Method and apparatus for manufacturing lithium ceramic pebbles for tritium breeding materials

Abstract

The present invention relates to a method and an apparatus for manufacturing lithium ceramic pebbles for tritium breeding materials and, more specifically, to a method and an apparatus for manufacturing lithium ceramic pebbles by using a fluid system. According to an embodiment of the present invention, core-shell pebbles are manufactured using a fluid system, thereby obtaining pebbles that supplement the shortcomings, such as unstable thermal stability and low mechanical strength and lithium density, of existing pebble raw materials. Additionally, according to an embodiment of the present invention, the production of pebbles through a fluid system can achieve low manufacturing process costs and construct mass production systems, leading to potential applications in nuclear fusion blankets in the future.

Description

Method for manufacturing lithium ceramic pebbles for tritium breeder materials and device for manufacturing pebbles

[0001] The present invention relates to a method for manufacturing a lithium ceramic pebble for tritium breeder and a device for manufacturing the pebble, and more particularly, to a method for manufacturing a lithium ceramic pebble using a fluid system and a device for manufacturing the pebble.

[0002]

[0003] Recently, research is intensifying to verify the feasibility of nuclear fusion energy generation to achieve carbon neutrality. Nuclear fusion energy is produced by the thermal energy generated from the nuclear fusion reaction of tritium and deuterium. For continuous nuclear fusion energy generation, the production of tritium, an element rarely found in nature, is essential. To produce tritium, a tritium breeder pebble is placed in a blanket within a nuclear fusion reactor. The byproducts of the nuclear fusion reaction react with neutrons to produce tritium. Considering tritium production efficiency, the optimal shape for the pebble is a spherical shape with a diameter of 1 mm.

[0004] Most pebble manufacturing methods use wet methods, including the sol-gel method, the slurry droplet wetting method, and the rotating granulation method. A common wet method involves dropping spherical pebbles from the air using needles with a diameter of 0.3 to 0.8. The aforementioned pebble manufacturing methods have difficulties in obtaining pebbles with a sphericity close to 1 and a uniform size. In addition, approximately 100 tons of pebbles are required to apply breeder material to a nuclear fusion reactor, making mass production difficult with the aforementioned manufacturing methods, and the long time required to manufacture pebbles reduces economic feasibility.

[0005] Lithium oxide is a typical pebble raw material, and a material with a high lithium density and a short half-life is selected considering factors such as tritium production efficiency and half-life. Examples of the above-mentioned materials include Li4SiO4 (lithium orthosilicate), Li2TiO3 (lithium titanate), Li2O (lithium oxide), and Li2ZrO3 (lithium zirconate). Among the above-mentioned materials, Li4SiO4 and Li2O have the highest lithium density among the candidate materials, but their thermal and mechanical stability are low due to this. On the other hand, Li2TiO3 and Li2ZrO3 have higher thermal and mechanical stability than the two materials mentioned above, but their lithium density is low. A pebble manufacturing method that can offset the complementary advantages and disadvantages of pebble raw materials is needed.

[0006]

[0007] The present invention has been devised to solve the above-mentioned problem, and one embodiment of the present invention provides a method for manufacturing a lithium ceramic pebble for tritium breeder, which comprises manufacturing a pebble having a core-shell structure using a fluid system method to compensate for the shortcomings of lithium oxide materials, which are raw materials for the pebble.

[0008] In addition, another embodiment of the present invention provides a device for manufacturing lithium ceramic pebbles for tritium breeder.

[0009] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0010]

[0011] As a technical means for achieving the aforementioned technical task, one aspect of the present invention is,

[0012] A method for manufacturing a lithium ceramic pebble is provided, comprising the steps of: manufacturing a core-use dispersed phase and a shell-use dispersed phase; preparing a continuous phase; introducing the core-use dispersed phase, the shell-use dispersed phase, and the continuous phase into a fluid system to manufacture core-shell droplets; reacting the core-shell droplets with cations in the fluid system to form a core-shell gel; and drying and sintering the core-shell gel. The present invention provides a method for manufacturing a lithium ceramic pebble, characterized in that the core-use dispersed phase and the shell-use dispersed phase each include different oxides containing lithium.

[0013] The above lithium-containing oxide may be characterized by being at least one selected from the group consisting of Li4SiO4 (lithium orthosilicate), Li2TiO3 (lithium titanate), Li2O (lithium oxide), LiAlO2 (lithium aluminate), and Li2ZrO3 (lithium zirconate).

