• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method for producing halogen salts, which are substantially free of water and oxygen, of an alkali metal, or an alkaline earth metal, or a transition metal, or a metal of group 13 or 14 of the periodic table, wherein the halogen salt is heated at a heating rate of 0.2 K/min to 30 K/min, in particular 1.0 K/min to 10 K/min, starting from the ambient temperature. The invention also relates to the heat storage material obtained and to the use thereof.
    公开号:ES2685342A2
    申请号:ES201890032
    申请日:2016-11-17
    公开日:2018-10-08
    发明作者:Louis Maksoud；Thomas Bauer
    申请人:Deutsches Zentrum fuer Luft und Raumfahrt eV；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Heat storage material for the high temperature range and procedure for its production
    The present invention relates to a process for preparing a heat storage material, the heat storage material to be obtained and the use thereof.
    Heat storage systems represent a cross-sectional technology, which can also be used in other fields, such as cogeneration, increased flexibility of fossil power plants and heat recovery, in addition to solar thermal plants. In particular, they allow a time-varying energy supply to be reconciled with a demand for time-varying energy. Heat storage systems are basically classified into three different classes. These are sensible heat storage systems, latent heat storage systems with phase transition materials and thermochemical heat storage systems. Liquids, such as water or solids, can be used for the storage of sensible heat. In this case, the storage material itself is heated and the heated material is stored in this way. The amount of thermal energy stored is, in a good approximation, proportional to the temperature difference of the material used.
    On the contrary, the storage of thermochemical heat is based on reversible thermochemical reactions. Energy is stored in the form of chemical compounds formed in an endothermic reaction. In the corresponding exothermic inverse reaction, the stored energy can be released again.
    Energy storage with latent heat storage materials is associated with a phase transition (change of the state of matter) of the storage material. The corresponding materials are often referred to as MCF (phase change materials). The phase transition is usually from solid to liquid. The phase change is associated with storage or heat release and always takes place at a constant temperature.
    For some years, liquid salt storage systems have been used commercially in solar thermal plants. These allow thermal energy to
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    Store for power plants on a large scale and economically. As a storage medium, a mixture of two nitrate salts, the so-called solar salt, is used, which consists of 60% by weight of NaNO3 and 40% by weight of KNO3. It is cost effective and temperature stable for the usual fields of application. However, other nitrate salt mixtures are also known, with which an attempt is made to vary the temperature range in which the salt mixtures can be used as liquid salts. The salt mixtures used have a defined working range in terms of minimum temperatures (due to the melting temperature) and the maximum temperature (due to thermal decomposition). The maximum temperature of the usual solar salts is limited to approximately 560 ° C due to the thermal decomposition of the nitrate salts used. Another possible field of application for liquid salts is in the field of heat carriers and thermal control of reactors in the process industry.
    The drawbacks of the solar salts commonly employed include the minimum limited temperature, and in particular, the maximum temperature of about 560 ° C, above which the nitrate salts will decompose. There are no known alternative nitrate salts or mixtures of nitrate salts with superior thermal stability.
    Generally, solar salts have to be produced synthetically, because naturally occurring nitrate salts have many impurities, which results in high corrosion rates. However, the purification of salts is very complicated in terms of process technology. However, the synthetic production of nitrate salts through the Haber-Bosch process also implies high energy consumption.
    In mixtures of nitrate salts, the reduction of the melting temperature and, therefore, of the lower temperature limit is possible by the addition of additional salts. Although the temperature can be reduced by adding calcium nitrate to potassium nitrate and sodium nitrate, this is detrimental to thermal stability. The addition of lithium nitrate would increase the cost. On the contrary, the addition of sodium nitrite results in a greater potential risk to humans and the environment.
