Thermodynamics of the Reciprocal NaCl-KCl-NaNO 3 -KNO 3 System. Project: Thermodynamics of Salt Systems for Thermal Energy Storage
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1 Thermodynamics of the Reciprocal NaCl-KCl-NaNO 3 -KNO 3 System Project: Thermodynamics of Salt Systems for Thermal Energy Storage Dmitry Sergeev, Elena Yazhenskikh, Nawfel Talukder, Dietmar Kobertz, Michael Müller 1
2 Russian Winter (-30 C) 2
3 Sensible Thermal Energy Storage SiO 2 +Al 2 O 3 3
4 Heat Increment 50KNO 3-50NaNO 3 50SiO 2-50Al 2 O 3 Latent Heat at the melting point 4
5 Solar Power Plant Thermal Energy Storage 5
6 Weight of TES 24 m 9 m m= kg 6
7 Cascaded Latent Heat Storage MgCl 2 /KCl/NaCl, m H = 400 kj/kg KOH, m H = 134 kj/kg KNO 3, m H = 95 kj/kg 380 C 360 C 335 C KNO 3 /KCl, m H = 74 kj/kg NaNO 3, m H = 172 kj/kg 320 C 306 C Dinter F., Geyer M., Tamme R., "Thermal Energy Storage for Commercial Applications" Berlin, Heidelberg, New York, usw.: Springer-Verlag;
8 0.1 Equivalent fraction Cl/(NO3+Cl) Phase Diagram of the Na NaCl-KCl-NaNO - K - NO 3-3 -KNO 3 system (Na[+] + K[+]) = (NO3[-] + Cl[-]), 1 atm NaCl (801 o ) 0.1 KCl (771 o ) 657 C scanned data [1] NaCl-KCl solid solution 285 C 275 C 1 K 2 ClNO 3 (s) 0.1 (Na,K)NO3-HT solid solution NaNO KNO 3 (306 o ) Equivalent fraction K/(Na+K) (334 o ) R.N. Nyankovskaya, Izv. Sekt. Fiz.-Khim. Anal., 21 (1952)
9 0.1 Equivalent fraction Cl/(NO3+Cl) Phase Diagram of the Na NaCl-KCl-NaNO - K - NO 3-3 -KNO 3 system (Na[+] + K[+]) = (NO3[-] + Cl[-]), 1 atm NaCl (801 o ) 0.1 KCl (771 o ) 657 C scanned data [1] NaCl-KCl solid solution 285 C 275 C 1 K 2 ClNO 3 (s) 0.1 (Na,K)NO3-HT solid solution NaNO KNO 3 (306 o ) Equivalent fraction K/(Na+K) (334 o ) R.N. Nyankovskaya, Izv. Sekt. Fiz.-Khim. Anal., 21 (1952)
10 Phase Diagrams of the NaCl-KCl System 50:50 10
11 Differential Scanning Calorimetry DSC 404C Netzsch Sample holder 11
12 Heat capacity of the 50NaCl-50KCl 484 C 484 C 340 C What does the initial temperature 340 C mean? 12
13 Heat capacity of the NaCl-KCl system 13
14 Phase Diagramm 340 C? 14
15 Drop Calorimeter mhtc 96 Seteram 15
16 Sample (10-100mg) at room temperature Drop Calorimetry Heat Flow (μv) at a constant T Experimental data Hot zone, constant temperature T 16
17 Enthalpy increment in the 50NaCl 50KCl mixture Latent Heat at the melting point 2 kj/mol 17
18 Heat capacity of the 50NaCl-50KCl 484 C T H T H = C p T dt 18
19 Enthalpy increment in the 50NaCl 50KCl mixture 390 C 19
20 Enthalpy increment in the 50NaCl 50KCl mixture Literature data obtained by solution calorimetry of quenched solid solutions at room temperature 2.7 kj/mol ss H, kj/mol Barret (1954) 4.4 Bunk (1953) 4.5 Popov (1940) 4.4 Zemczuzny (1910) C ss H=4.2 kj/mol 20
21 Heat capacity of the 50NaCl-50KCl 315 C 484 C What does the initial temperature (340 C) mean? 21
22 Enthalpy increment in the 50NaCl 50KCl mixture 390 C 22