[0014] The oxide containing lithium included in the dispersion phase for the core may be a lithium-density oxide such as Li4SiO4 (lithium orthosilicate) or Li2O (lithium oxide), and the oxide containing lithium included in the dispersion phase for the shell may be LiAlO2 (lithium aluminate), Li2TiO3 (lithium titanate), or Li2ZrO3 (lithium zirconate).

[0015] The above-mentioned core-use dispersion phase or shell-use dispersion phase may be characterized by being manufactured by including a step of mixing an oxide containing lithium, a dispersion medium, a dispersant, and a solidifying agent; and a step of defoaming the slurry manufactured after the mixing. The dispersion medium may be characterized by being any one of distilled water and alcohol.

[0016] The above dispersant may be a surfactant, characterized by being either a cationic surfactant or an anionic surfactant.

[0017] The cationic surfactant may be characterized by including at least one selected from the group consisting of dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyltrimethylammonium bromide, cetyldimethylethylammonium bromide, alkyl-trimethyl-ammonium bromide, alkylamines, alkyl imidazolines, ethoxylated amines, quaternary compounds and quaternary esters, alkylamine oxides, lauramine oxide, dicetyldimonium chloride, cetrimonium chloride, primary, secondary or tertiary polyethoxylated fatty amine salts, quaternary ammonium salts, tetraalkylammoniums, alkylamidoalkylammoniums, trialkylbenzylammoniums, trialkylhydroxyalkylammoniums, alkylpyridinium chlorides or bromides, imidazoline derivatives, and cationic amine oxides.

[0018] The above anionic surfactant is sodium dodecyl sulfate, alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonate, alkyl ester sulfonate, alkyl sulfate, alkyl alkoxy sulfate, alkyl sulfonate, alkyl alkoxy carboxylate, alkyl alkoxylated sulfate, monoalkyl (ether) phosphate, dialkyl (ether) phosphate, sarcosinate, sulfosuccinate, sodium bis (2-ethylhexyl) sulfosuccinate, glycolic acid ethoxylate 4-nonylphenyl ether, isethionate, taurate, ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl Sulfate, Monoethanolamine Laureth Sulfate, Diethanolamine Lauryl Sulfate, Diethanolamine Laureth Sulfate, Lauric Acid Monoglyceride Sodium Sulfate, Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Potassium Lauryl Sulfate, Potassium Laureth Sulfate, Sodium Lauryl Phosphate, Sodium Tridecyl Phosphate, Sodium Behenyl Phosphate, Sodium Laureth-2 Phosphate, Sodium Ceteth-3 Phosphate, Sodium Trideceth-4 Phosphate, Sodium Dilauryl Phosphate, Sodium Ditridecyl Phosphate, Sodium Ditrideceth-6 Phosphate, Sodium Lauroyl Sarcosinate, Lauroyl Sarcosine, Cocoyl Sarcosine, Ammonium Cosyl Sulfate, Sodium Cosyl Sulfate, Sodium Trideceth sulfate, sodium tridecyl sulfate, ammonium trideceth sulfate, ammonium tridecyl sulfate, sodium cocoyl isethionate, disodium laureth sulfosuccinate, sodium methyl oleoyl taurate, sodium laureth carboxylate, sodium trideceth carboxylate, sodium lauryl sulfate, potassium cosyl sulfate, potassium lauryl sulfate, monoethanolamine cosyl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate,and may be characterized by including at least one from the group consisting of sodium dodecyl sulfate.

[0019] The above-mentioned solidifying agent may be characterized as being an alginate, and being either sodium alginate or potassium alginate.

[0020] The above mixing step may be characterized by mixing by stirring for 1 to 6 hours or mixing using a planetary ball mill for 30 minutes to 1 hour.

[0021] The above continuous phase may be characterized by being at least one selected from the group consisting of mineral oil, polyalphaolefin (PAO), alkylbenzene, alkylnaphthalene, polyvinyl ether, polyalkylene glycol, polycarbonate, polyol ester, ethylene alphaolefin copolymer, polybutene, aromatic ester, hindered ester, dibasic ester, paraffinic mineral oil, and naphthenic mineral oil as a non-hydrophilic solvent.

[0022] The above cation may be characterized by being at least one of calcium, magnesium, sodium, and potassium.