    The application for storage systems requires large amounts of nitrate salt. Thus, for example, the Andasol plant in Spain with 50 MWel and a storage time of 7 hours requires around 28,000 tons of solar salt. The annual amount in the world market or the production capacities of sodium nitrate
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    they are relatively low for such storage application. Nitrates are mainly used as fertilizers, so there may be price effects between fertilizer markets and energy storage. However, there are drawbacks related to the availability of nitrate salts.
    Therefore, on the one hand, there is a need for alternatives to solar salt that can also be used at temperatures above 560 ° C, in particular at 700 ° C or more, up to 1000 ° C, that is, in the range of high temperatures.
    On the other hand, it is also desirable that there is no dependence on products that are also predominantly used for other products.
    Surprisingly, it has been found that halogen salts can be used as an alternative to nitrate salts as heat storage materials for the high temperature range. From the literature, it is known that halogen salts are highly corrosive to metallic materials. However, it is only the stainless steel metallic materials that are used in solar thermal plants or other thermal plants, since the generation of heat and energy must be profitable, and the stainless steel components can be produced at low cost. Now, it has been proven that the reason for corrosion is contaminants in the melt. Thus, for example, magnesium oxide and HCl are formed from magnesium chloride in the presence of water according to the following equation I:
    MgCl2 + H2O ^ MgO + 2HCl (I)
    Contaminants in the halogen salt fusion, for example, from oxides or hydroxides, are formed by contact with air, moisture and the breakdown of hydrate salts.
    Therefore, the objective of the present invention is to achieve acceptable metal corrosion rates of halogen salts so that they can be used as a liquid salt, and thus provide an alternative to solar salt that is thermally stable even at temperatures of 500 ° C or more. , and especially 700 ° C or more. In particular, the cost factor is also critical, since electric power must be provided as economically as possible.
    In a first embodiment of the present invention, the object of the present invention is
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    achieved by a process to produce halogen salts essentially free of water and oxygen from an alkali or alkaline earth metal, or from a transition metal, or from a metal of groups 13 or 14 of the Periodic Table, in which the minus a halogen salt with a heating rate of 1.0 K / min at 30 K / min, especially 1.0 K / min at 25 K / min or 20 K / min, preferably 3.5 K / min or from 3.7 K / min at 15 K / min or at 10 K / min, from room temperature (20 ° C). Surprisingly, it has been proven that the purity of halogen salts is a factor in the matter of corrosivity.
    It has now been found that a particularly low oxide content can be achieved in the melt at the mentioned heating rates. As can be seen from equation I, the oxide content of the melt is an essential parameter to evaluate the purity of the salt. Surprisingly, it has now been discovered that the oxide content of the melt can already be significantly reduced at low heating rates of, for example, 0.2 K / min or 0.3 K / min or 0.5 K / min, that is, less than 1.0 K / min. Small scale heating provided oxide contents of approximately 60%. In larger systems, heating rates can be very variable since the heat input by thermal conduction in the volume represents an essential limitation. Surprisingly, it has now been discovered that heating rates of 1 K / min or more result in significantly lower oxide contents of less than 30%. Especially suitable are heating rates within a range of 3.5 to 10 K / min because the time required for heating the halogen salt is within an acceptable range on the one hand; On the other hand, the oxide content can be kept low. Therefore, the heating rate is preferably 0.2 K / min or more, especially 0.5 K / min or more, preferably 1.0 K / min or more, or 3.5 K / min or more. However, a heating rate of more than 30 K / min does not perform better, and partly worsens, so that the heating rate is preferably 30 K / min or less, especially 25 K / min or less, or 20 K / min or less, especially 15 K / min or less, and preferably 10 K / min or less.
    Figure 1 illustrates measurements at different heating rates. As the halogen salt, MgCh is used in the form of commercially available hexahydrate, for example, from the company Alfa Aesar. Water molecules are present as water of crystallization and, due to the hygroscopic property of MgCh, as bound water. Only for the elimination of water of crystallization, it is generally considered to be particularly
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    effective heating as slowly as possible and, therefore, low heating rates. Surprisingly, it has now been discovered that very low heating rates have the opposite effect.
