Hydrogen storage, distribution and infrastructure

Transcription

1 Hydrogen storage, distribution and infrastructure Dr.-Ing. Roland Hamelmann D Bad Schwartau Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary

2 Hydrogen storage Storage principles Gas Fluid Physically bound Chemichally bound Example - CNG, Pressure vessels - Cryo tanks - Metal hydride storage, C-fibre - Sodiumborhydride, Ammonia Criteria Gravimetric density [kwh/kg] Volumetric density [kwh/m³] Safety Efficiency Application - Weight limited applications - Volume limited applications - Duty, accident - Energetic effort for in- and output - Mobile/stationary - continous / discontinous - heat coupling Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary

3 Stationary storages Identical with CNG-storage Large storages (> 10 6 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 % H 2 ) Small storages: sperical pressure vessels Low pressure sphere (1,4 MPa, Nm³, D=29m) Cylinder (D = 2,8 m, H = 7,3/10,8/19 m, 1305/2250/4500 Nm³ 4,5 MPa) Steel bottles (2-50 dm³): 8,3 Nm³ 20 MPa, 50 dm³; 11,8 Nm³ 30 MPa Saline caverns Source: KBB Underground

4 Saline cavern potential Source: KBB Underground Existing caverns Source: KBB Underground

5 Cavern spacing Source: KBB Underground Capacity Source: KBB Underground

6 Cavern building Source: KBB Underground Pressure vessels Source: Wasserstoff, Info-Blatt Messer Griesheim

7 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 (V 1 = 100 m³, p 1 = 250 bar, T 1 = 300 K) 1) Standard volume V 2 = V 1 * p 1 /p 2 * T 2 /T 1 * Z 2 /Z 1 = 100 m³ * 250 * 300/293 * 1/1,142 = m³ 2) Energy content E = H i * V = 3,0 kwh/m³ * m³ = kwh = 67, 2 MWh 3) Electrical equivalent E el = E * η 67,2 MWh * 40 % = 26,9 Mwh el 4) Storage density d s = 26,9 Mwh el / 100 m³ = 269 kwh el / m³ Mobile pressure vessels Similar to pressure tanks for CNG-mobility Composite tanks are % 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 Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)

8 Mobile storage density Stahl Komposit volume [dm³] pressure [bar] diameter [mm] length [mm] weight [kg] stored energy [MJ] stored energy [kwh] 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 Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003) Hydrogen compression Similarity to natural gas compression Specific compression work (isothermal) w t,isoth. = R H2 * T * Z * ln (p 2 /p 1 ) mit R H2 = 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 p 1 = start pressure p 2 = end pressure Compressor power P = w t,isoth. * m/t * 1/h with m/t = flux h = effective efficiency (hydraulical und mechanical losses) Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)

9 Ex. Hydrogen compression w t,isoth. for compression of 1 Nm³ H 2 at 20 C from a) 1 auf 200 bar: kj/kg 0,149 kwh 5,5 % b) 30 auf 200 bar: kj/kg 0,054 kwh 2,0 % 8,0% Eigenenergieverzehr H2-Kompression (h=85%) Eigenenergieverzehr 7,0% 6,0% 5,0% 4,0% 3,0% 2,0% 1,0% 0,0% Startdruck 1 bar Startdruck 30 bar Zieldruck [bar] Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary

10 Cryo storage Source: Bünger, Wasserstoffspeicherung Entwicklungsstand und perspektiven, Vortrag Haus der Technik, Essen (2001) Cryo storage: data similarities to liquid helium handling temperature at boiling point (20,4 K), pressure 1-10 bar double wall vessel with vacuum superinsulation ( 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, 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 Source:

11 Back-cooling Source: Wolf, Handbook of Fuel Cells Vol 3, S. 95 (2003) Application example

12 Hydrogen liquefaction 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 kwh el. / dm³ LH 2 (plus 45 dm³ water) Future prospects: 0,35 kwh el. / dm³ LH 2 with magnetocaloric process Liquefaction consumption / energy content (2,36 kwh th. / dm³ LH 2 ) Currently 38,1 % Future 14,8 % Source: Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary

13 Metal hydrides Base is reversible storage of hydrogen in metals: M + ½x H 2 MH x + heat Van t Hoffs equation: ln p = ΔH/RT ΔS/R (ΔH, ΔS < 0) hydrogen loading is exothermal hydrogen deloading is endothermal Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003) MH examples Source: Hubert, Otto, Energiewelt Wasserstoff, TÜV Süddeutschland S. 35 (2003)

14 MH: characteristics 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 ( /Nm³ H2) used metals: La, Ti, Zr, Mg, Ca, Fe, Ni, Mn, Co, Al Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003) MH vs. CH 2 CH 2 MH Dosing 0 0 Heat exchange + - Costs + - Compression - + Safety - + Weight + - Volume - + Cleaning Advantagel 0 Equal - Disadvantage Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003)

15 MH: research materials Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary

16 Sodium borhydride Reaction: NaBH H 2 O 4 H 2 + NaBO 2 Masses: 10,84 Gew.-% H 2, 51,2 Gew.-% NaBH 4 Reaction enthalpy: ΔH = -225 kj/mol ~ -56 kj/mol H 2 Hydrogen on Demand Pysiologic certain Source: Suda, Handbook of Fuel Cells Vol 3, S. 115 (2003) Ammonia Reaction: 2 NH 3 N H 2 Reaction enthalpy: ΔH = 46 kj/mol Common chemical, worldwide logistic chain With low pressure stored as liquid Compared to LH 2 contains ammonia the 1,7-fold amount of hydrogen (by volume) Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)

17 NH 3 -equilibrium Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003) NH 3 : catalytic splitting Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)

18 NH 3 : railway application Source: Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary

19 Hydrogen supply options Source: Wasserstoff, Info-Blatt Messer Griesheim Hydrogen pipelines Source: Wurster, LBST, Möglichkeiten der Wasserstoffbereitstellung, Hessischer Mobilitätstag (2003)

20 Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary 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:

21 Structure 1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound 2. Hydrogen distribution 3. Hydrogen infrastructure 4. Summary 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.