[0023] The above drying may be characterized by drying at 60 to 80°C for 12 to 24 hours, and the above sintering may be characterized by sintering at 900 to 1200°C for 1 to 5 hours.

[0024]

[0025] Another aspect of the present invention is:

[0026] A fluid system for manufacturing lithium ceramic pebbles is provided.

[0027] The fluid system may be characterized in that the length of the channel is 50 to 100 mm, the height is 0.1 to 5 mm, and the interior of the fluid system includes a channel into which a dispersed phase for the core is injected, a channel into which a dispersed phase for the shell is injected, and a channel into which a continuous phase is injected, and the width of the channel into which the dispersed phase for the core is injected is 0.5 to 1.5 mm, the width of the channel into which the dispersed phase for the shell is injected is 1.0 to 3 mm, and the width of the channel into which the continuous phase is injected is 1 to 4 mm.

[0028]

[0029] Another aspect of the present invention is:

[0030] A lithium ceramic pebble is provided, which is formed by drying and sintering a core-shell gel formed by reacting a core-shell droplet with a cation in a fluid system, the core-shell gel comprising a core including a first oxide containing lithium; and a shell including a second oxide containing lithium, which is provided on a surface of the core and is different from the first oxide.

[0031]

[0032] According to an embodiment of the present invention, by manufacturing a core-shell pebble using a fluid system, a pebble can be obtained that overcomes the shortcomings of existing pebble raw materials, such as unstable thermal stability, low mechanical strength, and lithium density.

[0033] In addition, according to one embodiment of the present invention, when a pebble is manufactured through a fluid system, the manufacturing process cost is low, and a mass production system can be built, so that it can be applied to a nuclear fusion blanket in the future.

[0034] The effects of the present invention are not limited to the above-described effects, and should be understood to include all effects that can be inferred from the composition of the invention described in the description or claims of the present invention.

[0035]

[0036] Figure 1 is a flowchart showing a process for manufacturing a lithium ceramic slurry for tritium breeding material and a core-shell pebble according to one embodiment of the present invention.

[0037] FIG. 2 is a drawing illustrating a process of injecting slurry for a core and shell and forming a core-shell according to one embodiment of the present invention.

[0038] FIG. 3 is an optical microscope photograph of a core-shell pebble manufactured according to one embodiment of the present invention.

[0039] FIG. 4 is a scanning electron microscope (SEM) photograph and an energy dispersive spectroscope (EDS) photograph of a cross-section of a core-shell pebble manufactured according to one embodiment of the present invention.

[0040] FIG. 5 is a graph comparing the mechanical strength of a core-shell pebble manufactured according to one embodiment of the present invention with the mechanical strength of a Li4SiO4 pebble.

[0041]

[0042] Hereinafter, the present invention will be described in more detail. However, the present invention may be implemented in various different forms, and the present invention is not limited to the embodiments described herein, but is defined only by the claims set forth below.

[0043] Additionally, the terminology used herein is solely for the purpose of describing specific embodiments and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. Throughout the specification of the present invention, the term "including" or "comprising" a component does not exclude other components, but rather implies the inclusion of other components, unless specifically stated otherwise.

[0044] Throughout the specification, when a part is said to be "connected (connected, contacted, or coupled)" to another part, this includes not only cases where it is "directly connected," but also cases where it is "indirectly connected" with another part in between. Furthermore, when a part is said to "include" a component, this does not exclude other components, but rather implies that it may include other components, unless otherwise specifically stated.

[0045] The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

[0046]

[0047] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0048]

[0049] Example 1: Preparation of slurry and core-shell pebble for core-shell pebble production

[0050] Figure 1 is a flowchart illustrating a method for manufacturing a core-shell pebble. Referring to Figure 1, to manufacture a pebble using a fluid system, a slurry for the core and shell was first prepared.

[0051] First, lithium oxide powder (Li4SiO4, Li2TiO3) was prepared, and distilled water as a dispersion medium, SDS (sodium dodecyl sulfate) as a dispersant, and sodium alginate as a solvent for pebble solidification were added to a beaker, and then stirred for more than 5 hours to prepare a slurry for the core (dispersion phase 1) and a slurry for the shell (dispersion phase 2). The sodium alginate has the effect of solidifying the pebbles by reacting with the collection solution during the process of collecting the spheroidized pebbles. SDS, used as a dispersant, is an anionic surfactant that has the effect of evenly dispersing lithium oxide particles within the slurry so that they do not clump together.

