• 专利附录
  • 专利说明
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    • 专利摘要:
    This application calls for the innovative formulation of mixtures of nitrate salts, whose composition is based mainly on strontium nitrate and other alkali metal nitrates. These salts, in a composition determined in this patent, produce a eutectic mixture whose melting point is lower than 210º c, in a ternary formulation and its decomposition occurs at a temperature higher than 500º c. Additionally, other non-eutectic compositions are determined in order to adapt their melting point to the various applications if it is considered necessary. On the other hand, this ternary formulation is more competitive from the economic point of view than the formulations currently in the market. This formulation of salts has its direct application as a heat storage fluid, as well as a thermal transfer vehicle, being applicable for heat accumulation and transmission systems in solar thermal power plants, as well as in any other application where temporary storage is required. Thermal energy and its subsequent transfer. The main contribution of this invention is that of a fluid capable of maintaining its liquid state for a longer time and at a lower temperature than the existing formulations on the market, without the need for external heat input and also to ensure the stability thereof. Higher temperatures. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2579763A1
    申请号:ES201530038
    申请日:2015-01-15
    公开日:2016-08-16
    发明作者:Francisco LORMAN MARTINEZ；Maria Pilar PENA CASTRO；Luis CONTRERAS SANCHEZ；Francisca Galindo Paniagua
    申请人:Quim Del Estroncio S A U；Quimica Del Estroncio SAU；
    IPC主号:
    专利说明:

    New nitrate salt formulations for use as storage fluid and heat transfer
    Object of the invention
    The present invention is part of the Renewable Energy Sector, in particular in the field of Thermal Energy. It is aimed at an innovative formulation of nitrate salt mixtures, whose composition is based primarily on Strontium Nitrate and
    two other alkali metal nitrates. Its use is also contemplated in the storage and transfer or transport of thermal energy.
    Background of the invention
    One of the important challenges for the development of renewable energy is its
    storage and this is one of the main problems in the production of solar energy in solar thermal plants. The thermal energy produced is necessary to transport and store it for later use.
    For transport, the use of synthetic thermal oils is quite widespread, mainly due to its wide range of working temperatures, usually between approximately 12 oC and 390 oC, without freezing, boiling or decomposing. However, these fluids are not suitable for heat storage, due to their
    Properties of low density, low heat capacity, high viscosity and high cost, mainly.
    Until now the most used system, mainly in solar thermal plants with heat storage, is a fluid consisting of molten binary salts of nitrates. These salt mixtures have several advantages such as storage fluids, such as their high density, high heat capacity, high decomposition temperature (generally higher than 500 ° C) and competitive cost. In addition, their physical-chemical properties make them suitable for use as heat storage fluids in large tanks.
    However, the main problem facing a storage of thermal energy with molten salts as a thermal fluid is the risk of solidification of the salt, so it is necessary to keep the melt perfectly insulated and with external heat input in case the temperature decreases to values close to the melting point. On the other hand,
    Although the decomposition temperatures are generally much higher than those of thermal oils, it is sought to work at the maximum temperature allowed by the intermediate fluid (thermal oil or others such as the salts themselves) to increase the efficiency of the Rankine cycle when delivering the Stored energy. The stability of these salts at high temperature is of the utmost importance, since decompositions in products that can cause corrosion or that could be toxic should be avoided.
    The alkali metal and alkaline earth metal nitrate salts are the most suitable for your
    application as thermal storage due to its good physical-chemical properties and its stability at high temperatures. They form very homogeneous molten mixtures and have eutectic mixtures with melting points lower than the melting points of each of the pure salts.
    The most commonly used nitrate mixture is a binary nitrate mixture
    Sodium and Potassium Nitrate (60%: 40% by weight) called Solar Salt (SS), for commercial reasons a formulation is used in a proportion different from that of the eutectic. The cost of KN03 is higher than that of NaN03, so a mixture with a higher proportion of NaN03 is cheaper even if its melting point is higher. The equilibrium diagram KN03 -NaN03 is shown in Figure 1, in this figure it can be seen that it is a system with a simple eutectic, the eutectic composition for this mixture of salts, is around 54% KN03 and 46% NaN03 in moles. The melting point of this binary salt is 222 ± 5 ° C. However, in the SS, the formation of crystals during cooling (liquidus temperature) begins at a higher temperature, so in practice, the stores maintain a temperature above 250 ° C (normally 280 ° C) to avoid solidification of the melt.
