CaBr{sub 2} hydrolysis for HBr production using a direct sparging contactor.
The calcium-bromine cycle being investigated is a novel continuous hybrid cycle for hydrogen production employing both heat and electricity. Calcium bromide (CaBr{sub 2}) hydrolysis generates hydrogen bromide (HBr) which is electrolyzed to produce hydrogen. The CaBr{sub 2} hydrolysis at 1050 K (777 C) is endothermic with the heat of reaction {delta}G{sub T} = 181.5 KJ/mol (43.38 kcal/mol) and the Gibbs free energy change is positive at 99.6 kJ/mol (23.81 kcal/mol). What makes this hydrolysis reaction attractive is both its rate and that well over half the thermodynamic requirements for water-splitting heat of reaction of {delta}G{sub T} = 285.8 KJ/mol (68.32 kcal/mol) are supplied at this stage using heat rather than electricity. Molten-phase calcium bromide reactors may overcome the technical barriers associated with earlier hydrolysis approaches using supported solid-phase calcium bromide studied in the Japanese UT-3 cycle. Before constructing the experiment two design concepts were evaluated using COMSOL{trademark} multi-physics models; (1) the first involved sparging steam into a calcium-bromide melt, while (2) the second considered a 'spray-dryer' contactor spraying molten calcium bromide counter-currently to upward-flowing steam. A recent paper describes this work. These studies indicated that sparging steam into a calcium-bromide melt is more feasible than spraying molten calcium bromide droplets into steam. Hence, an experimental sparging hydrolysis reactor using a mullite tube (ID 70 mm) was constructed capable of holding 0.3-0.5 kg (1.5-2.5 x 10{sup -3} kg mol) CaBr{sub 2} forming a melt with a maximum 0.08 m (8 cm) depth. Sparging steam at a steam rate of 0.02 mol/mol of CaBr{sub 2} per minute (1.2-2.3 x 10{sup -5} kg/s), into this molten bath promptly yielded HBr in a stable operation that converted up to 25% of the calcium bromide. The kinetic constant derived from the experimental data was 2.17 x 10{sup -12} kmol s{sup -1} m{sup -2} MPa{sup -1} for the hydrolysis reaction. The conversion rate is highly dependent on melt depth and the design for steam sparging. This experimental data provides a basis for designing a larger-scale sparging hydrolysis reactor for the calcium bromide thermochemical cycle where the endothermic heat of reaction can be effectively supplied by heat transfer coils embedded in the melt.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- NE
- DOE Contract Number:
- DE-AC02-06CH11357
- OSTI ID:
- 967948
- Report Number(s):
- ANL/ES/JA-64754; IJHEDX; TRN: US200924%%150
- Journal Information:
- Int. J. Hydrogen Energy, Vol. 34, Issue 18 ; Sep. 2009; ISSN 0360-3199
- Country of Publication:
- United States
- Language:
- ENGLISH
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