[0052] The manufactured core slurry and shell slurry were subjected to a slurry defoaming process using a vacuum pump and then applied to pebble production. Mineral oil was used as a non-hydrophilic solvent, different from dispersed phases 1 and 2, as the continuous phase.

[0053]

[0054] Experimental Example 1: Sphericity Analysis of Core-Shell Pebbles

[0055] The core-shell pebble manufactured in Example 1 was confirmed through an optical microscope. As shown in Fig. 3, the diameter of the core-shell pebble was measured to be 1.09 mm, and upon surface observation, it was confirmed that the inside and outside of the core-shell pebble had different shapes.

[0056]

[0057] Experimental Example 2: Scanning Electron Microscopy (SEM) Analysis for Cross-Section Observation of Core-Shell Pebbles

[0058] Figure 4 shows scanning electron microscope (SEM) images of a core-shell pebble cross-section manufactured using a fluid system, and the element distribution of the cross-section observed using energy dispersive spectroscopy (EDS). As can be seen in the SEM and EDS images, the core and shell of the pebble are clearly distinguished, and the EDS image shows that Si in Li4SiO4 in the core pebble and Ti in Li2TiO3 in the shell are properly arranged in the core-shell form of the pebble.

[0059]

[0060] Experimental Example 3: Mechanical Strength Analysis of Core-Shell Pebbles

[0061] Figure 5 shows the results of a comparative analysis of the mechanical strength enhancement of a core-shell pebble manufactured according to one embodiment of the present disclosure and a single-material Li4SiO4 pebble. It can be confirmed that the core-shell pebble exhibits improved mechanical strength compared to a single pebble composed solely of the core pebble raw material, Li4SiO4.

[0062]

[0063] The first aspect of this article is,

[0064] The present invention provides a method for manufacturing a lithium ceramic pebble, comprising: a step of manufacturing a core-type dispersed phase and a shell-type dispersed phase; a step of preparing a continuous phase; a step of introducing the core-type dispersed phase, the shell-type dispersed phase, and the continuous phase into a fluid system to manufacture core-shell droplets; a step of forming a core-shell gel by reacting the core-shell droplets with cations in the fluid system; and a step of drying and sintering the core-shell gel; wherein the core-type dispersed phase and the shell-type dispersed phase each comprise a different oxide containing lithium.

[0065]

[0066] Hereinafter, a method for manufacturing a lithium ceramic pebble according to the first aspect of the present invention will be described in detail.

[0067]

[0068] In one embodiment of the present invention, the lithium-containing oxide may be at least one selected from the group consisting of Li4SiO4 (lithium orthosilicate), Li2TiO3 (lithium titanate), LiAlO2 (lithium aluminate), Li2O (lithium oxide), and Li2ZrO3 (lithium zirconate), and more preferably, it may be any one of Li4SiO4 and Li2TiO3. Among the lithium oxides described above, Li4SiO4 and Li2O have high lithium densities among the candidate materials, but have low thermal stability and mechanical stability due to this. On the other hand, Li2TiO3, Li2ZrO3, and LiAlO2 have higher thermal stability and mechanical stability than the two materials, but have low lithium densities. In order to offset the complementary advantages and disadvantages of pebble raw materials, the tritium breeding efficiency of the pebble can be improved and the stability of the pebble can be improved by using a raw material with a high lithium density and low thermal stability as the core pebble and coating the pebble raw material with a raw material with high mechanical and thermal stability or a raw material that can protect the core pebble.

[0069] In one embodiment of the present invention, the oxide containing lithium included in the dispersion phase for the core may be Li4SiO4 (lithium orthosilicate) or Li2O (lithium oxide), and the oxide containing lithium included in the dispersion phase for the shell may be Li2TiO3 (lithium titanate), LiAlO2 (lithium aluminate), or Li2ZrO3 (lithium zirconate).

[0070] In one embodiment of the present invention, the core dispersion phase or the shell dispersion phase may be manufactured by including a step of mixing an oxide containing lithium, a dispersion medium, a dispersant, and a solidifying agent; and a step of defoaming the slurry manufactured after the mixing. In one embodiment of the present invention, the dispersion medium may be any one of distilled water and alcohol.

