hydrogen – potentials and perspective...slide 4 properties h(ydrogenium) hydrogen h is the most...

Hydrogen – Potentials and Perspective

Dr. Manfred KlellHyCentA Research GmbH, Graz

A3PS, Vienna, 18. November 2010

Hydrogen

• Motivation

• Properties

• Production

• Storage

• Application

Internal Combustion Engine

Turbine

Fuel Cell

Mo

tiva

tio

n

Source: Züttel 2010

Hydrogen provides a sustainable energy cycle with closed loop feedstock:

Production from water through electrolysis with electricity from water power

Storage as compressed gas, liquified or in compounds

Combustion in fuel cells, turbines or internal combustion engines emitting water

Hydrogen Economy

Pro

pe

rtie

s

H(ydrogenium)

Hydrogen H is the most abundant element, more than 90 % of all atoms are

hydrogen, main component and main energy source of stars, simplest atom,

one proton and one electron only, very reactive, combines to the molecule H2,

in inorganic (H2O, NH3) and organic compounds (hydrocarbons, alcohols, acids,

proteins).

Hydrogen H2 is a colorless, odorless gas with no toxic effects, lowest density, high

diffusion and heat transfer coefficients, low melting and boiling points, explosive

atmosphere with air in a wide range of mixtures, high flame speed, high adiabatic

combustion temperature.

Pro

du

cti

on

Annual production: 600 Mrd. Nm³,

6,5 EJ/year (1,5 % of primary energy consumptiuon)

In chemistry (NH3), refining & metallurgic processes

• 40 % by-product (Chlor-Alkali-Electrolysis)

• 50 % Reforming (η to 80 %)

• 10 % Electrolysis (η to 70 %)

• Gasification (η to 50 %)

• Chemical water splitting (lab scale)

• Biochemical methods (lab scale)

-

-

- -

--

Anode + K athode -

½ O2

H2

2 H2O + 2 e− → H2 + 2 OH−

2e-

2 OH -

2 OH− → H2O + ½ O2 + 2 e−

H2O

2e-

2e-2e-

+ -

--

--

-- --

----

Anode + K athode -

½ O2

H2

2 H2O + 2 e− → H2 + 2 OH−

2e-

2 OH -

2 OH− → H2O + ½ O2 + 2 e−

H2O

2e-

2e-2e-

+ -

Production

Sto

rag

e

Compressed gaseous hydrogen CGH2:

compressed gas at ambient temperature and pressures of 200 – 700 bar

compression consumes 10 - 15 % of energy content Hu

issue: safety of storage system

gravimetric storge capacity: pure: 33.3 kWh/kg

system 700 bar: 1 kg H2/ 20 kg tank (5 mass%), 1.7 kWh/kg

volumetric storge capacity 700 bar: pure 1.3 kWh/dm³

system 700 bar: 0.02 kg H2/dm³, 0.7 kWh/dm³

Compressed Gas CGH2

Sto

rag

e

Liquid hydrogen LH2:

cryogenic storage at ambient pressure at temperatures around −250°C

liquefaction consumes 20 - 30 % of energy content Hu

complex and open storage system – boil off losses (1% to 3% per day)

gravimetric storge capacity: pure: 33.3 kWh/kg

system: 1 kg H2/ 18 kg tank (7 mass%), 2 kWh/kg

volumetric storge capacity: pure 2.3 kWh/dm³

system: 0.04 kg H2/dm³, 1.2 kWh/dm³

Cryogenic Liquid LH2

Sto

rag

e

Physical adsorption and chemical absorption:

H2 molecules are bound on the surface, e. g. of carbon (nanotubes,

microspheres) or in are bound in the atomic lattice of metals (Mg, Al, Na, Li)

or in liquids (alcohol, gasoline, oil, diesel, NH3)

high theoretical energy densities

practically difficult conditions for charging and decharching

(high or low temperatures, high pressures, long time, irreversible)

at lab scale

Storage in compounds

Sto

rag

e

1 kg gasoline ≈ 0,36 kg H2, 1 kg H2 = 2,77 kg gasoline

13

,9

1,6

1,8 2 0,4

0,1

5 3,8

7,4 8

11

,5

13

,9

33

,3

33

,3

33

,3

0

2

4

6

8

10

12

14

28

30

32

34

GH2

(350 bar)

GH2

(700 bar)

LH2

(2 bar)

Solid

Storage MH

Li Ion

Battery

CNG

(200 bar)

LNG Gasoline

Gra

vim

etr

ic E

ne

rgy

De

ns

ity

[k

Wh

/kg

]

Gravimetric Energy Density Pure

Gravimetric Energy Density System

Gravimetric Energy Density

Sto

rag

e

1 l (dm³) gasoline = 3,84 dm³ LH2 = 6,95 dm³ GH2 bei 700bar

0,8

1,3

2,2

2,2

5,8

8,8

0,5 0,9 1,2

3,3

7

0,8

0,2

7

1,5

0

2

4

6

8

10

GH2

(350 bar)

GH2

(700 bar)

LH2

(2 bar)

Solid

Storage MH

Li Ion

Battery

CNG

(200 bar)

