WORKSHOP FUEL CELLS

The International Center of Condensed

Matter Physics – ICCMP
University of Brasilia
Brasília, 09 a 13 de Abril de 2007

The Hydrogen Technologies in Brazil

Prof. Dr. Ennio Peres da Silva

Hydrogen Laboratory - LH2
University of Campinas - UNICAMP
Brazilian Reference Center for Hydrogen Energy - CENEH
 University of Campinas

 Founded in 1966
 4 campuses (4 cities)
 66 research units
 19 libraries
 2 hospitals
 1,761 professors
 12,476 undergraduate students
 12,765 graduate students (4,500 PhD students)
 University of Campinas

 UNICAMP is the site for 3 energy study centers:

 The Hydrogen Laboratory (LH2) at the Physics Institute

 The Interdisciplinary Center for Energy Planning (NIPE)

 The Brazilian Reference Center for Hydrogen Energy

(CENEH)
 Hydrogen Laboratory –
Physics Institute

 LH2 has been working on H2

technology since 1975.

 Some research topics:

 Hydrogen economy;
 Hydrogen in metals;
 Automotive hydrogen technologies;
 Alkaline water electrolysis for H2
generation;
 Trace gas analysis and gas standards;
 Electrode surface treatment.
 Brazilian Reference Center
for Hydrogen Energy

Ministry of Science & Tech.

University of Campinas
University of Sao Paulo
Environmental Secretary –SP
Power Generator Co.
N G Organization www.ifi.unicamp.br/ceneh
ceneh@ifi.unicamp.br

SMA/SP
 Brazilian Reference Center
for Hydrogen Energy

 CENEH was founded in March, 2001.

 Its objectives are:

 To promote energy uses of hydrogen  Fuel Cells;

 To collect and disseminate information about hydrogen
technologies;
 To conduct research, developments and studies;
 To promote events and congresses;
 To help the government with energy policies.
H2 for Energy Purposes

Energy Hydrogen Production Support

Processes Uses
Sources Activities
Hydropower Integração
Device
ICE a
Veículos Dispositivos
Assembly
Vehicles
Small Hydro Combustão
Interna Integração
System
Wind Power
Photovoltaic
Electric
Energia
Elétrica
Power
Eletrólise
Water
Electrolysis
da Água H2 Electric
Geração de
Power
Eletricidade
Turbine s
Sistemas
Integration

Armazena/,
Storage,
Turbogeradores Transportation,
Transporte,
Nuclear Distribuição
Distribution
Geração
Heat
Generation
de Calor
Segurança
Safety
Thermosolar Thermochemical
Eletrólise
Heat Separação
Purification
Nuclear Water
da Água
Splitting Células
Fuel a Códigos,
Codes,
Combustível
Cells Standards
Padrões
Líquidos
Liquids Reforma
Steam
Biomassa
Biomass
Etanol,
Ethanol,Óleos,
Oils, Bagasse
Bagaço Gases Reforming
a Vapor

Estacionárias
Stationary Móveis
Mobile Portable
Fossil
Fósseis
Fuels Distributed
En. Elét rica
Po wer Veic
Vehicles
ular Electronic
GN,
NG,Gasolina,
Gasoline,C arvão
Coal Sólidos
Solids Gaseificação
Gasification Co
Cogeração
geration U.A. Potê
APUncia Devices

CENEH’s areas of interest

Water Electrolysis: Grid

Wind

Hydro

Solar

Wind Energy and Production of Hydrogen and Electricity — Opportunities for Renewable Hydrogen – Preprint. J. Levene, B. Kroposki, and G.
Sverdrup. Conference Paper NREL/CP-560-39534. March 2006
Water Electrolysis: Grid

Electrolysis for Energy Storage & Grid Balancing in West Denmark. A possible first step toward the creation of a transport hydrogen
Infrastructure in West Denmark. Report of the Work Group - Incoteco (Denmark) ApS - EFP04 – 0330-0034 - 2004
 Water Electrolysis: off Grid

SOLAR-WASSERSTOFF-BAYERN HYDROGEN DEMONSTRATION PROJECT AT NEUNBURG VORM WALD, GERMANY

INTERNATIONAL ENERGY AGENCY - HYDROGEN IMPLEMENTING AGREEMENT - TASK 11: INTEGRATED SYSTEMS. Final report of Subtask A:
Case Studies of Integrated Hydrogen Energy Systems. Chapter 1 of 11. T. Schucan. Paul Scherrer Institute, Switzerland, IEA/H2/T11/FR1-2000.
 Water Electrolysis: off Grid