[0071] In one embodiment of the present invention, the dispersant is a surfactant, which may be any one of a cationic surfactant and an anionic surfactant, and the cationic surfactant is selected from the group consisting of dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyltrimethylammonium bromide, cetyldimethylethylammonium bromide, alkyl-trimethyl-ammonium bromide, alkylamines, alkyl imidazolines, ethoxylated amines, quaternary compounds and quaternary esters, alkylamine oxides, lauramine oxide, dicetyldimonium chloride, cetrimonium chloride, primary, secondary or tertiary polyethoxylated fatty amine salts, quaternary ammonium salts, tetraalkylammonium, alkylamidoalkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium, alkylpyridinium chloride or bromide, It may include at least one from the group consisting of imidazoline derivatives, and cationic amine oxides, wherein the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonate, alkyl ester sulfonate, alkyl sulfate, alkyl alkoxy sulfate, alkyl sulfonate, alkyl alkoxy carboxylate, alkyl alkoxylated sulfate, monoalkyl (ether) phosphate, dialkyl (ether) phosphate, sarcosinate, sulfosuccinate, sodium bis (2-ethylhexyl) sulfosuccinate, glycolic acid ethoxylate 4-nonylphenyl ether, isethionate, taurate, ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, Triethanolamine Laureth Sulfate, Monoethanolamine Lauryl Sulfate, Monoethanolamine Laureth Sulfate, Diethanolamine Lauryl Sulfate, Diethanolamine Laureth Sulfate, Lauric Acid Monoglyceride Sodium Sulfate, Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Potassium Lauryl Sulfate, Potassium Laureth Sulfate, Sodium Lauryl Phosphate, Sodium Tridecyl Phosphate, Sodium Behenyl Phosphate,Sodium Laureth-2 Phosphate, Sodium Ceteth-3 Phosphate, Sodium Trideceth-4 Phosphate, Sodium Dilauryl Phosphate, Sodium Ditridecyl Phosphate, Sodium Ditrideceth-6 Phosphate, Sodium Lauroyl Sarcosinate, Lauroyl Sarcozine, Cocoyl Sarcozine, Ammonium Cosyl Sulfate, Sodium Cosyl Sulfate, Sodium Trideceth Sulfate, Sodium Tridecyl Sulfate, Ammonium Trideceth Sulfate, Ammonium Tridecyl Sulfate, Sodium Cocoyl Isethionate, Disodium Laureth Sulfosuccinate, Sodium Methyl Oleoyl Taurate, Sodium Laureth Carboxylate, Sodium Trideceth Carboxylate, Sodium Lauryl Sulfate, Potassium Cosyl Sulfate, Potassium Lauryl Sulfate, It may be at least one selected from the group consisting of monoethanolamine cosyl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and sodium dodecyl sulfate. Preferably, it may be an anionic surfactant, and more preferably, it may be sodium dodecyl sulfate (SDS). SDS is an anionic surfactant that has the effect of evenly dispersing lithium oxide particles within the slurry so that they do not clump together.

[0072] In one embodiment of the present invention, the solidifying agent is an alginate, which may be either sodium alginate or potassium alginate, and preferably sodium alginate. Sodium alginate reacts with the collection solution during the process of collecting the spheroidized pebbles, thereby solidifying the pebbles.

[0073] In one embodiment of the present invention, the mixing step may be mixing by placing the mixture in a beaker and stirring for 1 to 6 hours or mixing using a planetary ball mill for 30 minutes to 1 hour. If the mixing time is less than 30 minutes, the mixing may be non-homogeneous, and the slurry defoaming process after mixing may not proceed properly. In addition, if the mixing time is 6 hours (stirring) or 1 hour (ball milling) or longer, the reaction time may be excessively long, which may cause a problem of an overall increase in process costs.

[0074] In one embodiment of the present invention, the continuous phase may be at least one selected from the group consisting of mineral oil, polyalphaolefin (PAO), alkylbenzene, alkylnaphthalene, polyvinyl ether, polyalkylene glycol, polycarbonate, polyol ester, ethylene alphaolefin copolymer, polybutene, aromatic ester, hindered ester, dibasic ester, paraffinic mineral oil, and naphthenic mineral oil as a non-hydrophilic solvent, and preferably may be mineral oil.

[0075] In one embodiment of the present invention, the cation may be one or more of calcium, magnesium, and potassium.

[0076] In one embodiment of the present invention, the drying may be performed at 60 to 80°C for 12 to 24 hours, and the sintering may be performed at 900 to 1200°C for 1 to 5 hours. If the drying range is outside the above range, a problem of reduced mechanical strength of the core-shell pebble may occur, and if the sintering range is outside the above range, a problem of reduced reaction or increased pebble crystallinity may occur.

