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Task 42 Annex 24 Compact Thermal Energy Storage: Material Development for System Integration I 2012Report SecondProgress-Report Semi-annual Status Objectives • Identify, design and develop new materials and composites • Develop measuring and testing procedures • Improve performance, stability, and costeffectiveness • Develop multi-scale numerical models • Develop and demonstrate novel storage systems • Assess the impact of new materials on systems performance • Disseminate the acquired knowledge and experience • Create an active and effective research network Scope Classes of materials: • phase change materials • sorption and thermochemical materials From small to large-scale: • molecular/particle material synthesis, micro-scale mass transport, sorption reactions, … • bulk heat/mass transport, wall-material interactions, reactor design, … • system economical feasibility studies, case studies, system tests, … Organisational Structure Application Related Activities Test and Characterisation High Temp. Applications Heating / DHW Cooling Material Related Activities Material Engineering / Processing Numerical Modelling Apparatus / Components Theoretical Limits Organisational Structure Materials: Material Engineering / Processing Test and Characterization Numerical Modelling Apparatus and Components Applications: Cooling (0 °C – 20 °C) Heating / DHW (20 °C – 100°C) High Temp.Appl. (> 100 °C) Cross Cutting: Theoretical Limits WG Leader Elena Palomo (Univ.Bordeaux) Stefan Gschwander (ISE) Camilo Rindt (TUE) Wim van Helden (ECN) Motoi Yamaha (Chubu Univ.) Jane Davidson (Univ.Minnesota) Luisa Cabeza (Univ.Lleida) Eva Günther (ZAE) Meetings 1 2 3 4 5 6 7 8 Place Bad Tölz Lleida Bordeaux Graz Belfast Minneapolis Tokyo Petten Country Germany Spain France Austria United Kingdom United States Japan The Netherlands Date 11-13 February, 2009 21-23 September, 2009 7+8 July, 2010 26-28 September, 2010 20+21 February, 2011 20-22 September, 2011 27-29 March, 2012 18-19 October, 2012 # part. 69 71 51 56 36 30 28 WG C: Physical Limits the enthalpy of reactions increases with temperature of reaction equilibrium Chemical Reactions Is there a rule? 200 Chemical Reaction Evaporation Melting (Elements) Melting (Molecules) CaCO3 <-> CaO + CO2 s=~183 J/(mol K) 150 h / (kJ/mol) Ca(OH)2 <-> CaO + H2O 2NH3 <-> N2 + 3H2 100 Evaporation Troutons‘s Rule Na s=~87 J/(mol K) Hg C16H34 50 H 2O CaCl2*6H2O HCl 0 H2 0 Melting of Elements Richardson‘s Rule Ge Al Zn H 2O Mg 500 Ba 1000 T/K Ca s=~13 J/(mol K) 1500 WG C: Physical Limits / Reaction Enthalpy Reaction in Equilibrium: ∆G = 0 » » » ∆H = T * ∆S as shown in the graph before According to Sizmann ∆S should be a function of the difference of gaseous moles (n) of both sides of the reaction Since entropy is generated when condensed matter is converted to gas We studied some reactions and found: ∆S / (kJ/mol) = 0.876 * n + 0.631 WG C: Physical Limits / Reaction Enthalpy Difference in entopy of some reactions as a function of additional moles of gas released ∆S / (kJ/mol) = 0.876 * n + 0.631 WG C: Physical Limits / Reaction Enthalpy Enthalpy of reaction as a function of temperature and the difference of gaseous moles WG C: Physical Limits / Reaction Enthalpy List of reactions studied: 1 mole gas production: 1 CaO(s) + 1 H2O(g) ↔ 1 Ca(OH)2(s) 1 MgO(s) + 1 CO2(g) ↔ 1 MgCO3(s) 1 CaO(s) + 1 CO2(g) ↔ 1 CaCO3(s) 4 HCl(g) + 1 O2(g) ↔ 2 Cl2(g) + 2 H2O(g) 2 H2(g) + 1 CO2(g) ↔ 1 C(s) + 2 H2O(g) + 1 H2O(g) 2 moles gas production: 3 H2(g) + 1 N2(g) ↔ 2 NH3(g) 1 CO(g) + 3 H2(g) ↔ 1 CH4(g) 4 moles gas production 5 H2(g) + 4 C(s) ↔ 1 C4H10(g) 1 C6H6(g) + 3 H2(g) ↔ 1 C6H12(l) + 7 C(s) ↔ 1 C7H16(l) 8 moles gas production 8 H2(g) „New“ Annex / Extension Why should the work of Annex 24 be continued? • An international network of experts has been established (ECES/SHC, Material/System…) • „Unknown“ R&D demand could be identified e.g. test and chracterization, theoretical limits (economical limits?) • New promising classes of materials are currently under investigation, like solid-solid PCM or MOFs • The identification of material requirements for relevant applications, by means of numerical simulation of storage technologies, using the simulation modules developed e.g. in Phase I could now start. Economical Evaluation Applications and System Integration „New“ Annex / Extension Material Engineering and Processing Test and Characterization Numerical Modelling