    This high melting temperature means that these molten salts cannot be used directly as a thermal transport fluid and that the storage system is more energy efficient, reducing the number of hours of operation without heat input.
    Another factor to consider in the salts currently used for application as a heat accumulator, is the danger of corrosivity. This is mainly due to the presence of impurities and possible decompositions of nitrates in nitrous gases at high temperatures. An ideal mixture should have a totally stable composition in the range of working temperatures, so that there are no impurities or compounds capable of producing corrosion in the work equipment.
    Description of the figures
    Figure 1: Binary eutectic system KN03-NaN03. Eutectic compositions are indicated
    (E) And of Solar Salt (SS). Reference: O. Senes, R.J.M. Konings, S. Wurzer, M. Sierig, A. Oockendorf. "A ose study of the NaN03-KN03 system using an innovative encapsulation technique" Thermochimica Acta 509 (2010) 62-66.
    Figure 2 KN03-NaNÜ3-Sr (N03) 2 ternary system: a) Isopletal section, at 10% by weight of Sr (N03) 2 in which the influence of the composition on the melting temperature of ternary mixtures can be observed; b) Isopletal section between the binary eutectic NaN03-KN03 and Mr (N03) 2 in which the influence of strontium on the melting temperature can be observed
    of ternary mixtures.
    Figure 3: Liquidus surface of the ternary eutectic system Sr (N03) 2-NaN03-KN03.
    Figure 4: Thermal conductivity of Solar Salt (SS) and solar salt with strontium nitrate (T88) in the temperature range of 60 ° C to 280 ° C.
    Figure 5: Variation of viscosity with temperature for binary and ternary salts in the temperature range of 250 to 400 ° C.
    Figure 6: Specific heat variation in binary (SS) and ternary eutectic compositions with strontium nitrate (TSS) determined experimentally by differential calorimetry.
    Figure 7: MES-EOX microanalysis of the stainless steel-ternary salt interface after 5000 h in contact with the ternary salt with strontium nitrate (TSS) at 565 oC.
    Figure 8: a) ATO curve of the eutectic composition of the binary system, 54% KN03: 46% molar NaN03, showing the melting behavior during 4 heating
    consecutive with intermediate cooling; b) Detail of the ATO during cooling of the compositions 50% KN03 -50% NaN03 and 54% KN03 -46% molar NaN03.
    Figure 9: Detail of the ATO curve of the eutectic composition of the binary system Sr (N03) 2-KN03 (26%: 74 molar%) in which the typical behavior during cooling of a eutectic composition can be observed.
    Figure 10: ATO of the eutectic composition of the binary system Sr (N03) 2-NaN03 (20%: 80% molar) in which the typical fusion behavior of an eutectic can be seen. The first endothermic peak at 273 ° C corresponds to the polymorphic transformation of NaN03.
    Figure 11: Detail of the ATO curve of the ternary eutectic mixture during the second heating-cooling cycle from room temperature to 350 ° C showing: a) the endothermic peak corresponding to the eutectic fusion with a maximum at 207 ° C and b) the exothermic peak corresponding to crystallization during cooling that starts at 202.5
    oC
    Figure 12: ATO curve of a composition away from the eutectic of the ternary system Sr (N03) 2-NaN03-KN03 Description of the invention
    To overcome the problems and needs of the state of the art, the authors of the present invention after an important research work have developed a fluid capable of maintaining its liquid state for a longer time and at a temperature lower than the existing formulations in the market , without the need for heat input
    external and also ensuring its stability at higher temperatures.
    This new formulation is based on a ternary mixture of salts, based on Nitrates, including in its composition Strontium Nitrate. This salt formulation has direct application as a heat storage fluid and as a heat transfer vehicle, being applicable for heat accumulation and transmission systems in
    solar thermal power plants, as well as in any other application where temporary storage of thermal energy and its subsequent transfer is required.
    Thus, in a main embodiment of the invention a composition comprising a ternary mixture of nitrate salts is contemplated, one of the components being Strontium Nitrate and the remaining two alkali nitrate salts.
    These new salt formulations have a low melting point and a high decomposition temperature.
    The composition of the invention has formulations such as those represented in the table
    1, consisting of mixtures of salts of Strontium Nitrate and alkaline Nitrates such as Sodium and Potassium.
