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Frontiers of Chemical Science and Engineering

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ISSN 2095-0187(Online)

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Front. Chem. Sci. Eng.    2018, Vol. 12 Issue (3) : 564-576    https://doi.org/10.1007/s11705-018-1720-0
REVIEW ARTICLE
Corrosion behavior of metallic alloys in molten chloride salts for thermal energy storage in concentrated solar power plants: A review
Wenjin Ding1(), Alexander Bonk1, Thomas Bauer2
1. Institute of Engineering Thermodynamics, German Aerospace Center (DLR), 70569 Stuttgart, Germany
2. Institute of Engineering Thermodynamics, German Aerospace Center (DLR), 51147 Cologne, Germany
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Abstract

Recently, more and more attention is paid on applications of molten chlorides in concentrated solar power (CSP) plants as high-temperature thermal energy storage (TES) and heat transfer fluid (HTF) materials due to their high thermal stability limits and low prices, compared to the commercial TES/HTF materials in CSP-nitrate salt mixtures. A higher TES/HTF operating temperature leads to higher efficiency of thermal to electrical energy conversion of the power block in CSP, however causes additional challenges, particularly increased corrosiveness of metallic alloys used as containers and structural materials. Thus, it is essential to study corrosion behaviors and mechanisms of metallic alloys in molten chlorides at operating temperatures (500–800 °C) for realizing the commercial application of molten chlorides in CSP. The results of studies on hot corrosion of metallic alloys in molten chlorides are reviewed to understand their corrosion behaviors and mechanisms under various conditions (e.g., temperature, atmosphere). Emphasis has also been given on salt purification to reduce corrosive impurities in molten chlorides and development of electrochemical techniques to in-situ monitor corrosive impurities in molten chlorides, in order to efficiently control corrosion rates of metallic alloys in molten chlorides to meet the requirements of industrial applications.
Keywords corrosion mechanisms      impurities      metallic corrosion      salt purification      electrochemical techniques     
Corresponding Author(s): Wenjin Ding   
Just Accepted Date: 05 March 2018   Online First Date: 07 June 2018    Issue Date: 18 September 2018
 Cite this article:   
Wenjin Ding,Alexander Bonk,Thomas Bauer. Corrosion behavior of metallic alloys in molten chloride salts for thermal energy storage in concentrated solar power plants: A review[J]. Front. Chem. Sci. Eng., 2018, 12(3): 564-576.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1720-0
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I3/564
Fig.1  Concentrated solar power plants with molten salts as TES and HTF materials (source: US Department of Energy)
Fig.2  110-MWe Crescent Dunes tower CSP plant in Tonopah, Nevada, USA, with 10 h of thermal storage in ~32000 tons solar salt (source: SolarReserve)
Fig.3  A molten salt storage tank (container) for the Crescent Dunes solar power plant. Size of tank: 12.2 m tall and 42.7 m in diameter; storage capacity: 32000 tons molten salt (source: SolarReserve)