    In Figure 1, the heating rate in Kelvin per minute (K / min) is represented on the x-axis. The y-axis represents the amount of MgO in% by weight, based on 100% by weight of the total weight of the sample after heating. After heating, the sample consists of dry MgCh and MgO, which are formed due to hydrolysis. Thus, for example, a heating rate of 0.3 K / min produces a formation of 58% by weight of MgO, which means that it has a content of 58% by weight of MgO, based on the total weight of the sample .
    Heating is carried out from room temperature to the maximum temperature of the corresponding halogen salt. The maximum temperature is the melting temperature of the salt, which individually depends on the type of halogen salt. In a subsequent use, liquid salts are used above the melting temperature up to the maximum operating temperature. For a mixture of MgCh-KCl-NaCl, a preferred working range is 400 ° C to 700 ° C, for example.
    The salt purification process according to the invention allows the production of a mixture of halogen salt, solid or liquid, essentially free of water and oxygen, with a content of 90% by weight or more of pure halogen salt. These pure halogen salts react poorly to metallic materials.
    Halogen salts within the meaning of the present invention include individual halogen salts. However, mixtures of different halogen salts are also included. Due to the mixtures, the temperature range in which the halogen salts can be used can be extended in terms of minimum operating temperature. This is achieved by lower melting temperatures of salt mixtures compared to individual salts. Other properties, such as heat capacity, thermal stability and chemical stability, can also be adjusted in this way. Thus, for example, a halogen salt of an alkali metal can be combined with that of an alkaline earth metal in any mixing ratio. Currently, different halogen salts are also included, for example, an alkali metal or an alkaline earth metal or one of the mentioned transition metals or metals. Mixtures as used herein may include two, three, four or more different halogen salts with
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    different cations (for example, Li, Na, K, Ca, Mg, Sr, Ba, Zr, Ti, Cr, Mn, Fe, Cu, Zn, Al, Pb) and anions (for example, F, Cl, Br) .
    According to the invention, heating can be carried out continuously or discontinuously. "Continuously" means that the heating rate remains constant throughout the heating time, that is, the heating rate is adjusted at the beginning of the heating and remains unchanged subsequently, that is, there is a fixed heating rate.
    However, it is also possible for the heating rate to vary during heating. The corresponding variable heating rates allow the heating rate to adapt to the corresponding halogen salt. For example, if the sample must not contain water more clearly before the melting temperature is reached and, therefore, before the end point of the heating, then the heating rate can be increased so that the heating process takes less time. The cleavage of water (crystallization) from the halogen salt can be controlled by thermal analysis (determination of mass loss).
    Variable heating rates also allow a heating program with temperature ramps and isothermal segments. This means that the temperature is kept constant at those temperatures at which the excision of the water from the halogen salt proceeds particularly effectively, provided there is still excision of the water. Only after that, the temperature increases even more. Also in this case, the heating rate can be adjusted and adopted according to the mass loss observed until then. The temperatures at which the temperature is kept constant, that is, the isothermal segments, differ from one halogen salt to another and can be determined by those skilled in the art by means of thermal analysis.
    Surprisingly, it has been found that the oxide content in the melt can also be reduced by adding an additive. The additive is a reducing agent. It is added to the halogen salt in an amount of 1% by weight to 40% by weight, especially 5% by weight to 30% by weight, or 7% by weight to 25% by weight, especially 10% by weight. 20% weight by weight, or up to 15% by weight. These values mean that, starting from 100% by weight of the halogen salt, for example, additionally 10% by weight of the additive is added, so that an amount of 110% by weight is present after the addition of the additive.