    Table 1 shows the melting temperature of different binary and ternary alkali nitrate compositions (KN03 and NaN03) and Strontium Nitrate, determined
    experimentally by Differential Thermal Analysis and by the polydermal method. In the compositions with Strontium it has been found that during cooling (marked with * in Table 1) subcooling phenomena appear. The values obtained from "Phase Diagrams for Ceramists" published by "American Ceramic Society / NIST" are available.
    Table 1.
    Heating system / speed Composition (mol EYE)Experimental melting range (± 5 ° C)
    Sr (N03l2 NaN03KN03SolidusLiquidusBibliography
    Composition A (3ºC / min) 16.1040.2943.59209/203 '340
    Composition F (3ºC / min) 9.145.745.19208/204 '260
    Composition Z (3ºC / min) 4.7042.9452.35209/203 '210-
    Eutectic KN03-NaN03 (3ºC / min) OR4753219222
    Eutectic KN03 -Sr (N03) 2 (3ºC / min) 2674OR270276
    Eutectic NaN03-Sr (N03) 2 2. 377ORn.d.294.6
    Eutectic Sr (N03kKN03 -NaN03 4.6943.2452.07208/203 '208n.d.
    KN03 (1ºC / min) OROR100327333.8
    NaN03 (1 ° C / min) OR100OR291306.6
    Sr (N03) 2 (1 ° C / min; decomposes at T> 600 ° C) 100OROR600ºC645
    In a particular embodiment, at least one of the alkali nitrate salts present in the composition is selected from Sodium Nitrate and Potassium Nitrate. So
    5 preferred, the composition of the invention comprises a mixture of Strontium Nitrate, Potassium Nitrate and Sodium Nitrate. Preferably, Strontium Nitrate constitutes 550% by weight and alkaline nitrate salts 95-50% by weight of the composition.
    In a preferred embodiment, this ternary mixture of nitrate salts is an eutectic mixture whose melting point is less than 2100e and its decomposition occurs at a temperature greater than 500 ° C.
    The eutectic composition stands at 10%: 53%: 37% by weight of Strontium, Potassium and Sodium Nitrates respectively_ In Figures 2 and 3 it is observed that the melting temperature of this eutectic is 208 ± 1.4 oC.
    Additionally, other non-eutectic compositions 15 are contemplated in the present invention in order to adapt their melting point to various applications if deemed necessary. On the other hand, these ternary formulations can be more competitive from the point of
    economic view that the formulations currently on the market, because the price of Strontium Nitrate is much lower than that of Potassium Nitrate. Among them, a ternary composition with representative strontium nitrate, called TSS, has been chosen to show the physical-chemical properties. This composition ranges from 5-20% of Sr (N03) 2,
    20-50% of KN03 and 40-70% of NaN03, in% weight. The ternary compositions contemplated in the present invention are not only of interest for their minimum melting point, but certain compositions present in the primary crystallization fields of sodium nitrate and strontium nitrate have
    25 better physical-chemical properties, so that slightly increasing the melting point can significantly improve its behavior.
    The characteristics of this salt formulation outweigh the binary combinations of salts currently marketed for their physicochemical properties, their high stability at elevated temperatures (above 500 ° C) and most importantly, their lower melting point and their lower cost per already mentioned lower cost of Mr (N03) 2 compared to KN03. Therefore, the facilities operating with this formulation as storage salt can work at a higher temperature in the Rankine cycle, so the efficiency would be higher. There are less problems of crystallization, being able to consider working temperatures close to 215 ° C as a lower working limit (which extends the working range). This allows to improve the operability of the solar thermal plants and reduce the energy expenditure in the periods of no external heat input, besides being able to be used during more prologized times for the same storage.
    These properties together with those of high temperature stability, low corrosivity in the range of working temperatures studied for pure components, low vapor pressure, high thermal conductivity and high heat capacity that characterize the compositions of the invention, as well as the Low viscosity at high temperatures, make this formulation suitable for use as a thermal storage fluid.
    Another important property of the formulations presented in this invention is the absence of hydrates, so that the handling of solid salts, as well as their melts, does not present problems in contact with the environment. However, other formulations, for example with Calcium or Magnesium Nitrate, which form hydrates in contact with ambient humidity, present multiple problems in phase changes,
    not only in changes of state, but also in changes between different states
    hydrated
    All these properties, which characterize the compositions of the invention, allow their direct application as a heat storage fluid and as a heat transfer vehicle, being applicable for heat accumulation and transmission systems in solar thermal power plants, as well as in any another application where temporary storage of thermal energy is required and its subsequent transfer.