LNG Gasoline

Vo

lum

etr

ic E

ne

rgy D

en

sity [kW

h/d

m3]

Volumetric Energy Density Pure

Volumetric Energy Density System

Volumetric Energy Density

Inte

rna

l C

om

bu

sti

on

En

gin

e

over 1 billion internal combustion engines worldwide

Advantages:

simple, robust and cheep (€ 30/kW)

high energy density (of engine and fuel)

multy fuel ability (liquid, gaseous)

Disadvantages:

low efficiency (Carnot)

emissions (pollutants and noise)

Combustion engine with hydrogen:

+ no emissions except NOx

- no H2 Infrastrukture

Internal Combustion Engine

1807 Francois de Rivaz built the first vehicle with a simple internal combustion

engine with hydrogen

1860 Etienne Lenoir built the first commercially available internal combustion

engine with hydrogen that he also used in a vehicle

HistoryIn

tern

al C

om

bu

sti

on

En

gin

e

The efficiency of internal combustion engines

is limited by the Carnot-efficiency

for the conversion of heat

into mechanical energy.

Efficiency increases with

combustion ratio

and air/fuel ratio.

Efficiency of hydrogen

engines reaches values

between gasoline and

diesel engines.

Verdichtungsverhältnis ε [−]

70

65

60

55

50

45

40

35

30

a=1,8

4 6 8 10 12 14 16 18 20 22

a=1,4

Volllast

a=2,8; λ=1,7 a=1,9; λ=1,6

21,61,41,2

64

pmax: 90 bar 200 bar 180 bar 160 bar

Ottomotoren Dieselmotoren

Laderm. Saugm. Großm. LKW PKW

a=3,0; λ=2,0

0,9

0,8

1

EfficiencyIn

tern

al C

om

bu

sti

on

En

gin

e

OH2

yCOxO

4

yxHC 222yx +→

++

400

270

233

200

00

118127

164

270

0

50

100

150

200

250

300

350

400

Kohle C C7H15 Propan C3H8 Methan CH4 Wasserstoff H2

g C

O2

/Wh

, g

H2

O/k

Wh

g CO2/kWh

g H2O/kWh

Ideal CombustionIn

tern

al C

om

bu

sti

on

En

gin

e

Depending on the air/fuel ratio λ, real combustion produces a number of pollutants apart from water and carbondioxide:

incomplete combustion with local deficiency of air produces carbonmonoxide,

hydrocarbons and carbon as basis for soot and particulate matter,

high temperatures cause formation of nitronoxides

....ON

NO

C

HCCO

OHCO

N 2

yx

21,0

79,0 O

2

yx HC

2O2N

xNO

RussRuss

mnHCCO

2OH2CO

22yx

22

x

mn

22

+++

++

++

+++

++

→

+⋅+

+⋅+

nn

n

n

nn

nn

λλ

Real CombustionIn

tern

al C

om

bu

sti

on

En

gin

e

Vehicles with internal combustion engines for gasoline / methane (natural gas, biogas)

/ hydrogen / mixtures of methane and hydrogen are regarded as bridging

technology:

conventional functionality is combined with the option of CO2-free mobility

Advantages:

proven, tested and cheep engines

use of existing production facilities

use of existing infrastructure

gradual introduction of a new infrastructure

reducion of carbon based pollutants

CO, CO2, CH

synergy effects with components,

infrastructure and customer acceptance

Mixtures hydrogen - methaneIn

tern

al C

om

bu

sti

on

En

gin

e

Prototype by IVT TU Graz, HyCentA

SAE paper 2009-01-1420

IJVD 45 2 2010

Model Mercedes E, CNG

Fuel gasoline, natural gas, hydrogen

Swept volume 1796 cm³

Power gasoline/hydrogen 120 kW / 70 kW

Tank gasoline/hydrogen 65 l / 2 kg at 350 bar

Range gasoline/hydrogen 700 km / 125 km

Multi-Flex-Fuel VehicleIn

tern

al C

om

bu

sti

on

En

gin

e

OEM BMW

Model 760 h

Fuel gasoline and hydrogen

Swept volume 5972 cm³

Power gasoline/hydrogen

191 kW

Tank gasoline/hydrogen

75 l / 8 kg cryo

Range gasoline/hydrogen

500 km / 200 km

Source: BMW AG

BMW Hydrogen 7In

tern

al C

om

bu

sti

on

En

gin

e

Source : MAZDA Motor Corporation

OEM Mazda

Model Premacy

Fuel hydrogen / electricity

Swept volume 2 x 654 cm³

Power 110 kW

Tank 2,5 kg / 350 bar

Range 200 km

Mazda 5 RE & RX-8 HyIn

tern

al C

om

bu

sti

on

En

gin

e

Tu

rbin

e

Also in gas turbines, hydrogen allows for carbon-free combustion.

To avoid nitrogen oxides:

Pure oxygen instead of air (Graz Cycle)

Advantages:

no emissions

high efficiency

Disadvantages:

high costs

high temperatures

Source : Jericha

Turbine

Advantages:

high theoretical efficiency

no emissions tank to wheel

no moving parts

wide variety of applications

Disadvantages:

high costs (catalyst)

no H2 infrastructure

durability ??