Molten salts composition/wt-% Melting point /°C Stability limit /°C Density /(g?cm−3) Heat capacity /(kJ?kg−1?K−1) Material cost /(US $?kg−1)
Solar salt
KNO3/nANO3
(40/60)		 240 [8] 530–565 [8] ~1.8 [8] (400 °C) ~1.5 [8] (400 °C) 0.8 [4], 0.5 [7]
Hitec
KNO3/NaNO3/NaNO2 (53/7/40)		 142 [8] 450–540 [8] ~1.8 [8] (400 °C) 1.5 [8] (400 °C) 0.9 [7]
LiNaK carbonates
K2CO3/ Li2CO3/Na2CO3
(32/35/33)		 397 [8] >650 [8] 2.0 [8] (700 °C) 1.9 [8] (700 °C) 2.5 [4], ~1.3 [7]
LiNaK fluorides
KF/LiF/NaF
(59/29/12)		 454 [8] >700 [8] 2.0 [8] (700 °C) 1.9 [8] (700 °C) >2*
ZnNaK chlorides
KCl/NaCl/ZnCl2
(23.9/7.5/68.6)		 204 [7] 850 [7] ~2.0 [9] (600 °C) 0.8 [7] (300–600 °C) 0.8 [4],<1 [7]
MgNaK chlorides
KCl/MgCl2/NaCl
(17.8/68.2/14.0)		 380 [10] >800 [4] ~1.7 [9] (600 °C) ~1.0 [9] (500–800 °C) <0.35 [4]
Tab.1  Properties and prices of commonly used molten salts as TES/HTF in CSP
Fig.4  High temperature molten salt loop schematic with potential surface and fluid temperatures [4]. Adapted from Concentrating Solar Power Gen3 Demonstration Roadmap of NREL, USA
Gases O2 H2O HCl Cl2 CO2 H2
Henry’s law constant /(1012 mol·cm−3·Pa−1) ~10−3
(chlorides) [12]		 0.95 (NaCl, 900 °C) [16]
1.1 (KCl, 900 °C) [16]		 0.13 (NaCl, 907 °C) [16]
0.25 (KCl, 907 °C) [16]
8.4 × 10−2(MgCl2, 904 °C) [16]
0.2(MgCl2/KCl, 50/50 mol-%, 875 °C) [16]		 5.4 × 10−2 (NaCl, 900 °C) [16]
0.19(KCl, 900 °C) [16]
7.3 × 10−2(MgCl2, 925 °C) [16]
3.4 × 10−2(MgCl2/NaCl/KCl, 50/27.7/23.3 wt-%, 903 °C) [16]		 6.19 × 10−2 (NaCl, 904 °C) [16]
7.9 × 10−2(KCl, 903 °C) [16]
0.36(MgCl2, 850 °C) [16]		 4.3 × 10−3 (LiF-BeF2, 66–34 mol-%, 600 °C) [16]
Interaction Yes [12,17]Chlorination4Cl−(l) + O2(l,g) → 2Cl2(l,g) + 2O2–(l) Yes [11,18]HydrolysisH2O(l,g) + Cl−(l) → HCl(l,g) + OH−(l) – – – –
Tab.2  Gas solubilities in molten halides and gas interaction with pure molten chlorides.
Fig.5  Vapor pressure of H2O and HCl over the hydrates of MgCl2 [19]
Fig.6  Cyclic voltammogram in MgCl2/KCl/NaCl at 500 °C obtained by a tungsten working electrode. Sweep rate: 200 mV·s−1. Tungsten reference electrode. ip(B): peak current density for reaction B. Adopted from [24]
Fig.7  Peak current densities vs. concentrations of corrosive MgOH+ in molten MgCl2/KCl/NaCl (60/20/20 mol-%) at (a) 500, 600 °C and (b) 700 °C. Error bars represent the standard deviations in the CV (three measurements) and AC measurements (three measurements). Adopted from [24]
Molten salts /wt-% Alloy /Ni wt-% T /°C Atmosphere Method Corrosion rate /(µm?year−1) Ref.
KCl/NaCl/ZnCl2 (24.0/7.4/68.6) Ha N (~71) 250 Air PDP 37 [30]
500 Air PDP 160 [30]
Ha C-22 (~56) 250 Air PDP 16 [30]
500 Air PDP 50 [30]
Ha C-276 (~57) 250 Air PDP 11 [30]
500 Air PDP 42 [30]
SS 304 (8–11) 250 Air PDP 22 [31]
500 Air PDP 381 [31]
400 Absence of air I+M (1000 h) 14 [31]
Ha C-22 (~56) 250 Air PDP 15 [31]
500 Air PDP 42 [31]
400 Absence of air I+M (1000 h) 8 [31]
800 Absence of air I+M (1000 h) 14 [31]
Ha C-276 (~57) 500 Air PDP 40 [31]
800 Air PDP 500 [31]
400 Absence of air I+M (1000 h) 3 [31]
800 Absence of air I+M (1000 h) 4 [31]
500 Air I+M (1000 h) 80 [31]
CaCl2/MgCl2/NaCl
(43.6/17.7/38.7)		 Inc 625 (~62) 600 Air I+M (504 h) 121 [29]
Ha X (~47) 600 Air I+M (504 h) 153 [29]