[0077]

[0078] The second aspect of the original text is,

[0079] A fluid system for manufacturing lithium ceramic pebbles is provided.

[0080] Detailed explanations of parts that overlap with the first aspect of the present application have been omitted, but the explanations of the first aspect of the present application may be applied equally even if the explanations are omitted in the second aspect.

[0081]

[0082] Hereinafter, the fluid system according to the second aspect of the present invention will be described in detail.

[0083] In one embodiment of the present invention, the fluid system may be characterized in that the length of the channel is 50 to 100 mm, the height is 0.1 to 5 mm, the interior of the fluid system includes a channel into which a dispersed phase for the core is injected, a channel into which a dispersed phase for the shell is injected, and a channel into which a continuous phase is injected, and the width of the channel into which the dispersed phase for the core is injected is 0.5 to 1.5 mm, the width of the channel into which the dispersed phase for the shell is injected is 1.0 to 3 mm, and the width of the channel into which the continuous phase is injected is 1 to 4 mm.

[0084] The shape of the lithium ceramic pebble produced from the above fluid system is influenced by the Weber number and the Capillary number, which are concepts for analyzing fluid flow. The two concepts mentioned above are commonly influenced by the viscosity of the fluid flowing from the fluid system and the dimensions of the system channels. Therefore, in the present invention, a lithium ceramic pebble was produced by considering the flow of the dispersed phase and the continuous phase based on the above two concepts. The sol-gel reaction between alginate and calcium ions was applied based on the fluid system. As shown in Fig. 2, the slurry for the core, which is the dispersed phase 1 injected from channel 3, is fused with the slurry for the shell, which is the dispersed phase 2 injected from channel 2, to cause fluid flow, and droplets are formed by the continuous phase injected from channel 1. At this time, the slurries of the dispersed phase 1 and the dispersed phase 2 include alginate to induce solidification of the droplets, and the continuous phase is a fluid having properties opposite to those of the dispersed phase. The formed droplets are captured by a continuous flow into a collection device outside the fluid system, and the droplets react with calcium ions inside the collection device to form a gel.

[0085]

[0086] The third aspect of this foundation is,

[0087] A lithium ceramic pebble is provided, which is formed by drying and sintering a core-shell gel formed by reacting a core-shell droplet with a cation in a fluid system, the core-shell gel comprising a core including a first oxide containing lithium; and a shell including a second oxide containing lithium, which is provided on a surface of the core and is different from the first oxide.

[0088]

[0089] Detailed descriptions of overlapping parts with the first and second aspects of the present application have been omitted, but the contents described with respect to the first and second aspects of the present application may be equally applied even if the description is omitted with respect to the third aspect.

[0090]

[0091] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0092] The scope of the present invention is indicated by the claims set forth below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

[0093]

[0094] According to one embodiment of the present invention, by manufacturing a core-shell pebble using a fluid system, a pebble can be obtained that overcomes the shortcomings of existing pebble raw materials, such as unstable thermal stability, low mechanical strength, and lithium density. Therefore, this method enables a low-cost manufacturing process, enables the establishment of a mass production system, and is expected to be applicable to future nuclear fusion blankets, thereby significantly contributing to related industries.

Claims

1. A step of manufacturing a dispersion phase for the core and a dispersion phase for the shell; Steps to prepare a continuous phase; A step of manufacturing core-shell droplets by introducing the dispersed phase for the core, the dispersed phase for the shell, and the continuous phase into a fluid system; A step in which the core-shell droplets react with cations in a fluid system to form a core-shell gel; and A step of drying and sintering the core-shell gel; A method for manufacturing a lithium ceramic pebble, characterized in that the dispersed phase for the core and the dispersed phase for the shell each contain different oxides containing lithium.

2. In paragraph 1, A method for manufacturing a lithium ceramic pebble, characterized in that the oxide containing lithium is at least one selected from the group consisting of Li4SiO4 (lithium orthosilicate), Li2TiO3 (lithium titanate), Li2O (lithium oxide), LiAlO2 (lithium aluminate), and Li2ZrO3 (lithium zirconate).