23 0.1 Equivalent fraction Cl/(NO3+Cl) Reciprocal NaCl-KCl-NaNO - K - NO 3 - Cl 3 -KNO 3 system (Na[+] + K[+]) = (NO3[-] + Cl[-]), 1 atm NaCl (801 o ) 0.1 KCl (771 o ) 657 C scanned data [1] NaCl-KCl solid solution 285 C 275 C 1 K 2 ClNO 3 (s) 0.1 (Na,K)NO3-HT solid solution NaNO KNO 3 (306 o ) Equivalent fraction K/(Na+K) (334 o ) R.N. Nyankovskaya, Izv. Sekt. Fiz.-Khim. Anal., 21 (1952)
24 T(C) T(C) T(C) T(C) Modelling results of the binary salt systems 1000 NaCl - KCl 1 atm FactSage Calculated, Table 2, Pelton [1985] measured, Vesnin [1979] 900 Measured, Table 1, Pelton [1985] measured, D.Sergeev [2014] liq_salt NaCl-KCl NaCl-KCl NaCl-KCl + NaCl-KCl#2 NaNO 3 - NaCl 1 atm exp.data, Ko[1963] data, Ko[1963] as Ref. in Sangster [1987] data, Perman[1922] as Ref. in Sangster [1987] data, Luzhnaja [1935] as Ref. in Sangster [1987] liq_salt + ClNa(s) ClNa(s) + NNaO 3(s2) ClNa(s) + NNaO 3(s) FactSage NaCl/(NaCl+KCl) (mol/mol) NaCl 1000 exp. data, Ko [1963] liq_salt NaNO 3 /(NaNO 3 +NaCl) (mol/mol) NaNO 3 Solidus, DSC, Kramer [1980] Liquidus, DSC, Kramer [1980] Liquidus, cooling, DSC, Greis [1985] Solidus, cooling, DSC, Greis [1985] Solidus, heating, DSC, Greis [1985] C NaNO 3 - KNO 3 1 atm KCl KNO 3 Solidus, DSC, Zhang [2003] Liquidus, DSC, Zhang [2003] lambda, heating, DSC, Greis [1985] lambda, cooling, DSC, Greis [1985] NaNO3 transition, DSC, Klement [1974] FactSage scanned PED-data, Bergman [1947] liq_salt liq_salt + ClK(s) ClK(s) + K 2ClO 3N(s) ClK(s) + KNO 3(s2) ClK(s) + KNO 3(s) KNO 3 - KCl 1 atm exp.point, cryst/melt, Kefer [1969] exp.point, eutectic, Kefer [1969] exp.point inc decomposition, Kefer [1969] exp.point, transformation KNO3, Kefer [1969] exp.point, solid phase process, Kefer [1969] liq_salt + K 2ClO 3N(s) K 2ClO 3N(s) + KNO 3(s2) FactSage KNO 3 /(KNO 3 +KCl) (mol/mol) liq_salt + NaNO3-KNO3-HT NaNO3-KNO3-HT liq_salt liq_salt + NaNO3-KNO3-HT 150 NaNO3-KNO3-HT + NNaO 3(s) 100 KNO3-LT-solution 50 KNO3-LT-solution + NNaO 3(s) NaNO 3 /(NaNO 3 +KNO 3 ) (mol/mol)
25 0.1 Equivalent fraction Cl/(NO3+Cl) Univariant line of the NaCl-KCl-NaNO - K - NO 3-3 -KNO 3 system (Na[+] + K[+]) = (NO3[-] + Cl[-]), 1 atm NaCl (801 o ) 0.1 KCl (771 o ) 657 C scanned data [1] NaCl-KCl solid solution 1 K 2 ClNO 3 (s) 0.1 (Na,K)NO3-HT solid solution NaNO KNO 3 (306 o ) Equivalent fraction K/(Na+K) (334 o ) [1] R.N. Nyankovskaya, Izv. Sekt. Fiz.-Khim. Anal., 21 (1952)
![T(C) T(C) 1000 KNO 3 - NaCl 1 atm Diagonal Systems 900 800 scanned points, Nyankovskaya [1952] other points: D. Sergeev [Sept.](/docs-images/76/73390956/images/26-0.jpg "2014] 700 600 liq_salt 500 liq_salt + NaCl-KCl 400 300 200 NaCl-KCl + NaNO3-KNO3-HT liq_salt + NaCl-KCl + NaCl-KCl#2 NaCl-KCl + NaCl-KCl#2 + NaNO3-KNO3-HT liq_salt + NaCl-KCl liq_salt + NaNO3-KNO3-HT")