Fuel CellF

ue

l C

ell

1838 Friedrich Schönbein discovered the polarisation effect, the

electrochemical production of electricity from water and oxygen in an

electrolyte,

Based on this discovery William Grove 1839 built the first fuel cell

First vehicles with fuel cells were built 1966 by General Motors

and 1970 by Karl Kordesch

HistoryF

ue

l C

ell

The reaction of hydrogen and oxygen yields electricity in a

“cold combustion”

Anode (-):

H2 (g) + 2 OH− (aq) → 2 H2O (l) + 2 e−

oxidation (donation of electrons)

Kathode (+):

H2O (l) + ½ O2 (g) + 2 e−→ 2 OH− (aq)

reduction (acceptance of electrons)

As the voltage of a fuel cell is low, many cells

have to be combined to form a stack

H2 (g) + ½ O2 (g) → H2O (l) ∆RH = − 286 kJ/mol

-

-

- -

--

Anode - K athode +

½ O2

H2

H2O + ½ O2 + 2 e− → 2 OH−

2e-

2 O H -

H2 + 2 OH− → 2 H2O + 2 e−

H2O

2e-

--

--

-- --

----

Anode - K athode +

½ O2

H2

H2O + ½ O2 + 2 e− → 2 OH−

2e-

2 O H -

H2 + 2 OH− → 2 H2O + 2 e−

H2O

2e-

V48,1As/mol964852

J/mol10286 30

mR0 =⋅

⋅−−=

⋅

∆−=

Fz

HE

PrincipleF

ue

l C

ell

The theoretical high efficiency of the fuel cell is decreased by a number of

electrochemical processes, practically efficiencies of a cell range from

60 to 80 %, of a stack from 40 to 60 %.

Heizwertspannung EH0

Standardpotenzial E0

Nernstspannung EN

Entropiedifferenz

Zellspannung EZ

Strom I [A]

Ze

llsp

an

nu

ng

E [

V]

Bereich der Aktivierungsüberspannungen

Bereich der Widerstandsüberspannungen

Bereich der Diffusionsüberspannungen

Zellenleistung

T S

z F

⋅∆

⋅

EfficiencyF

ue

l C

ell

Fuel cells are used in a wide variety of portable, mobile and stationary

applications. Fuel cells can be distinguished based mainly on the operation

temperature and the electrolyte used.

Brennstoffzelle Leistung [kW] el. Wirkungsgrad [%] Anwendung

AFC 10-100 Zelle 60-70, System: 60 Raumfahrt, Fahrzeuge

PEMFC 0,1-500 Zelle 50-70, System 30-50 Raumfahrt, Fahrzeuge

DMFC 0,01-1 Zelle 20-30 Kleingeräte

PAFC bis 10.000 Zelle 55, System 40 Kleinkraftw.

MCFC bis 100.000 Zelle 55, System 50 Kraftwerke

SOFC bis 100.000 Zelle 60-65, System 55-60 Kraftwerke und APU

ApplicationF

ue

l C

ell

Source : HONDA Motor

OEM Honda

Model Clarity FCX

Battery Lithium-Ionen Akku

Electric motor 100 kW

Fuel cell 100 kW

Hydrogen tank 4,1 kg / 350 bar

Range 430 km

Green Car of the Year 2009

Honda Clarity FCXF

ue

l C

ell

Source : Daimler AG

OEM Daimler

Model B Klasse

Battery Lithium-Ionen Akku

Electric motor 100 kW

Fuel cell 100 kW

Hydrogen tank 3,5 kg / 700 bar

Range 400 km

Daimler f-CellF

ue

l C

ell

Fu

el C

ell

Source : Daimler AG

OEM Daimler AG

Model Citaro FC Hybrid

Battery (A123) Lithium-Ionen Akku 26 kWh

Electric hub motor 2 x 80 kW

Fuel cell (AFCC) 2 x 60 kW

Hydrogen tank 7 x 205 l,

35 kg / 350 bar

Range 250 km

Mercedes Benz Citaro

Project BioEnergieSupply:

Biogas /

Natural gas Reforming

PurificationElectrification

Electricity

Heat

Hydrogen

Local production of electricity, heat and fuel(hydrogen) from biogas/natural gas

Fuel Cell-System ProviderVehicle-System Provider Service & Maintenance

H2 InfrastructureProvider

Technical assessment and

project management

Test customers,

industrial field trialEcological & economical

assessment

Project E-LOG-BioFleet

Hydrogen permits a CO2-free sustainable closed energy cycle:

• produced from water by electrolysis using electricityfrom alternative sources (sun, wind, water)

• stored as compressed gas at medium energy densitiesat acceptable technical complexity

• combustion in internal combustion engines as bridgingtechnology, especially in mixtures with (bio)methane

• combustion in fuel cells at high efficiencies, with high vehicledriving ranges and short filling times

Expensive and sophisticated technology

Political support necessary (CO2-tax)

Potentials and Perspective

hydrogen – potentials and perspective...slide 4 properties h(ydrogenium) hydrogen h is the most...

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