EUTECTIC SALT FORMULATIONS DEVELOPED BY ......Grant Agreement No. 720749 6 M€ DE PRESUPUESTO...
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EUTECTIC SALT FORMULATIONS DEVELOPED BY FERTIBERIA
Transcript of EUTECTIC SALT FORMULATIONS DEVELOPED BY ......Grant Agreement No. 720749 6 M€ DE PRESUPUESTO...
EUTECTIC SALT FORMULATIONS DEVELOPED BY
FERTIBERIA
Relevant Information• Leading producer of fertilizers in the Iberian
Peninsula with over 30% of market share in Spain.
• Access to low-cost Algerian gas, used for 60% of our production.
• Integrated business model, combining a privileged position in terms of cost (Algerian assets) with an excellent distribution platform in the Iberian Peninsula.
Grupo Fertiberiahas consolidated its position as
one of the main players in thefertilizer market worldwide
Grupo Fertiberia - general overview
Production Highlights• Total production capacity of 8 millions
of tonnes.
• Integration of the value chain from ammonia to NPK.
• 16 production facilities located in Spain, Portugal, Algeria and France.
• More than 3,000 employees.
Arzew--------------
Ammonia
Nitric Acid
AN
Nitrog. Sol.
Annaba-----------------
Ammonia
Nitric Acid
AN
NPK
Nitrog. Sol.
SSP
Avilés--------------Nitric Acid
NAC
NPK
ASN
Huelva---------------------
NPK
MAP
DAP
Palos------------------
Ammonia
Urea
N Solutions -AdBlue
Puertollano--------------Nitric Acid
Ammonia
Urea
NAC/NA
Nitrog. Sol.
.
Sagunto-------------------
Nitric Acid
NAC/NA
Nitrog. Sol.
.
PRODUCTION SITES
❑ 11 factories
❑ 8 Million Tm of production capacity
❑ 3.200 Employees
Alverca/
Lavradio------------------
Nitirc Acid
NAC
Calcium nitrate
Setubal------------------NPK/Phosphates
Cartagena-------------------
Nitrates
Nitrog. Sol.
.
THESTO (INTERCONNECTA)OBJETIVO: DESARROLLO DE SISTEMAS DE ALMACENAMIENTO
TÉRMICO PARA GENERACIÓN DIRECTA DE VAPOR
7.8 M€ DE PRESUPUESTO
CONSTRUCCIÓN 3 PLANTAS PILOTO
Grant Agreement No. 720749
6 M€ DE PRESUPUESTO
OBJETIVO: MEJORAR LA TECNOLOGÍA TERMOSOLAR POR ENCIMA DE LAS TECNOLOGÍAS DE GENERACIÓN ELÉCTRICA ACTUALES
CONSTRUCCIÓN PLANTA PILOTO 500 kW
IN POWER (H2020)
W.E. DISTRICT(H2020)OBJETIVO: DISTRICT HEATING & COOLING COMO SOLUCIÓNINTEGRADA QUE APROVECHA LA COMBINACIÓN DETECNOLOGÍAS RENOVABLES, ALMACENAMIENTO TÉRMICO YRECICLAJE DE CALOR RESIDUAL
14 M€ DE PRESUPUESTO
CONSTRUCCIÓN PLANTA PILOTO 1 MW
Selection and optimization of Eutectic mixtureas TES materials
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High-level screening for promising new TES materials has been accomplished
Alkaline & alkaline-earth nitrates based
The development of other new TES materials continues
Use of Thermocalc & Factsage software for modelization
TES Material #1113°C - 550°CTES Material #2208°C - 575°C
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Selection and optimization of Eutectic mixture as TES materials
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Quaternary component salt system: 6 binarydiagrams + 4 ternary diagrams
Requires deep comprehension of basic subsystems
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Compound Polymorph Crystalline structure Stability (ºC) Melting (ºC)
KNO3 Low-KNO3 Orthorhombic Pmnc 25º - 128º
369º
High-KNO3 Rhombohedral R_3m 128º - 369º
NaNO3 Low-NaNO3 Trigonal R_3c 25º - 276º 307º
High-NaNO3 Rhombohedral R_3m 25º - 276º
LiNO3 LiNO3 Rhombohedral 25º - 253º 253º
Sr(NO3)2
Sr(NO3)2 Cubic PA-3 < 570º 645º
Selection and optimization of Eutectic mixture as TES materials
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Compound ΔG(T,p) Database
KNO3
Low-KNO3 SGTE Substance Database
High-KNO3 SGTE Substance Database
Liquid SGTE Substance Database
NaNO3
Low-NaNO3 SGTE Substance Database
High-NaNO3 SGTE Substance Database
Liquid SGTE Substance Database
LiNO3 LiNO3 SGTE Substance Database
Liquid SGTE Substance Database
Sr(NO3)2 Sr(NO3)2
SGTE Substance Database
Liquid X