    Therefore, in another main aspect of the invention the composition of the invention is contemplated for use in the storage and transfer or transport of thermal energy. In particular, it is applicable in heat accumulation and transmission systems in solar thermal power plants, as well as in any other application where temporary storage of thermal energy and its subsequent transfer is required.
    EXAMPLES
    Given the novelty of the compositions of the invention, there were no experimental data of
    ternary mixtures of the nitrate salts contemplated, so it was necessary to
    development of new compositions and characterization of the properties of interest of
    the aforementioned formulations.
    The experimentation for the development of the formulations object of this invention was carried out in collaboration with the Institute of Ceramics and Glass of the CSIC. The determination of some of the physicochemical properties of the formulations was also carried out at the Institute of Ceramics and Glass, such as Melting Temperature, Heat Capacity and
    Density.
    The methodology applied for the search of the eutectic mixture of each of the
    Formulations described below.
    The compositions tested were prepared by direct mixing of the different nitrates and, in order to minimize composition errors as well as possible contamination, they were homogenized by melting in a crucible of pt. The nitrates used had a very high purity as has been proven in the determination of their melting points.
    To establish the ternary system, two isopletal sections to said system were experimentally determined using the polydermal method and ATO: one with a constant content of Sr (N03) 2 of 10% by weight and another in which it has remained constant the KN03 / NaN03 ratio and the content of Sr (N03) 2 has been varied (Figure 2). The surface of Iiquidus of the ternary system Sr (N03) 2-NaN03-KN03 thus established is shown in Figure 3. The thick continuous lines separate the different primary fields of
    crystallization (Sr (N03) 2, NaN03 and KN03) and correspond to lines in which two solid phases and a liquid coexist, the intersection of the three lines defines the composition of the ternary eutectic (in which the three coexist at 210 ° C solid phases and a liquid). The intersection of each of the lines with the edges of the ternary system defines the three binary eutectic (Sr (N03) 2-NaN03; Sr (N03) 2-NaN03 and KN03-NaN03). Isotherms have been represented by dashed lines. The triangular points correspond to the different compositions studied, some of them listed in Table 1, to more fully define the system.
    Physicochemical properties
    The physicochemical properties of the ternary mixtures contemplated in the present invention are very similar to those of Commercial Solar Salt (60% weight of NaN03 and
    40% weight of KN03). The thermal conductivities of commercial Solar Salt (SS) and ternary salt with Strontium (TSS) are shown in Figure 4, where it can be seen that the difference between
    both is minimal at low temperatures, but at higher temperatures (higher zone
    interest) the TSS composition has superior thermal conductivity. The variation of viscosity with temperature for solar (SS) and ternary salt with Strontium (TSS) has been represented in Figure 5. The viscosity of the composition SS is between 6-3 mPa · s for a range of temperatures of 250-400 oC, while ternary compositions with strontium nitrate are around 2 mPa · s for the same temperature range, indicating significantly less viscous behavior with respect to the SS.
    In the case of density, ternary compositions with strontium nitrate result
    slightly denser than solar salt, between 2 and 5% higher.
    Figure 6 shows the Specific Heat of the ternary mixture with strontium (TSS) compared to commercial solar salt (SS). An equivalent behavior between one salt and another is appreciated, so they can be used for the same applications.
    Stability against high temperatures has been experienced keeping the formulations for a period of 15 hours cooling, reheating with a new maintenance period of 15 hours at different temperatures (400 ° C, 450 ° and 500 ° C),
    observing only a minimum weight loss <1% by weight in the early stages. This is justified by the presence of minimal impurities in the salts that form the mixture. When these impurities disappear, the formulation stabilizes, without presenting changes in weight, both when raising and decreasing the temperature. Thus, advantageously, the composition of the invention does not exhibit decompositions or chemical changes to
    temperatures below 550 ° C.
    The high temperature corrosion behavior of strontium ternary salt (TSS) is similar to that of commercial solar salt (SS). A series of commercial, carbon and stainless steels and other non-ferrous alloys have been tested, observing
    5 an equal corrosion mechanism for all salts studied including commercial solar salt. In the molten salt steel interface, the formation of layers of protective spinels with flaking losses similar to those of commercial solar salt are favored, with corrosion rates of the same order of magnitude for steels of greater interest.
