hydrogen storage, distribution and infrastructure - … 1 hydrogen storage, distribution and...
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Hydrogen storage, distribution and
infrastructure
Dr.-Ing. Roland Hamelmann
D-23611 Bad Schwartau
1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
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Hydrogen storage
Storage principles Example
Gas - CNG, Pressure vessels
Fluid - Cryo tanks
Physically bound - Metal hydride storage, C-fibre
Chemichally bound - Sodiumborhydride, Ammonia
Criteria
Gravimetric density [kWh/kg] - Weight limited applications
Volumetric density [kWh/m³] - Volume limited applications
Safety - Duty, accident
Efficiency - Energetic effort for in- and output
Application - Mobile/stationary
- continous / discontinous
- heat coupling
1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
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Identical with CNG-storage
Large storages (> 106 Nm³ ): Aquifere, Kavernen
• England: saline caverns for hydrogen storage (ICI) with 50 bar
• France (57-74): Aquifer-storage for für 330 Mio Nm³ town gas (50 % H2)
Small storages: sperical pressure vessels
• Low pressure sphere (1,4 MPa, 15.000 Nm³, D=29m)
• Cylinder (D = 2,8 m, H = 7,3/10,8/19 m, 1305/2250/4500 Nm³ volume @ 4,5 MPa)
• Steel bottles (2-50 dm³): 8,3 Nm³ volume @ 20 MPa, 50 dm³;
11,8 Nm³ volume @ 30 MPa
Stationary storages
Saline caverns
Source: KBB Underground
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Saline cavern potential
Source: KBB Underground
Existing caverns
Source: KBB Underground
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Cavern spacing
Source: KBB Underground
Capacity
Source: KBB Underground
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Cavern building
Source: KBB Underground
Source: Wasserstoff, Info-Blatt Messer Griesheim
Pressure vessels
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Hydrogen storage density
Ideal gas: p*V = m*R*T
Real gas: p*V = Z*m*R*T
p: pressure
V: volume
m: mass
R: gas constant
T: temperature
Z: compressibility factor
Example: energy content of a gasholder (V1 = 100 m³, p1 = 250 bar, T1 = 300 K)
1) Standard volume V2 = V1 * p1/p2 * T2/T1 * Z2/Z1
= 100 m³ * 250 * 300/293 * 1/1,142 = 22.414 m³
2) Energy content E = Hi * V
= 3,0 kWh/m³ * 22.414 m³ = 67.243 kWh = 67, 2 MWh
3) Electrical equivalent Eel = E * η ≈ 67,2 MWh * 40 % = 26,9 Mwhel
4) Storage density ds = 26,9 Mwhel / 100 m³ = 269 kWhel / m³
Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)
Similar to pressure tanks for CNG-mobility
Composite tanks are 50-75 % easier than steel
(carbon-fibre reinforced aluminium or plastic liner)
Advantages of liner material
aluminium plastic
Manufacturing ++ +
Permeability ++ +
Cyclebility + ++
Cost for liner ++ ++
Cost for fibres + ++
Cost total + ++
Total weight + ++
Safety ++ ++
Mobile pressure vessels
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Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)
Stahl Komposit
volume [dm³] 50 50 50 50
pressure [bar] 200 200 400 700
diameter [mm] 220 300 300 300
length [mm] 1.600 1.000 1.000 1.000
weight [kg] 70 25 45 85
stored energy [MJ] 87 87 156 238
stored energy [kWh] 24 24 43 66
stored hydrogen [kg] 0,70 0,70 1,30 2,00
grav. storage density [kWh/kg] 0,35 0,96 0,96 0,78
vol. storage density [kWh/dm³] 0,48 0,48 0,86 1,32
Mobile storage density
Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)
Similarity to natural gas compression
Specific compression work (isothermal)
wt,isoth. = RH2 * T * Z * ln (p2/p1) mit
RH2 = 4,124 kJ/(kg * K) = spec. Gas constant
T = temperature [K]
Z = (K(p1)+K(p2))/2K(p2) = compressibility factor K(p) = 1+p/150 MPa
p1 = start pressure
p2 = end pressure
Compressor power
P = wt,isoth. * m/t * 1/h with
m/t = flux
h = effective efficiency (hydraulical und mechanical losses)
Hydrogen compression
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Ex. Hydrogen compression
wt,isoth. for compression of 1 Nm³ H2 at 20°C from
a) 1 auf 200 bar: 6.030 kJ/kg ≙ 0,149 kWh ≙ 5,5 %
b) 30 auf 200 bar: 2.179 kJ/kg ≙ 0,054 kWh ≙ 2,0 %
Eigenenergieverzehr H2-Kompression (h=85%)
0,0%
1,0%
2,0%
3,0%
4,0%
5,0%
6,0%
7,0%
8,0%
0 100 200 300 400 500 600 700 800
Zieldruck [bar]
Eig
en
en
erg
ieve
rze
hr
Startdruck 1 bar
Startdruck 30 bar
1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
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Source: Bünger, Wasserstoffspeicherung – Entwicklungsstand und –perspektiven, Vortrag Haus der Technik, Essen (2001)
Cryo storage
Source: www.hyweb.de
similarities to liquid helium handling
temperature at boiling point (20,4 K), pressure 1-10 bar
double wall vessel with
vacuum superinsulation (70-100 layers, 25 mm) or
perlite-vacuuminsulation