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    Figure 2 shows the amount of magnesium oxide after the combination with an additive, currently NH4CL The y axis represents the amount of MgO in% by weight, based on 100% by weight of the total weight of the sample after heating. As in the measurements related to Figure 1, MgCh ^^ O was used as the halogen salt. Therefore, the addition of 20% by weight of NH4Cl results in the reduction of the oxide content, so that the sample contained only 5% by weight of MgO. In this case, the proportion of additive is established based on 100% by weight of MgCh. A sample with 20% by weight of additive should be understood in terms such that, for example, 20 g of additive are added to a sample of 100 g of halogen salt.
    Surprisingly, it has been found that a reduced oxide content is allowed simply by adding the additive. More preferably, heating at the preferred heating rates is effected in the presence of at least one additive, especially NH4CL. This process can achieve particularly good results in which the oxide content is particularly low.
    Figure 3 shows a measurement in the presence of 10% by weight of NH4CL MgCh-6H2O was used as the halogen salt and heated at different heating rates. The heating rates are represented on the x axis. The y-axis represents the amount of MgO in% by weight, based on 100% by weight of the total weight of the sample after heating. It is found that heating rates within a range of 3.7 K / min at 15 K / min or up to 10 K / min, in particular, produce particularly good results, that is, particularly low amounts of oxide in the chloride melt of magnesium
    The additive is preferably selected from ammonium chloride, silicon, magnesium and / or zirconium. Ammonium Chloride is particularly preferred. The additive is able to reduce the oxide content of the melt. There is a correlation between the amount of additive added and the oxide content in the melt. Therefore, preferably an amount of at least 5% by weight of additive is added, because smaller amounts do not result in a reduction of the oxide content such that corrosion is reduced to a significant degree.
    At the same time, however, the content of the additive should be kept as low as possible, since these are contaminants in the molten salt. For example, the zirconium, the
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    Magnesium or silicon react with the respective molten salts to form the respective oxide. Zirconium oxide or also silicon dioxide would then be visible as a precipitate in the molten salt, because they do not melt at the respective working temperature of the halogen salt. Although corrosivity is reduced in this case, other problems may arise. Therefore, ammonium chloride is preferred as an additive. In this case, ammonia (NH3) is obtained as a byproduct, which is a gas at the prevailing temperatures that can escape from the melt, so that there is no contamination of the molten salt.
    It has also been found that the oxide content of the melt is influenced by the atmosphere in which the melting occurs. Therefore, heating is preferably carried out under vacuum and / or in a protective atmosphere. The heating preferably takes place in a device that has at least one closed container (1) made of a halogen inert material, at least one device (5a, 5b) for adjusting the atmosphere inside the container and at least one external device ( 4) to adjust the temperature inside the container. Figure 6 schematically shows a device according to the invention in one embodiment. The device for adjusting the atmosphere inside the container is outside the container. Therefore, it is an external device (5a, 5b). This device for adjusting the atmosphere preferably comprises a vacuum pump (5a) and / or a gas supply line (5b) for an inert gas. In addition, the device (4) for adjusting the temperature inside the container is outside the container (1) and, therefore, is an external device.
    Now, the halogen salt (2) is inside the closed container (1) of the device according to the invention. The container (1) is not completely filled with the halogen salt (2). Rather, the interior of the container is divided into two zones. In one area, there is the halogen salt or, after heating, the melt of the halogen salt. Above, there is an atmosphere (3). At the beginning of the process, this area is usually filled with air. It has now been found that the oxide content in the melt can be reduced particularly well if the atmosphere (3), that is, the gas phase above the halogen salt (2), is free of oxygen if possible. This can be achieved by generating a vacuum. The pressure reached by the vacuum inside the vessel is preferably within a range of 10-3 mbar to 10-2 mbar (0.1-1 Pa). It is also possible to exchange the air against an inert gas, such as nitrogen, argon or helium. This can also prevent oxidation of the halogen salt and thereby reduce the oxide content in the melt. Therefore, by means of an inert gas, the oxide content
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    it can be reduced by at least 30% compared to air heating; under vacuum, values that are approximately 50% lower than those under the influence of air are reached.