    Figure 7 shows the microanalysis by dispersion of energies of the molten-steel ternary salt interface in a Scanning Electron Microscope (MEB-EOX) to one of the samples attacked, in an air-tight oven, during a 5000h period at 565 ° C.
    As can be seen, continuous protective layers are produced, generally thicker than those formed by commercial solar salt, avoiding more frequent attacks on the edge of grain more frequent in thinner layers.
    Fusion tests
    Fusion studies have been carried out in a differential and thermogravimetric thermal analysis (ATO-TG) equipment at heating and cooling rates that have varied
    20 depending on the case between 1, 2 and 3 oC / min. In order to homogenize the sample, three consecutive heating and cooling cycles have been carried out in each of the samples. The first cycle has been used to achieve a perfect mix of precursors, the results of this sequence have not been taken into account. The data from the other two cycles have been used to establish the melting temperature.
    25 The melting behavior of pure nitrates and well-known binary eutectic has been established to validate the ATO as an appropriate measurement method. Table 1 shows the results of three of the different compositions analyzed (B, G and H) in addition to the results of the binary eutectic of interest obtained from Phase Oiagrams for Ceramists published by American Ceramic Society / NIST.
    30 Figure 8a shows the ATO of the eutectic of the binary system KN03-NaN03, during 4 consecutive heating-cooling cycles (1, 2, 3 and 4), in the curve it is observed that the endothermic peak corresponding to the fusion it presents the maximum at the same temperature during the four cycles, which indicates a great stability of the composition and reproducibility in the measurement method. Figure 8b shows the ATO section of the compositions 50% KN03 -50% NaN03 and 54% KN03 -46% molar NaN03 corresponding to the ATO cooling in it the beginning of the exothermic peak at 219 ° C, associated with eutectic crystallization. The similarity of the behavior of both compositions during solidification can be observed. The temperature of the eutectic coincides within the measurement error with that established by other authors 222 ± 5 ° C for this invariant point.
    The melting behavior of the eutectic of the binary system Sr (N03) 2-KN03 (26 mol%: 74 mol%) is presented in Figure 9. The exothermic peak recorded during crystallization in cooling at 2 ° begins at 270 ° C, this temperature coincides with that of the eutectic determined by other authors.
    The eutectic fusion behavior of the binary system Sr (N03) 2-NaN03 (20 mol%: 80 45 mol%) is presented in Figure 10. The exothermic peak recorded during crystallization in the 2nd cooling starts at 297 ° C, this temperature coincides with that of the eutectic determined by other authors (294 ° C).
    The fusion behavior of the eutectic of the ternary system Sr (N03) 2-NaN03-KN03 is presented in Figure 11. It can be seen that the melting temperature during heating is 207 oC and during cooling 202.5 ° C. These differences between heating and cooling are due to subcooling phenomena. The lower crystallization point of the formulations of this invention that would protect the equipment from unwanted crystallizations, in turn increasing the working range, can be seen against those corresponding to the SS.
    In Figure 12 the melting behavior of a composition away from the
    eutectic of the ternary system Sr (N03) 2-NaN03-KN03, the ATO presents a first peak at
    2100C corresponding to the beginning of the fusion (eutectic) and a second peak at 262 ° C that we
    indicates the liquidus temperature of this composition. This total melting temperature is
    slightly higher (262 ° C) than the value of commercial solar salt (:::: 2600C).
    权利要求:
    Claims (13)
    [1]
    one. Composition comprising a ternary mixture of nitrate salts being one of the components of Strontium Nitrate and the remaining two, alkali nitrate salts.
    [2]
    2. Composition according to claim 1 wherein at least one of the alkali nitrate salts present in the composition is selected from Sodium Nitrate and Potassium Nitrate.
    [3]
    3. Composition according to claim 2 comprising Strontium Nitrate, Sodium Nitrate and Potassium Nitrate.
    [4]
    Four. Composition according to claim 3 wherein the composition is eutectic.
    [5]
    5. Composition according to claim 4 wherein the Strontium Nitrate constitutes from 5 to 50% and the sum of alkali nitrate salts from 50 to 95% by weight of the composition.
