindersat 300 bar

250

Zebus (bus)(Ballard powersystems)

Fuel cells 205 kW Compressedhydrogen

360

FCX (Car)(Honda)

Fuel Cells 100 kW 171 litre at 350bar

570

FCHV-4 (car)(Toyota)

PEM fuel cell+ Battery

80 kW 350 bar 250

Model U(Ford motor co.)

Internal combustionEngine

113 kW@4500rpm

7 kg @690 bar ---

NECAR 2(Daimler Benz)

Fuel cell 50 kW Compressed gas ---

Vehicles with liquid hydrogen storage


Energyconversiondevice

Net poweroutput

Storagesystem

Range ofVehicle(km)

BMW 750-hl(BMW Corporation)

Hybrid, 12 cylindercombustion engine

--- 140 liters, cryostorage at -2530C

400

Hydrogen 3(General motors)

Fuel cell 60 kW 4.6 kg LiquidHydrogen at -253oC

400

Necar4(Daimler Chrysler)

Fuel cell 70 kW --- 450

Vehicles with organic liquid storage


Energyconversion device

Net poweroutput

Storage system

NECAR 5(Daimler Chrysler)

Fuel cell 75 kW Methanol(On board reformer)

FC5(Ford Motor company)

Fuel cell 65kW --do--

Mazda Premacy(Ford Motor company)


FCX-V2(Honda Motor company)


Vehicles with metal hydride storage system


Energyconversion device

Net poweroutput

Storagesystem

HRX2(Mazda MotorCorporation)

Wankel RotatoryEngine

65kW TiFe

FCX-V1(Honda Motorcompany)

Fuel cell 60kW LaNi5

On-board storage + utilizationOption Cost

(Rs/km)

UAH/km

GHGg/km

Non-renewable energy use (MJ/km)

H2 use MJ/km

On-board storage

Energy conversion device

Compressed H2

Fuel cell 21.03(2.56)

17.8 0.24 0.83

Liquid H2 Fuel cell 21.06(2.56)

17.8 0.24 0.80

Metal hydride Fuel cell 21.92 (2.67)

26.9 0.36 0.88

Compressed H2

IC engine 1.23 (0.15)

0* 0* 2.47

Liquid H2 IC engine 1.35(0.16) 0* 0* 2.32

Metal hydride IC engine 4.17(0.51) 32 0.42 2.74

*Energy use and emissions in base case vehicle manufacturing neglected

Results for hydrogen storage (at filling stations)

Parameter Compressed hydrogen

Liquid hydrogen

Metal hydride

Unit

Delivery and storage cost

8.75 (1.07)

42.6(5.20)

33.7(4.11)

Rs/kgUAH/kg

GHG emissions 1.24 7.2 0.28 kg/kg

Non-renewable energy use

12.72 74 3.84 MJ/kg

PV-PL-C-FC

Cost break-up

1.2

19.95.8

2.6

0.0

0.1

8.6

Vehicle

Fuel cell

Photovoltaic

Electrolyzer

Transmission

Storage

◼ Specific fuel consumption- 6.9 g/km

◼ Cost- 29.6 Rs/km (3.6 UAH/km)

◼ GHG emissions- 59.1 g/km

BASE CASE

Rs 2.6/km

0.34UAH/km

GHG 180g/km

PV-PL-C-IC

Cost break-up

1.2

17.3

7.9

0.1

0.2

25.5Vehicle

Photovoltaic

Electrolyzer

Transmission

Storage


◼ Cost- 26.7 Rs/km (3.26UAH/km)

◼ GHG emissions- 123.2 g/km BASE CASE

Rs 2.6/km

0.34UAH/km

GHG 180g/km

WE-PL-C-IC

Cost break-up

1.2

2.9

5.2

0.1

0.2

8.5Vehicle

WECS

Electrolyzer

Transmission

Storage


◼ Cost- 9.7 Rs/km (1.18 UAH/km)

◼ GHG emissions- 66.1 g/km

BASE CASE

Rs 2.6/km

0.34UAH/km

GHG 180g/km

SMR-PL-C-IC/SMR-PL-C-FC

SMR-PL-C-IC◼ Specific fuel consumption- 20.6

g/km

◼ Cost- 2.5 Rs/km (UAH 0.30/km)

◼ GHG - 310 g/kmBASE CASE

Rs 2.6/km

0.34UAH/km

GHG 180g/kmSMR-PL-C-FC

◼Specific fuel consumption- 6.9 g/km

◼Cost- 21.5 Rs/km (UAH 2.62/km)

◼GHG - 122 g/km

BG-PL-C-IC


◼ GHG emissions- 158 g/km

◼ Cost

CASE 1 Biomass freely available

2.5 Rs/km ( UAH 0.30/km)

CASE 2 Biomass commercially grown

Depends on land price

4.7 Rs/km ( UAH 0.57/km)

BASE CASE

Rs 2.6/km

0.34UAH/km

GHG 180g/km

Cost break-up

1.2

0.9

2.3

0.1

0.2

3.5 Vehicle

Production

Land cost

Transmission

Storage

Cost break-up

1.2

0.9

0.1

0.2

1.2

Vehicle

Production

Transmission

Storage

Case 1 Biomass freely available

Case 2 Biomass grown commercially

Hydrogen fuel chain BG-PL-C-IC

Biomass

Pipeline transport

Production and

compression• Hydrogen 2 million kg per day

• Area for biomass growth 3800 km2 (380000 ha)