    According to the invention, it is also possible to combine the vacuum and the inert gas. Therefore, for example, heating can take place under vacuum. As soon as the maximum temperature (melting temperature of the halogen salt) is reached, the vacuum is disconnected and the container is filled with an inert gas, especially with argon. It is also possible that the heating takes place under an inert gas. In all cases, the inert gas can be introduced into the container only in the atmosphere (3) above the molten salt, or it is also possible that the inert gas is introduced into the molten salt. In this way, the gas, which then exits into the atmosphere, can drag water from the halogen salt, which further improves the cleaning performance.
    More preferably, the heating of the molten salt is carried out under vacuum. When the halogen salt is exposed to the air after the drying process, the formation of oxides in it will take place again. This is due to the moisture contained in the air and the hygroscopic properties of the halogen salts. Surprisingly, it has now been discovered that the formation of oxides in the molten salts that were dried under vacuum can be avoided for a longer period of time than that of the molten salts that were dried in the air.
    The MgCh-6H2O that was dried under vacuum was exposed to ambient air after drying, as would be done in a later use. The oxide content was determined 24 hours after the drying process. During this time, the halogen salt was in the air. Similar measurements were made with MgCh ^^ O which was dried under an air atmosphere. Although the vacuum dried salt absorbed only 3% by weight of water in 24 hours, this value was 37% by weight for the air dried salt.
    Therefore, it is particularly preferred that heating takes place under vacuum.
    Figure 4 shows the results of the measurements in different atmospheres. Again, MgCh ^^ O was used as the halogen salt. The y-axis represents the amount of MgO in% by weight, based on 100% by weight of the total weight of the sample after heating. The different atmospheres (air, vacuum and inert gas (argon, Ar)) are explained on the x-axis. Surprisingly, it has been proven that the content of oxides can be
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    significantly reduce by vacuum or an inert gas.
    In addition, surprisingly, it has been found that repetition of the heating in a second, third or additional cycle is not necessary, but is quite disadvantageous. Therefore, heating is preferably performed only once. After repeated heating, the oxide content in the molten salt will increase again, so that in this case an effect opposite to all expectations can be observed. Figure 5 shows the results of the corresponding measurements. The amount of MgO in% by weight, based on 100% by weight of the total weight of the sample after heating, is represented on the y-axis, and the number of repetitions is mentioned on the x-axis. After more than 2 repetitions, no further increase in the oxide content is found. However, after the first repetition (2x), the oxide content is approximately double that after a single heating cycle (1x).
    The oxide content in the melt was determined respectively by acid / base titration and vacuum filtration. On titration, the salt was dissolved in a 1M HCl solution, and a titration was performed with a 1M NaOH solution in the presence of phenol-phthalein as an indicator. In vacuum filtration, the salt was dissolved in water and subsequently filtered. The oxides formed (magnesium oxide, sodium oxide) are not soluble in water and can subsequently be weighed after drying. The values shown in Figures 1 to 5 are the average values of several measurements with one or both procedures.
    The container of the device according to the invention is made of a halogen inert material. These include, for example, non-metallic compounds, especially oxygen-free compounds, preferably nitrides, carbides, borides, sulfides and silicides, especially boron nitride, silicon nitride, graphite, glassy carbon or silicon carbide, preferably boron nitride and vitreous carbon It is also possible to produce a container that has two or more of the aforementioned materials. Preferably, the container consists substantially of one of the aforementioned materials. In addition, specific steel alloys are suitable for producing a corresponding container, especially 1.44 xx, 1.45 xx, 1.48 xx and 2. xxx alloys.
    A device according to the invention may have one, two or more containers. Preferably, the device comprises two containers, in which a first container is first filled with the halogen salt, and in this case the molten salt is prepared. The second
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    container, which is separated from it, preferably has a volume greater than that of the first container and serves as a storage vessel for molten salt.
    The device according to the invention further comprises at least one device for adjusting the atmosphere within the container. This can be, for example, a vacuum pump or a gas port, through which the gas phase above the molten salt is kept free of oxygen, either generating a vacuum or introducing an inert gas.