    [6]
    6. Composition according to claim 5 wherein the percentages by weight of Strontium Nitrate, Potassium Nitrate and Sodium Nitrate is 10% -53% -37% by weight.
    [7]
    7. Use of a composition, according to any of claims 1-6, in the storage and transfer of thermal energy.
    [8]
    8. Use according to claim 7, wherein the thermal energy is solar thermal.
    [700]
    700 .----- ~ ------ ~ ------ ~ ------ ~ - ~ __,
    [400 ]
    400
    ./
    / a: .- NaN 03SS + eL 300LLI ______________ ~~ .. ~~ ------ ~ ---- ~
    [0]
     0.0 0.2 0.4 0.6 0.8 1.0 X (KN0 3)
    FIGURE 1
    ~ oo ~ ---------------------------------------- ~
    KNO, + NaNO, + Mr {NO,)
    or 10twenty3040fiftyGO708090100
    KN03 % weightElder brother,
    Figure 2 a)
    600 ~ ------------------------------------------ r
    200 ~~~ -------, ~ --- T ~~~ ----------------- i ·
    , '~ 560 oc
    ~ 500 ,
    ~ ,, 1iquidus
    ro
    B 400
    ~
    Q) or .. E ~ 300 '"'" .. '"Mr (NO, h + Liq.
    223.4 oc KNO, + liq., .., '"i'" '"208, 6 ~ 1 40C
    solidus
    o 10 20 30 40 50 60 70 80 90 100
    NaNOJ-KNO,
    Sr (N03) 2
    Eutectic
    FIGURE 2 b)
    FIGURE 3
    0.6
    0.55
    0, 5
    ~
    AND
    ! 0.45
    - <
    0.4
    0.35
    0.3
    r --- · - · ---..- .. ··, --- · ----.... · --- · T · ...... -..- · - - · -T .. ---...------- T --'-'-- "'-,. - ._ ------'--- ;: ~ - ,
    OR
    [
    n
    or
    OR
    I-g --- or - + ----------- + ----- ·· ...----- f- · --------- l ------ O
    ----OR --..
    ._--
    I 8 8 8
    8 o [J 8 o rb o t ~ o
    O () O
    ) 00 OR iOO
    I
    ..____ L _______________ ... ... _______________L ______ .. _._.._
    ._ _ _ ____ ____ ___ --' - _--- '
    > -..._ _ .. _._.__ .. _._ .....
    50 80 110 140 170 200 230 260 290 I
    Tem ~ erat ~ ra (· c ~ ________..______. J
    FIGURE 4
    lIT (K · l)0.0012 0.0013 0.0014 0.0015 0.0016 0.0017 0.0018 0.0019 0.0020
    FIGURE 5
    18 16 14
    4 2 O
    190 220 250 280 310 340 370 400 430 460 Temperatu (a
    FIGURE 6
    FIGURE 7
    ~ .------------------------------------,
    '0
    ~
    ..;:; <l
    F:
    - <:
    · '0
    -1 --2 3 21O "C'-4
    ~ -'---, -----'-- r ---- r- ~ ---, - ~ - "
    75 1 ((1 12 ~ 15 <1 t7 ~, 2) (1 22S 250
    Temp € 1rBtuf'a re;
    to
    FIGURE 8
    the :;
    [5]
    5.
    or
    «
    270 oC
    10
    ·twenty
    160 180 200 220 240 260 280 300 320 340 Temperature (OC)
    FIGURE 9
    :;
    3rd
    r
    <{
    - 10
    3958 B NKS 1 to 3 "C · min with maintenance 15h · 2nd heating
    207 'e
    ~ O 100 1 ~ 0 200 2 ~ 0 300 Temperature ('C)
    b
    273 'C
    OR
    and
    [-]
    - .or
    - 10
    - fifteen
    297 'C
    - twenty
    O 100 200 300 400:, () or
    OC temperature
    FIGURE 10
    25 20 189 OC r
    :;. = or O> « 15 10
    202.5 oC /
    -5 160180200 T instep (oC)220240
    FIGURE 11
    ¡-ATO (/ I-lV) I
    42
    or
    - 4
    -6-8
    - 10
    - 12
    262 oc
     Temperature oc
    FIGURE 12
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    同族专利:
    公开号 | 公开日
    WO2016113438A1|2016-07-21|
    US20180230351A1|2018-08-16|
    ES2579763B1|2017-05-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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