SOLAR-WASSERSTOFF-BAYERN HYDROGEN DEMONSTRATION PROJECT AT NEUNBURG VORM WALD, GERMANY

INTERNATIONAL ENERGY AGENCY - HYDROGEN IMPLEMENTING AGREEMENT - TASK 11: INTEGRATED SYSTEMS. Final report of Subtask A:
Case Studies of Integrated Hydrogen Energy Systems. Chapter 1 of 11. T. Schucan. Paul Scherrer Institute, Switzerland, IEA/H2/T11/FR1-2000.
Water Electrolysis: Costs

Brazil, industry
$0.5/m3

Summary of Electrolytic Hydrogen Production. Milestone Completion Report. Johanna Ivy - National Renewable Energy Laboratory-NREL -
September 2004 • NREL/MP-560-36734 - Contract No. DE-AC36-99-GO10337
Brazil Electrolysis Technologies

UNICAMP 3,000 A unipolar electrolyser

Brazil Electrolysis Technologies

UNICAMP/CESP 4,000 A unipolar electrolyser

Brazil Electrolysis Technologies

UNICAMP/CESP 4,000 A unipolar electrolyser in Miracema Ind.

Brazil Electrolysis Technologies

VILLARES 50 m3/h bipolar electrolyser

Brazil Electrolysis Technologies

UNICAMP/CESP 15,000 A unipolar electrolyser

Brazil Electrolysis Technologies

UFPB- Campina Grande bipolar electrolyser

Brazil Electrolysis Technologies

UNICAMP/CEMIG 5 m3/h unipolar electrolyser

Reforming Processes

 More important processes:

Steam-reforming: fuel + steam + heat
Partial Oxidaction: fuel + O2 (partial)
Autothermic: fuel + steam + O2 (partial)

 More important fuels:

Hydrocarbons : methane (NG), LPG, gasoline
Alcoois: methanol, ethanol

 Complementary processes:
Methane shift reaction
CO reaction
H2 purification: CO and CO2 remotion
Brazil motivation for ethanol use

 Brazil is the largest sugar-cane producer in the world;

 Since 1975, bio-ethanol is used as a regular fuel for vehicles

and as an additive for gasoline (~25%);

 It is one of the most effective initiatives in the world to reduce

CO2 emissions in the transportation sector;

 Environmentally friendly: CO2 balance approaches zero;

 Energy balance “ethanol output / crop input”:

sugar-cane overcomes corn (7 : 1.3);

 Ethanol presents a very low toxicity;

Brazil motivation for ethanol use

 As a liquid fuel, ethanol presents a high energy density per

volume;

 Ethanol stores 11.5 times more energy compared to

compressed hydrogen (200 bar);

 This characteristic makes it well suited for on-board hydrogen

generation for FCV or FCHV;

 It is also an important trading opportunity for some developing

countries to be included in the hydrogen economy as ethanol
suppliers.
Ethanol processing

 Steam-reforming: catalytic reaction of the fuel with water:

C2H5OH + 3 H2O  6 H2 + 2 CO2

 Partial Oxidation: a small amount of oxidant and fuel react to

produce heat and water which reacts with the non-oxidized fuel
to generate the syn-gas:

C2H5OH + 1.5 O2  3 H2 + 2 CO2

 Autothermal reforming: two reactions are coupled - fuel oxidation

and steam-reforming:

C2H5OH + 1.8 H2O + 0.6 O2  4.8 H2 + 2 CO2

Ethanol processing

Species
distributions as a
function of
temperature
obtained from
Gibbs free energy
minimization.
Conditions:
P = 1 atm;
(C2H5OH)/(H2O)=
1:3 mol/mol

I. Fishtik et al / International Journal of Hydrogen Energy 25 (2000) 31-45.

Some ethanol reform catalysts

 1% Rh / CeO2 - ZrO2; 1% Rh / Al2O3; Rh / SiO2; Rh / MgO - Al2O3;

 1% Pt / Al2O3; 1% Pt / CeO2 - ZrO2; Pt / TiO2; Pt / MgO - Al2O3;
 0,5% Pd / Al2O3; 1% Pd / CeO2 - ZrO2; Pd sobre Sibunit® (Pd / C);
 Ru / Al2O3;
 5% Ni / Al2O3*; 5% Ni / CeO2 - ZrO2; Ni / MgO; Ni / La2O3;
 Co / Al2O3;
 Co / ZnO;
 ZnO;
 WCxOy / Al2O3;
 Perovskita;
 Cu / SiO2;
 Cu - Al LDH (“Layered Double Hydroxide”);
 Ni - Pt / Al2O3;
 Ni - Pd / Al2O3;
 CuO - ZnO / Al2O3;
 Cu - Zn - Cr / Al2Ox;
 Cu / SiO2; Ni / MgO;
 NiO - CuO / SiO2;
 y% Ni - z% Cu - 0,15% K / Al2O3.
Some CO shift catalysts