    In addition, the device includes at least one device for adjusting the temperature inside the container. This container is the first container according to the above definition, instead of the storage container. The device for adjusting the temperature is an external heat source that is in direct contact with the halogen salt and allows a gradual increase in the temperature of the halogen salt.
    In another embodiment, the object of the present invention relates to a heat storage material for the high temperature range comprising at least one halogen salt essentially free of water and oxygen of an alkali or alkaline earth metal, or of a metal of transition, or of a metal of groups 13 or 14 of the periodic table, especially of an alkali metal or alkaline earth metal.
    Preferably, the content of the halogen salt in the heat storage material is 90% by weight or more, based on 100% by weight for the heat storage material, especially 92% by weight or more, especially 95% by weight or more, or 97% by weight or more, preferably 98% by weight or more, or 99% by weight or more. This means that the purity of the halogen salt is high, and the oxide content in the melt is therefore kept low, so that the corrosivity towards metals is low.
    Preferably, the halogen salt is a bromine, fluorine or chlorine salt.
    The alkali metal is preferably selected from lithium, sodium and / or potassium. The alkaline earth metal is preferably selected from magnesium, calcium, strontium and / or barium. The metal and transition metal are preferably selected from zirconium, titanium, chromium, manganese, iron, copper, zinc, aluminum and / or lead. The selection of the respective metals is carried out, in particular, according to the cost. Metals must be available at low cost in sufficient quantities and form a salt with the mentioned halogens, especially
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    with chlorine The alkali, alkaline earth, transition and individual metal salts can be combined with each other, especially to reduce the melting temperature, and also to otherwise establish properties of the molten halogen salt.
    In another embodiment, the present invention relates to the use of halogen salts essentially free of water and oxygen of an alkali or alkaline earth metal, or of a transition metal, or of a metal of groups 13 or 14 of the Periodic Table, as heat storage material for the high temperature range, that is, temperatures of 560 ° C or more, especially 700 ° C or more.
    Example:
    MgCh-6H2O was purchased from the company Alfa Aesar. At 100% by weight of this salt, 10% by weight of NH4Cl was added as an additive.
    The salt and the additive were heated at a heating rate of 7 K / min starting at room temperature (20 ° C) to a temperature of 350 ° C. This was done under vacuum, in which a pressure was established within a range of 10-3 to 10-2 mbar (0.1-1 Pa)
    Subsequently it was determined that the oxide content was 8.56% by weight.
    The same salt was dried without air additive at a heating rate of 0.3 K / min. The oxide content was 59.01% by weight.
    The results are listed for comparison in the following table.
     MgCb-6H2O
     Terms  Without additive Heating rate: 0.3 K / min Heating in air 10% by weight of NH4Cl as additive Heating rate: 7 K / min Vacuum heating
     Hydrolysis (MgO,% by weight)  59.01 8.56
    权利要求:
    Claims (14)
    [1]
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    1. A process for producing halogen salts essentially free of water and oxygen from an alkali or alkaline earth metal, or a transition metal, or a metal from groups 13 or 14 of the Periodic Table, in which at least A halogen salt is heated with a heating rate of 0.2 K / min at 30 K / min, especially 1.0 K / min at 10 K / min, starting at room temperature.
    [2]
    2. The process according to claim 1, characterized in that the heating is carried out continuously or discontinuously.
    [3]
    3. The process according to claims 1 or 2, characterized in that a reducing agent is added as an additive to the halogen salt during heating, especially in an amount between 1% by weight and 40% by weight, especially from 7% by weight to 30% by weight, especially from 10% by weight to 15% by weight, based on 100% by weight of the halogen salt without the additive.
    [4]
    4. The process according to claim 3, characterized in that the additive is selected from ammonium chloride (NH4CO, silicon, magnesium and / or zirconium, in particular, ammonium chloride.