boil-off-rate:
vacuum-superinsulation appr. 0,4 %/d
vacuum-powderinsulation 1-2 %/d
Tank size:
Large: NASA, Cape Canaveral, sphere with 20 m diameter, 3.800
m³ storage volume (270 t LH2), boil-off 0,03 %/d
car: volume 120 dm³, passive safety by double wall hull, 100 kg
total weight; heat input 2W, standby-time 4 days, boil-off-rate 1%/d
Cryo storage: data
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Source: Wolf, Handbook of Fuel Cells Vol 3, S. 95 (2003)
Back-cooling
Application example
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Source: www.hyweb.de
Cryogenic process
Worldwide roughly 10 plants in operation (10 … 60 t/d each)
Small liquefiers for research purposes with 200 kg/d
Current effort: 0,9 kWhel. / dm³ LH2 (plus 45 dm³ water)
Future prospects: 0,35 kWhel. / dm³ LH2 with magnetocaloric
process
Liquefaction consumption / energy content (2,36 kWhth. / dm³ LH2)
Currently 38,1 %
Future 14,8 %
Hydrogen liquefaction
1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
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Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003)
Metal hydrides
Base is reversible storage of hydrogen
in metals:
M + ½x H2 ↔ MHx + heat
Van´t Hoffs equation:
ln p = ΔH/RT – ΔS/R (ΔH, ΔS < 0)
hydrogen loading is exothermal
hydrogen deloading is endothermal
Source: Hubert, Otto, Energiewelt Wasserstoff, TÜV Süddeutschland S. 35 (2003)
MH examples
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Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003)
Activation / hydrogen loading:
internal cracking
increasing specific surface
removing of passivation layers
Gas impurities:
lead to a loss of capacity
degrade kinetics
poison surface
Cycle-stability is influenced by metallugic processes (disintegration)
Safety aspects: toxic, combustible
Costs: metallurgical complex process, high precision needed
(200 – 700 €/Nm³ H2)
used metals: La, Ti, Zr, Mg, Ca, Fe, Ni, Mn, Co, Al
MH: characteristics
Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003)
CH2 MH
Dosing 0 0
Heat exchange + -
Costs + -
Compression - +
Safety - +
Weight + -
Volume - +
Cleaning - +
+ Advantagel 0 Equal - Disadvantage
MH vs. CH2
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MH: research materials
1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
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Source: Suda, Handbook of Fuel Cells Vol 3, S. 115 (2003)
Reaction: NaBH4 + 2 H2O → 4 H2 + NaBO2
Masses: 10,84 Gew.-% H2, 51,2 Gew.-% NaBH4
Reaction enthalpy: ΔH = -225 kJ/mol ~ -56 kJ/mol H2
„Hydrogen on Demand“
Pysiologic certain
Sodium borhydride
Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)
Reaction: 2 NH3 ↔ N2 + 3 H2
Reaction enthalpy: ΔH = 46 kJ/mol
Common chemical, worldwide logistic chain
With low pressure stored as liquid
Compared to LH2 contains ammonia the 1,7-fold amount
of hydrogen (by volume)
Ammonia
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Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)
NH3-equilibrium
Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)
NH3: catalytic splitting
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Source: www.fuelcelltoday.de
NH3: railway application
1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
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Source: Wasserstoff, Info-Blatt Messer Griesheim
Hydrogen supply options
Source: Wurster, LBST, Möglichkeiten der Wasserstoffbereitstellung, Hessischer Mobilitätstag (2003)
Hydrogen pipelines
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1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
General aspects
The installation of a hydrogen infrastructure for energetic purposes is
technical feasible
demand-oriented („chicken-egg-problem“)
expensive, but competitive to existing energy systems
an economical and ecological „must do“ for the next decades
Hardware is proved in R&D-projects, and the design and erection phase is
object of studies.
More details:
http://www.h2hamburg.de/downloads/MBA_HH%20H2.pdf
http://www.iea.org/work/2007/hydrogen_economy/modelling_seydel.pdf
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1. Hydrogen storage
a) gaseous
b) liquid
c) physically bound
d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Summary
The installation of a hydrogen infrastructure for energetic
purposes is oriented on solutions for the chemical industry.
They offer tailored storage and distribution hardware for
each demand.
The installation of a hydrogen infrastructure for energetic
purposes seems to be expensive, but their cost is within the
range of existing energy solutions.
The installation of a hydrogen infrastructure for energetic
purposes will develop within the next decades from local to
regional networks.