ΔG(Sr(NO3)2, liq)= ΔG(Sr(NO3)2, sol) + Δhfus - TΔsfus·
Due to complex decomposition & fusion mechanisms of Sr(NO3)2 there is not thermodynamic data available, so it was calculated from solid phase
No reported intermediate compounds Due to similar crystalline structure, solid solutions high-KNO3 & low-NaNO3 willbe modeled by aleatory substitution approachNo solid solutions in the rest binary systemsAs no immiscibility nor ionic species reported in liquid phase, aleatorysubstitution model will be used
Selection and optimization of Eutectic mixture as TES materials
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Aleatory substitution model
Selection and optimization of Eutectic mixture as TES materials
∆𝐺𝑝ℎ𝑎𝑠𝑒 = ∆𝐺𝑝ℎ𝑎𝑠𝑒𝑚𝑖𝑥 +∆𝐺𝑝ℎ𝑎𝑠𝑒
𝑖𝑑𝑒𝑎𝑙 + ∆𝐺𝑝ℎ𝑎𝑠𝑒𝑒𝑥
)])·((··[· ,1,1,0,1,1,0,0,0
BABAf
BAf
BAf
BAf
BA
exceso
fase xxLLTLLxxG −+++= −−−−
BAf
BAf
BAf
BAf LyLLL −−−−
,1,1,0,1,1,0,0,0 ,,Parameters to be adjusted to experimental results
Maggianu extrapolation method
Symmetric modelEqual contribution from binary systems
Binary systems
Ternary & quaternary systems
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Selection and optimization of Eutectic mixture as TES materials
NaNO3 – KNO3 KNO3 – Sr(NO3)2 NaNO3 – Sr(NO3)2
Binary Diagram %w NaNO3 %w KNO3 %w Sr(NO3)2 T eutectic (°C)
NaNO3 – KNO3 50 50 - 222,0
KNO3 – Sr(NO3)2 - 74,6 25,4 277,1
NaNO3 – Sr(NO3)2 83,9 - 16,1 291,9
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Selection and optimization of Eutectic mixture as TES materials
Ternary Diagram %w NaNO3 %w KNO3 %w Sr(NO3)2
T eutectic(°C)
NaNO3 – KNO3 – Sr(NO3)2 37,2 52,7 10,1 210,1
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Selection and optimization of Eutectic mixture as TES materials
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Similar procedure for the other binary & ternary phase diagramsFinal quaternary phase diagram
100°C 200°C 400°C 600°C 1000°C
SS TES | Aceite HTF
SS TES & HTF
HITEC TES | Aceite HTF
800°C
Cloruros TES | Agua/Aire HTF
SS estable < 550°C
OTROS COMPUESTOS ESTABILIZAN LAS COMPOSICIONES
Sistema actual: Doble tanque con
fluido caloportador
Primer avance:
Doble tanque sin fluido
caloportador
Gran volumenAlto coste
Baja Eficiencia por acoplamiento
Mismo volumenmenor coste
Sin acoplamiento
Segundo avance: Tanque único y único fluido caloportador
¡REDUCE EL VOLUMEN DE SALES ≈1/3!
Volumen mínimoMínimo coste
Physicochemical Properties
• TSS melting temperature = 208°C
• EC melting temperature = 113°C
• TSS thermally stable up to 575°C
• EC thermally stable up to 550°C
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Physicochemical Properties
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TSS EC
Corrosion tests
TSS
• Long-term corrosion tests up to 5500h @ 565°C
• Up to 6 SS studied (AISI 304, AISI 316/316L, AISI 316Ti, AISI 321, AISI 347/347H & AISI 430)
• Several tests to determine corrosion effect (SEM-EDX, XRD, Raman spectroscopy, physical effect)
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Corrosion tests
EC
• Long-term corrosion tests up to 3000h @ 425°C
• Up to 6 SS studied (AISI 304, AISI 316/316L, AISI 316Ti, AISI 321, AISI 347/347H & AISI 430)
• Several tests to determine corrosion effect (SEM-EDX, XRD, Raman spectroscopy, physical effect)
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Corrosion tests
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Corrosion tests
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Corrosion tests
TSS & EC
• SS suitable for application
• Low-velocity lineal corrosion kinetics for most SS tested
• No corrosion aggravation under stress nor welds
• Loss of thickness <1mm for most SS tested
• Negligible corrosion attack < 450°C
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CIERTOS CONSTITUYENTES MEJORAN EL COMPORTAMIENTO DE LAS CAPAS PROTECTORAS CONFIRIENDOLE MAYOR RESISTENCIA Y BAJA VELOCIDAD DE CORROSIÓN