    [5]
    5. The process according to any of claims 1 to 4, characterized in that the heating is carried out under vacuum or in a protective atmosphere.
    [6]
    6. The process according to any of claims 1 to 5, characterized in that the heating is carried out only once.
    [7]
    7. A heat storage material for the high temperature range comprising at least one halogen salt essentially free of water and oxygen from an alkali metal or an alkaline earth metal, or a transition metal, or a metal of groups 13 or 14 of the Periodic Table, especially of an alkali metal or an alkaline earth metal.
    [8]
    8. The heat storage material according to claim 7, characterized in that it contains the halogen salt in a proportion of 90% by weight or more, based on 100% by weight for the heat storage material,
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    especially 92% by weight or more, especially 95% by weight or more, or 97% by weight or more.
    [9]
    9. The heat storage material according to claims 7 or 8, characterized in that said halogen salt is a bromine, fluorine or chlorine salt.
    [10]
    10. The heat storage material according to any of claims 7 to 9, characterized in that said alkali metal is selected from lithium, sodium and / or potassium, and / or said alkaline earth metal is selected from magnesium, calcium, strontium and / or barium, and / or said transition metal and the metal are selected from zirconium, titanium, chromium, manganese, iron, copper, zinc, aluminum and / or lead.
    [11]
    11. A device for producing halogen salts essentially free of water and oxygen from an alkali or alkaline earth metal, or a transition metal, or a metal from groups 13 or 14 of the Periodic Table, especially an alkali metal or an alkaline earth metal, which includes
    a) at least one closed container (1) made of a halogen inert material,
    b) at least one external device (5a, 5b) to adjust the atmosphere within the
    container, and
    c) at least one external device (4) to adjust the temperature inside the container.
    [12]
    12. The device according to claim 11, characterized in that said container (1) is essentially made of one or more materials selected from nitrides, carbides, borides, sulfides and silicides, especially boron nitride, silicon nitride, graphite, carbon vitreous, silicon carbide, preferably boron nitride and vitreous carbon.
    [13]
    13. The device according to claims 11 or 12, characterized in that said device (5a, 5b) for adjusting the atmosphere inside the container comprises a vacuum pump (5a) and / or a gas supply line (5b) for an inert gas
    [14]
    14. Use of halogen salts essentially free of water and oxygen from a metal
    alkaline or alkaline earth, or a transition metal, or a metal of groups 13 or 14 of the Periodic Table, as heat storage material for the high temperature range.
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    同族专利:
    公开号 | 公开日
    DE102015224297A1|2017-06-08|
    ES2685342B2|2019-08-06|
    ES2685342R1|2018-10-22|
    WO2017093030A1|2017-06-08|
    US20180347912A1|2018-12-06|
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    FR2735779B1|1995-06-21|1997-07-18|Atochem Elf Sa|PARTICLES COMPRISING MAGNESIUM CHLORIDE, THE PROCESS FOR OBTAINING THEM AND POLYOLEFIN PARTICLES|DE102018222602A1|2018-12-20|2020-06-25|Deutsches Zentrum für Luft- und Raumfahrt e.V.|Method for storing an inorganic salt and storage device|
    DE102019106414A1|2019-03-13|2020-09-17|Deutsches Zentrum für Luft- und Raumfahrt e.V.|Contact component for a molten salt, use of a fiber-reinforced carbide ceramic material for a contact component, and method and device for conveying, transporting, storing a molten salt|
    CN113582579A|2020-12-11|2021-11-02|浙江大学|Metal manganese oxide heat storage material module and preparation method thereof|
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    DE102015224297|2015-12-04|
    DE102015224297.8A|DE102015224297A1|2015-12-04|2015-12-04|Heat storage material for the high temperature range and method for its production|
    PCT/EP2016/077967|WO2017093030A1|2015-12-04|2016-11-17|Heat storage material for the high-temperature range and method for the production thereof|
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