 Cu/ZnO/Al2O3;
 CuAl2O4;
 CuCr2O4;
 CuMn2O4;
 CuY2O5;
 CuFe2O4
 La2CuO4;
 Cu/M Ox-M’ Oy ; M, M’ = Al, Cr, Mg, Mn e Zn;
 M” -Cu/Al2O3-ZnO ; M” = Au, Pd, Pt, Rh e Ru.
Fuel Cell System requirements

 Usual syn-gases are composed by: H2, CO2, CH4 and CO;

 Ethanol processing could generate eight other by-products:

ethene (C2H4) dietil-ether (C2H5OC2H5)
ethane (C2H6) acetaldehyde (CH3CHO)
acetic acid (CH3COOH) carbon (C)
non-reacted ethanol water

 Several applications will demand gas purification.

Fuel Cell System requirements

 PEMFC systems:
Carbon monoxide interacts with the electro-catalysts, due to
the low temperature of this type of fuel cell (60-80ºC),
promoting irreversible losses in the electrical performance;

 [CO] ≤ 20 μmol.mol-1;

 Possible solutions:
Catalysts less selective for CO formation;
High and/or low temperature WGSR;
PSA, TSA, VSA, cryogenic or other purification method.
LH2 ethanol processing test bench
LH2 test bench characteristics

Control Panel
Hydrogen Exit

Water-Gas Shift Reactor

Condensation Column

Purification

Steam-reforming Reactor
LH2/Hytron 1 kW prototype

1 kW ethanol ATR for

PEMFC operation
First LH2/Hytron 1 kW prototype

1 kW ethanol ATR for

PEMFC operation
Second LH2/Hytron 1 kW prototype

1 kW ethanol ATR for

PEMFC operation
LH2/Hytron 5 kW prototype

5 kW ethanol ATR for

PEMFC operation
LH2/Hytron 5 kW prototype

5 kW ethanol ATR for

PEMFC operation
Why ethanol reforming

Comparative costs of electricity production: gasoline, Diesel and ethanol (FC- 50%)

Electricity Cost (fuel only)

2,80
2,60
n

2,40
2,20
2,00
kWh Cost (R$)

1,80
1,60
1,40
15%
1,20
1,00
Gasoline 25%
0,80
0,60
0,40 Diesel
15%

0,20
25%
0,00
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Reformer performance (% )
Why ethanol reforming

H2 from ethanol in a
FC vehicle is more
effective than direct
ethanol in a ICE
vehicle
Why ethanol reforming

0,45

0,40
Custo do Hidrogênio

0,31

0,30
(US$ m )
-3

0,22
0,27

0,20 0,22
0,12 0,12

0,10 0,12

0,06 0,08

0,00
Reforma GN OPNC Eletrólise Eletrólise Eletrólise
Eólico (Não especificada) Fotovoltaico

PADRÓ, C. E. G. & PUTSCHE, V., Survey of the economics of hydrogen technologies, National Renewable Energy Laboratory – NREL,
Technical report. Sept. 1999. NREL/TP – 570-27079, pp. 53, 1999.
Why ethanol reforming

- Eletrólise c/ Energia
Solar Fotovoltaica +
Eletrólise c/ Energia
Eólica

IMPACTOS Eletrólise c/ Energia CUSTO DO

AMBIENTAIS Hidroelétrica HIDROGÊNIO

Reforma-Vapor
de Etanol

Gaseificação
de Biomassa
+ Reforma de GN -
 THANK YOU!
QUESTIONS?

www.ifi.unicamp.br/lh2
www.ifi.unicamp.br/ceneh lh2@ifi.unicamp.br
ceneh@ifi.unicamp.br
Ethanol Reforming Process

 More importants process reactions:

General reaction:

C2H5OH + 3H2O  6H2 + 2 CO2

Partial Reactions:

C2H5OH + H2O  4H2 + 2CO

and
CO + H2O  H2 + CO2

 Reaction conditions:
- Temperature: 500 - 700°C
- Pression: 1 a 5 atm (not important influence)
- Catalistics: Cu, Ni, Cr, Zr, Co