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

8

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

10-12/07/2018

Selection and optimization of Eutectic mixture as TES materials

910-12/07/2018

10

Quaternary component salt system: 6 binarydiagrams + 4 ternary diagrams

Requires deep comprehension of basic subsystems

10-12/07/2018

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

1110-12/07/2018

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

1210-12/07/2018

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

1310-12/07/2018

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

14

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

10-12/07/2018

15

Selection and optimization of Eutectic mixture as TES materials

10-12/07/2018

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

Dirección Técnica 25

Physicochemical Properties

Dirección Técnica 26

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)

Dirección Técnica 27

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)

Dirección Técnica 28

Corrosion tests

Dirección Técnica 29

Corrosion tests

Dirección Técnica 30

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

Dirección Técnica 31

CIERTOS CONSTITUYENTES MEJORAN EL COMPORTAMIENTO DE LAS CAPAS PROTECTORAS CONFIRIENDOLE MAYOR RESISTENCIA Y BAJA VELOCIDAD DE CORROSIÓN