Ha B-3 (~65) 600 Air I+M (504 h) 144 [29]
KCl/MgCl2/NaCl
(20.4/55.1/24.5)		 SS 304 (8–11) 450–500 Vacuum I+M (1000 h) <10 [14]
SS 316 (10–14) 450–500 Vacuum I+M (1000 h) ~10 [14]
SS 347 (9–12) 450–500 Vacuum I+M (1000 h) ~120 [14]
Ha N (~71) 450–500 Vacuum I+M (1000 h) ~50 [14]
SS 304 (8–11) 900 N2-(0.1–1%H2O)-(1–10%O2) I+M (144 h) Disintegrated [14]
SS 316 (10–14) 900 N2-(0.1–1%H2O)-(1–10%O2) I+M (144 h) Disintegrated [14]
In 800H (30–35) 900 N2-(0.1–1%H2O)-(1–10%O2) I+M (144 h) 23725 [14]
Ha 230 (~57) 900 N2-(0.1–1%H2O)-(1–10%O2) I+M (144 h) 20345 [14]
KCl/NaCl/VCl2
(53.3/41.7/5.0)		 SS 316L (13.5–15.0) 750 Argon I+M (6 h) 54000 [34]
750 Argon PDP (6 h) 1600 [34]
SS 316Ti (12–14) 750 Argon I+M (6 h) 61000 [34]
750 Argon PDP (6 h) 7000 [34]
SS 321 (9–11) 750 Argon I+M (6 h) 22200 [34]
750 Argon PDP (6 h) 15100 [34]
KCl/NaCl
(56.1/43.9)		 SS 316L (13.5–15.0) 750 Argon I+M (80 h) ~157 [35]
SS 316Ti (12–14) 750 Argon I+M (80 h) ~168 [35]
SS 321 (9–11) 750 Argon I+M (80 h) ~225 [35]
KCl/LiCl
(55.8/44.2)		 SS 304 (8–11) 400 Absence of air I+M (–) 2 [14]
500 Absence of air I+M (–) 6 [14]
SS 316 (10–14) 400 Absence of air I+M (–) 2 [14]
SS 347 (9–12) 500 Absence of air I+M (–) 2 [14]
LiCl/NaCl
(68.6/34.4)		 SS 347 (9–12) 650 Nitrogen PDP 7490 [32]
SS 310 (~20.5) 650 Nitrogen PDP 6420 [32]
700 Nitrogen PDP 12450 [32]
In 800H (30–35) 650 Nitrogen PDP 5940 [32]
700 Nitrogen PDP 14310 [32]
Inc 625 (~62) 650 Nitrogen PDP 2800 [32]
MgCl2/NaCl
(52/48)		 Ni (>99.97) 520 Air I+M (140 h) 57 [33]
GH 4033 (Ni72.1/Cr20.5/Fe4.0/Ti2.6/Al0.8) 520 Air I+M (140 h) 142 [33]
GH 4169 (Ni52.9/Cr19.0/Fe18.5/Ti0.9/Al0.84/Mo3.1/Nb5.2) 520 Air I+M (140 h) 246 [33]
Tab.3  Results of corrosion studies metallic alloys in molten chloridesa)
Fig.8  Interaction between molten chlorides with corrosive impurities and metallic alloys
Molten chlorides /wt-% Alloys Atmosphere temperature /°C Procedures Corrosion mechanism Ref.
CaCl2/MgCl2/NaCl
(43.6/17.7/38.7)		 Ni-based commercial superalloys Air /600 SEM, EDS, XRD, TC Preferential depletion of Cr and Fe,
intergranular corrosion		 [29]
MgCl2/NaCl
(52/48)		 Ni-based alloys (Ni 52.9–99.97 wt-%) Air /520 SEM, EDS, XRD Combined effect of alloy dissolved as anode, preferential oxidization and chlorination [33]
KCl/NaCl
(56.1/43.9)		 Stainless steels Argon /750 EAS, XRM, SEM, OCP, LV, EIS Intergranular corrosion,
preferential depletion of Cr, Fe and Mn		 [35]
KCl-ZnCl2
(69.1/30.9)		 NiAl and FeAl model alloys Air /400–450 SEM, EDX, XRD, EPMA Preferential depletion of Al,
formation of Al2O3 within the pores of corrosion layer		 [17]
MgCl2/NaCl
(MgCl2 wt-% 0.0, 48.9, 61.0, 93.6)		 GH 1140
(Ni37.5/Cr21.5/Fe35.85/Ti0.9/Al0.4/Mo2.25/W1.6)		 Air /850 SEM, EDS, XRD Without MgCl2:
dissolution as anode–oxidizing–peeling off of oxide film,
with MgCl2: dissolution as anode–oxidation–reduction–peeling off of oxide film		 [37]
Tab.4  Corrosion of metallic alloys in molten chloridesa)
Elements Al Mn Cr Fe Ni
E0m /V vs. Pt2+/Pt −1.886 (Al3+/Al) −1.794 (Mn2+/Mn) −1.396 (Cr2+/Cr)
−1.131 (Cr3+/Cr)		 −1.183 (Fe2+/Fe)
−0.852 (Fe3+/Fe)		 −0.792 (Ni2+/Ni)
Tab.5  Standard electrode potentials of metallic elements in molten MgCl2/KCl/NaCl (50/20/30 mol-%) at 475 °C [39]
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