• Power required 124 MW (for delivery at 10 bar)

• Biomass gasifier rating 2000 MWe

H2-IC engine

Vehicle

Compressed Hydrogen storage and delivery

• Storage tank autonomy period half day

• Storage capacity 1 million kg

• Volume of storage 40 million liters @ 200 bar (40000 m3, sphere of 21.2 meter radius,)

• Compressor power required 143 MW (for hydrogen compression from 10 to 200 bar)

Filling

stations

On-board compressed hydrogen storage with IC engine

• Hydrogen use: 2.47 MJ/km

• 4.47 kg storage capacity for 217 km range

• Storage tank

o Weight ~220 kg

o Water capacity @ 200 bar 180 liters

• 2 million kg H2 per day for 1 million vehicles (100 km daily travel)

Biomass

gasification

Conclusions

◼ Renewable hydrogen based fuel chains viable based on GHG emission and non-renewable energy use criteria

◼ Cost (Rs/km) higher (for photovoltaics, electrolyzer and fuel-cell based system) than the existing petrol based fuel chain.

◼ IC engine vehicles have lower cost but higher energy consumption than the fuel cell vehicles.

◼ Hydrogen fuel chain based on SMR process (with compressed hydrogen storage and IC engine) is economically viable. However this fuel chain has higher GHG emissions.

Conclusions ..

◼ If biomass is available freely, hydrogen fuel chain based on biomass gasification (with compressed hydrogen storage and IC engine) performed better than the existing petrol based fuel chain on all three criteria

◼ If biomass is grown commercially biomass gasification based fuel chain also becomes economically unviable.

◼ Land requirement may pose a constraint to widespread adoption of biomass based fuel chain.

◼ Hydrogen Technology/ Systems development – can be guided by multi-criteria analysis

References

◼ Maruti udyog limited, "http://maruti800.marutiudyog.com/specifications.asp," 2005.

◼ National Renewable Energy Laboratory, "http://www.ctts.nrel.gov/analysis/advisor.html," 2005.

◼ The Federal Environmental Agency, "http://www.umweltbundesamt.de/uba-info-daten-e/daten-e/carbon-dioxide-emissions.htm," 2005.

◼ Specht M, Staiss F, Bandi A, and Weimer T, "Comparison of the renewable transportation fuels, liquid hydrogen and methanol, with gasoline-Energetic and economic aspects," International Journal of Hydrogen Energy, vol. 23, no. 5, pp. 387-396, 1998.

◼ Das A and Parikh J, "Transport scenarios in two metropolitan cities in India: Delhi and Mumbai," Energy Conversion and Management, vol. 45, pp. 2603-2625, 2004.

◼ Manish S, Indu R Pillai, and Rangan Banerjee, "Sustainability analysis of renewables for climate change mitigation," Energy for Sustainable Development, vol. 10, no. 4, pp. 25-36, 2006.

◼ Oney F, Veziroglu TN, and Dulger Z, "Evaluation of pipeline transportation of hydrogen and natural gas mixtures," International Journal of Hydrogen Energy, vol. 19, no. 10, pp. 813-822, 1994.

http://maruti800.marutiudyog.com/specifications.asp,

http://www.ctts.nrel.gov/analysis/advisor.html,

http://www.umweltbundesamt.de/uba-info-daten-e/daten-e/carbon-dioxide-emissions.htm,

References ..

◼ Pehnt M, "Life-cycle assessment of fuel cell stacks," International Journal of Hydrogen Energy, vol. 26, pp. 91-101, 2001.

◼ Newson E, Haueter TH, Hottinger P, Von Roth F, Scherer GWH, and Schucan TH, "Seasonal storage of hydrogen in stationary systems with liquid organic hydrides," International Journal of Hydrogen Energy, vol. 23, no. 10, pp. 905-909, 1998.

◼ Sarkar A and Banerjee R, "Net energy analysis of hydrogen storage options," International Journal of Hydrogen Energy, vol. 30, pp. 867-877, 2005.

◼ Sandrock G, "A panoramic overview of hydrogen storage alloys from a gas reaction point of view," Journal of Alloys and Compounds, no. 293-295, pp. 877-888, 1999.

◼ Syed MT, Sherif SA, Veziroglu TN, and Sheffield JW, "An economic analysis of three hydrogen liquifaction systems," International Journal of Hydrogen Energy, vol. 23, no. 7, pp. 565-576, 1998.

◼ Amos WA, "Costs of storing and transporting hydrogen," National Renewable Energy Laboratory,NREL/TP-570-25106, 1998.

Thank you (Dyakuyu)

hydrogen economy and hydrogen treatment of materials

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