26 T(C) T(C) 1000 KNO 3 - NaCl 1 atm Diagonal Systems scanned points, Nyankovskaya [1952] other points: D. Sergeev [Sept. 2014] liq_salt 500 liq_salt + NaCl-KCl NaCl-KCl + NaNO3-KNO3-HT liq_salt + NaCl-KCl + NaCl-KCl#2 NaCl-KCl + NaCl-KCl#2 + NaNO3-KNO3-HT liq_salt + NaCl-KCl liq_salt + NaNO3-KNO3-HT liq_salt + NaCl-KCl + NaNO3-KNO3-HT NaCl-KCl + NaNO3-KNO3-HT 100 NaCl-KCl + NaCl-KCl#2 + KNO3-LT-solution NaCl-KCl + KNO3-LT-solution KNO 3 /(KNO 3 +NaCl) (mol/mol) liq_salt NaNO 3 - KCl 1 atm scanned points from Nyankovskaya [1952] other points: D. Sergeev [Sept 2014] 500 liq_salt + NaCl-KCl 400 NaCl-KCl + NaNO3-KNO3-HT + NNaO 3 (s liq_salt + NaCl-KCl liq_salt + NaCl-KCl + NaCl-KCl#2 NaCl-KCl + NaCl-KCl#2 + NaNO3-KNO3-HT 100 ClK(s) + NNaO 3 (s) 0 ClK(s) + NNaO 3 (s) 0 1 NaCl-KCl + NaNO3-KNO3-HT NaNO 3 /(NaNO 3 +KCl) (mol/mol) liq_salt + NaCl-KCl + NaNO3-KNO3-HT 26
![Liquidus, DSC, Kramer [1980] Liquidus, cooling, DSC, Greis [1985] Solidus, cooling, DSC, Greis [1985] Solidus, heating, DSC, Greis [1985] scanned points from Nyankovskaya [1952] other points: D.](/docs-images/76/73390956/images/27-1.jpg "Sergeev [Sept 2014] liq_salt + NaCl-KCl NaCl-KCl + NaNO3-KNO3-HT NaNO 3 /(NaNO 3 +KCl) (mol/mol) NaNO 3 - KNO 3 1 atm Solidus, DSC, Zhang [2003] Liquidus, DSC, Zhang [2003] lambda, heating, DSC,")
27 T(C) Diagonal System T(C) liq_salt KCl + NaNO NaNO 3 /(NaNO +KNO 3 ) (mol/mol) liq_salt + NaCl-KCl 3 = KNO 3 + NaCl liq_salt + NaCl-KCl + NaCl-KCl#2 NaCl-KCl + NaCl-KCl#2 + NaNO3-KNO3-HT ClK(s) + NNaO 3 (s) 500 NaNO 3 - KCl atm 100 KNO3-LT-solution 50 liq_salt + NaNO3-KNO3-HT NaNO3-KNO3-HT Solidus, DSC, Kramer [1980] Liquidus, DSC, Kramer [1980] Liquidus, cooling, DSC, Greis [1985] Solidus, cooling, DSC, Greis [1985] Solidus, heating, DSC, Greis [1985] scanned points from Nyankovskaya [1952] other points: D. Sergeev [Sept 2014] liq_salt + NaCl-KCl NaCl-KCl + NaNO3-KNO3-HT NaNO 3 /(NaNO 3 +KCl) (mol/mol) NaNO 3 - KNO 3 1 atm Solidus, DSC, Zhang [2003] Liquidus, DSC, Zhang [2003] lambda, heating, DSC, Greis [1985] lambda, cooling, DSC, Greis [1985] liq_salt + NaCl-KCl + NaNO3-KNO3-HT NaCl-KCl + NaNO3-KNO3-HT + NNaO 3 (s) ClK(s) + NNaO 3 (s) 0 1 liq_salt KNO3-LT-solution + NNaO 3 (s) NaNO3 transition, DSC, Klement [1974] liq_salt + NaNO3-KNO3-HT FactSage NaNO3-KNO3-HT + NNaO 3 (s) NaNO 3 KNO 3 27
28 0.1 Equivalent fraction Cl/(NO3+Cl) Reciprocal NaCl-KCl-NaNO - K - NO 3 - Cl 3 -KNO 3 system (Na[+] + K[+]) = (NO3[-] + Cl[-]), 1 atm NaCl (801 o ) 0.1 KCl (771 o ) 657 C scanned data [1] NaCl-KCl solid solution 287 C 277 C 1 K 2 ClNO 3 (s) 0.1 (Na,K)NO3-HT solid solution NaNO KNO 3 (306 o ) Equivalent fraction K/(Na+K) (334 o )
29 0.1 Equivalent fraction Cl/(NO3+Cl) Reciprocal NaCl-KCl-NaNO - K - NO 3 - Cl 3 -KNO 3 system (Na[+] + K[+]) = (NO3[-] + Cl[-]), 1 atm NaCl (801 o ) 0.1 KCl (771 o ) 657 C scanned data [1] 7.5KCl-92.5NaNO 3 NaCl-KCl solid solution 287 C 277 C 1 K 2 ClNO 3 (s) 0.1 (Na,K)NO3-HT solid solution NaNO KNO 3 (306 o ) Equivalent fraction K/(Na+K) 12.5NaCl-87.5KNO 3 (334 o )
30 Heat Increment T = 30 C H = 18 kj/mol 30
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