Latent Thermal Energy Storage System for Heat Recovery between 120 and 150 °C: Material Stability and Corrosion †
Abstract
:1. Introduction
2. Phase Change Materials Screening and Selection
2.1. Selection Criteria
- Physical: besides the suitable transition temperature, the PCM should have:
- -
- High volumetric enthalpy (high latent heat and high density) to provide high-density storage. The value of 50 kWh·m−3 was taken as a reference. It corresponds to the variation enthalpy of water in a temperature range of approximately 0–43 °C;
- -
- High thermal conductivity to increase the heat transfer and provide high thermal storage\discharge power (may be optimized by the system geometry);
- -
- Low thermal expansion coefficient to avoid mechanical stress on PCM envelope;
- -
- Good phase equilibrium (no segregation during phase change), as phase segregation during transition disrupt heat transfer and can be partially irreversible;
- -
- No supercooling that delays crystallization.
- Chemical:
- -
- Long-term chemical stability to avoid performance degradation through thermal cycling;
- -
- Compatibility with enveloping materials to avoid corrosion;
- -
- No toxicity nor fire hazards.
- Economics:
- -
- PCM should be industrially available in large quantities;
- -
- For a cost-effective storage system, the PCM price should remain affordable. This is highly dependent on the targeted application: for a short-term storage (about 3 cycles per day), the International Renewable Energy Agency (IRENA) estimated a viable investment cost at 225 EUR·KWh−1 for the whole system [27]. Accounting for approximately 45% of this investment for the phase change material [28], its cost should remain under 100 EUR·KWh−1.
2.2. Materials Screening
- Metals, for their high costs. Two PCMs fit in the temperature range [30]: Indalloys 255 (55.5%mBi + 44.5%mPb, toxic) and 281 (58%mBi + 42%mSn), with the respective melting temperatures of 125 °C and 138 °C. They show a similar volume enthalpy variation to organic PCMs (respectively, 58 and 107 kWh·m−3), but their thermal conductivity is ~100 higher, supporting higher power.
- Eutectics, for their complex industrial production which hinders a precise and stable eutectic. Five PCMs could have been selected for their melting temperature [17,31]: 30%mLiNO₃ + 18%mNaNO₃ + 52%mKNO₃ (120 °C), 33%mLiNO₃ + 67%mKNO₃ (125 °C), 38.2%mLiNO₃ + 61.8%mCO(NH2)2 (125 °C), 44%mCa(NO₃)₂ + 44%mNaNO₃ + 12%mKNO₃ (140 °C), and 40%mNaNO₂ + 7%mNaNO₃ + 53%mKNO₃ (142 °C).
- High cost (- -): mandelic acid, valporic acid, suberic acid, methyl-4′-acetanilide [30], chlorobenzoic acid, and xylose-L;
- Early damage (decomposition temperature closer than 20 °C to the melting temperature): urea, malonic acid, maleic acid, DL-malic acid, trans cinamic acid, fructose-D, and glucose-D;
- Hazardousness (flammability, toxicity): picric acid, benzamide, phenacetine, and anthranilic acid;
- Significant supercooling (more than 30 °C): erythritol (despite a very attractive latent heat) and tromethanol (in addition to a high cost) [36].
Name | Formula | ρ [kg·m−3] | Tm [°C] | ∆Hm [kJ·kg−1] | ΔHm, vol [kWh·m−3] | N° CAS | Price [EUR kWh−1] | Comments | Ref |
---|---|---|---|---|---|---|---|---|---|
Erythritol | C4H10O4 | 1480 | 118–120 | 340 | 140 | 149-32-6 | + + + | Supercooling > 80 °C | [36] |
Succinic anhydride acid | C4H4O3 | 1560 | 118–121 | 206 | 89 | 108-30-5 | + + | * | |
Mandelic acid | C6H5CH(OH)CO2H | 1300 | 118–121 | 161 | 58 | 90-64-2 | - - | High cost | [30] |
Valporic acid | C₈H₁₆O₂ | 904 | 120 | 203 | 51 | 99-66-1 | - - | High cost | [30] |
Benzoic acid | C₇H₆O₂ | 1266 | 121.7 | 143 | 50 | 65-85-0 | + + | Supercooling: 22 °C | * |
Picric acid | C6H3N3O7 | 1760 | 122 | 75 | 37 | 88-89-1 | Flash point 150 °C, explosive | * | |
HDPE | (C₂H₄)n | 940 | 125 | 167 | 44 | 9002-88-4 | Enthalpy < 50 kWh·m−3 | [35] | |
Stilbene | C₁₄H₁₂ | 970 | 126 | 167 | 45 | 103-30-0 | Enthalpy < 50 kWh·m−3 | * | |
Benzamid | C₉H₇NO | 1341 | 127.2 | 169 | 63 | 55-21-0 | Toxic | * | |
Tromethamine/Tromethanol | C4H11NO3 | 1353 | 131 | 285 | 107 | 77-86-1 | - | Supercooling: 66 °C, High cost | [36] |
Anydride phthalic | C₈H₄O₃ | 1530 | 131 | 159 | 68 | 85-44-9 | + + + | Supercooling: 23 °C | [38] |
Sebacic acid | C₁₀H₁₈O₄ | 1209 | 131–133 | 243 | 82 | 111-20-6 | + + | [39] | |
Maleic acid | C₄H₄O₄ | 1590 | 131–140 | 235 | 104 | 110-16-7 | Decomposition ~145 °C | * | |
DL- malic acid | C₄H₆O₅ | 1601 | 131–140 | 225 | 100 | 6915-15-7 | Decomposition ~150 °C | * | |
Urea | CO(NH₂)₂ | 1323 | 132 | 251 | 92 | 57-13-6 | Low stability | * | |
Malonic acid | C₃H₄O₄ | 1620 | 132–136 | 141-82-2 | Decomposition ~135 °C | * | |||
Trans cinnamic acid | C₉H₈O₂ | 1250 | 133 | 153 | 53 | 140-10-3 | Decomposition ~146 °C | * | |
Phenacetin | C₁₀H₁₃NO₂ | 1240 | 134 | 175 | 60 | 62-44-2 | Toxic | * | |
Chrolobenzoic acid | C7H5ClO2 | 1540 | 140 | 164 | 70 | 118-91-2 | - - | High cost | * |
Suberic acid | C₈H₁₄O₄ | 1020 | 141–144 | 245 | 69 | 505-48-6 | - - | High cost | [30] |
Dimethyl terephtalate | C₁₀H₁₀O₄ | 1290 | 142 | 170 | 61 | 120-61-6 | + + | * | |
Fructose-D | C₆H₁₂O₆ | 1690 | 144–145 | 145 | 68 | 57-48-7 | Early degradation | * | |
Isomalt | C12H24O11 | 1040 | 145 | 170 | 71 | 64519-82-0 | - | [37] | |
Trans-1,4-polybutadiene (TPB) | C4H6 | 1010 | 145 | 144 | 40 | 25038-44-2 | Enthalpy < 50 kWh·m−3 | [6] | |
Maltitol | C₁₂H₂₄O₁₁ | 1620 | 145–152 | 173 | 78 | 585-88-6 | + + + | * | |
Methyl-4′-acetanilide | C9H11NO | 1370 | 146–151 | 180 | 69 | 103-89-9 | - - - | High cost | [30] |
Lactitol | C₁₂H₂₄O₁₁ | 1690 | 146–152 | 135–149 | 70 | 585-86-4 | + + + | Industrial availability | * |
Anthranilic acid | C6H4(NH2)COOH | 1410 | 147 | 148 | 58 | 118-92-3 | Flash point 150 °C | * | |
Xylose-D | C₅H₁₀O₅ | 1525 | 147–151 | 216–280 | 118 | 58-86-6 | + + + | * | |
Xylose -L | C₅H₁₀O₅ | 1525 | 147–151 | 213 | 90 | 609-06-3 | - - - | High cost | * |
Glucose -D | C₆H₁₂O₆ | 1540 | 149–152 | 180 | 82 | 50-99-7 | Low stability | * | |
Adipic acid | C₆H₁₀O₄ | 1360 | 151–155 | 260 | 98 | 124-04-9 | + + + | * |
2.3. Calorimetric Analysis
2.3.1. Material & Method
Differential Scanning Calorimetry (DSC)
Thermogravimetry Analysis (TGA)
- A 10 min isothermal step at 35 °C below the melting temperature;
- A 2 °C·min−1 slope up to 100 °C above the melting temperature.
2.3.2. Results and Analysis
3. Stability and Corrosion Study
3.1. Materials and Method
3.1.1. Stability Study: PCM Thermal Aging
3.1.2. Corrosion Study: PCM and Envelope Thermal Aging
3.2. PCM Thermal Aging
3.3. PCM and Envelope Thermal Aging
3.3.1. Sebacic Acid
3.3.2. Adipic Acid
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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DSC (2nd, 38th, and 75th Cycles) | TGA | |||||||
---|---|---|---|---|---|---|---|---|
Tonset [°C] | ΔHm, vol [kWh·m−3] | ΔTmean [°C] | T1% [°C] | |||||
Precision | ±0.4 °C | ±1.3% | ±0.4 °C | - | ||||
Succinic anhydride | 115.3 | 115.7 | 115.3 | 77.6 | 74.5 | 71.9 | 60.8 | 115.7 |
Benzoïque acid | 121.5 | 120.5 | 120.7 | 49.6 | 47.1 | 46.4 | 25.0 | 122.4 |
Phtalic anhydride | 129.1 | 128.9 | 129 | 65.9 | 60.4 | 58.7 | 27.3 | 124.0 |
Sebacic acid | 131.5 | 130.3 | 130.8 | 75 | 70 | 71 | 11.7 | 181.0 |
Dimethyl terephtalate | 140.2 | 139.9 | 140.4 | 58.4 | 54.8 | 53.4 | 9.7 | 128.7 |
Adipic acid | 150.0 | 149.1 | 149.6 | 95.2 | 92.6 | 92.2 | 10.0 | 186.1 |
Corrosion Speed [mm·Year−1] | Recommendations |
---|---|
>2 | Completely ruined in a few days |
0.2–2 | Not recommended for use longer than one month |
0.1–0.2 | Not recommended for use longer than one year |
0.02–0.1 | Use carefully depending on conditions |
<0.02 | Long-term use |
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Lalau, Y.; Rigal, S.; Bédécarrats, J.-P.; Haillot, D. Latent Thermal Energy Storage System for Heat Recovery between 120 and 150 °C: Material Stability and Corrosion. Energies 2024, 17, 787. https://doi.org/10.3390/en17040787
Lalau Y, Rigal S, Bédécarrats J-P, Haillot D. Latent Thermal Energy Storage System for Heat Recovery between 120 and 150 °C: Material Stability and Corrosion. Energies. 2024; 17(4):787. https://doi.org/10.3390/en17040787
Chicago/Turabian StyleLalau, Yasmine, Sacha Rigal, Jean-Pierre Bédécarrats, and Didier Haillot. 2024. "Latent Thermal Energy Storage System for Heat Recovery between 120 and 150 °C: Material Stability and Corrosion" Energies 17, no. 4: 787. https://doi.org/10.3390/en17040787