3. In paragraph 1, The oxide containing lithium included in the dispersion phase for the core is Li4SiO4 (lithium orthosilicate) or Li2O (lithium oxide). A method for manufacturing a lithium ceramic pebble, characterized in that the oxide containing lithium included in the dispersion phase for the shell is Li2TiO3 (lithium titanate), LiAlO2 (lithium aluminate), or Li2ZrO3 (lithium zirconate).

4. In paragraph 1, The above dispersed phase for the core or dispersed phase for the shell is, A method for manufacturing a lithium ceramic pebble, characterized in that it comprises the steps of mixing an oxide containing lithium, a dispersing medium, a dispersant, and a solidifying agent; and the step of defoaming a slurry manufactured after the mixing.

5. In paragraph 3 or 4, A method for manufacturing lithium ceramic pebbles, characterized in that the dispersion medium is either distilled water or alcohol.

6. In paragraph 3 or 4, A method for manufacturing lithium ceramic pebbles, characterized in that the dispersant is a surfactant, and is either a cationic surfactant or an anionic surfactant.

7. In paragraph 6, A method for producing a lithium ceramic pebble, characterized in that the cationic surfactant comprises at least one selected from the group consisting of dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyltrimethylammonium bromide, cetyldimethylethylammonium bromide, alkyl-trimethyl-ammonium bromide, alkylamines, alkyl imidazolines, ethoxylated amines, quaternary compounds and quaternary esters, alkylamine oxides, lauramine oxide, dicetyldimonium chloride, cetrimonium chloride, primary, secondary or tertiary polyethoxylated fatty amine salts, quaternary ammonium salts, tetraalkylammoniums, alkylamidoalkylammoniums, trialkylbenzylammoniums, trialkylhydroxyalkylammoniums, alkylpyridinium chlorides or bromides, imidazoline derivatives, and cationic amine oxides.

8. In paragraph 6, The above anionic surfactant is sodium dodecyl sulfate, alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonate, alkyl ester sulfonate, alkyl sulfate, alkyl alkoxy sulfate, alkyl sulfonate, alkyl alkoxy carboxylate, alkyl alkoxylated sulfate, monoalkyl (ether) phosphate, dialkyl (ether) phosphate, sarcosinate, sulfosuccinate, sodium bis (2-ethylhexyl) sulfosuccinate, glycolic acid ethoxylate 4-nonylphenyl ether, isethionate, taurate, ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl Sulfate, Monoethanolamine Laureth Sulfate, Diethanolamine Lauryl Sulfate, Diethanolamine Laureth Sulfate, Lauric Acid Monoglyceride Sodium Sulfate, Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Potassium Lauryl Sulfate, Potassium Laureth Sulfate, Sodium Lauryl Phosphate, Sodium Tridecyl Phosphate, Sodium Behenyl Phosphate, Sodium Laureth-2 Phosphate, Sodium Ceteth-3 Phosphate, Sodium Trideceth-4 Phosphate, Sodium Dilauryl Phosphate, Sodium Ditridecyl Phosphate, Sodium Ditrideceth-6 Phosphate, Sodium Lauroyl Sarcosinate, Lauroyl Sarcosine, Cocoyl Sarcosine, Ammonium Cosyl Sulfate, Sodium Cosyl Sulfate, Sodium Trideceth sulfate, sodium tridecyl sulfate, ammonium trideceth sulfate, ammonium tridecyl sulfate, sodium cocoyl isethionate, disodium laureth sulfosuccinate, sodium methyl oleoyl taurate, sodium laureth carboxylate, sodium trideceth carboxylate, sodium lauryl sulfate, potassium cosyl sulfate, potassium lauryl sulfate, monoethanolamine cosyl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate,A method for manufacturing a lithium ceramic pebble, characterized in that it comprises at least one from the group consisting of sodium dodecyl sulfate.

9. In paragraph 3 or 4, A method for manufacturing a lithium ceramic pebble, characterized in that the solidifying agent is an alginate, and is one of sodium alginate and potassium alginate.

10. In paragraph 3 or 4, A method for manufacturing a lithium ceramic pebble, characterized in that the mixing step comprises mixing by stirring for 1 to 65 hours or mixing using a planetary ball mill for 30 minutes to 1 hour.

11. In paragraph 1, A method for manufacturing a lithium ceramic pebble, characterized in that the continuous phase is at least one selected from the group consisting of mineral oil, polyalphaolefin (PAO), alkylbenzene, alkylnaphthalene, polyvinyl ether, polyalkylene glycol, polycarbonate, polyol ester, ethylene alphaolefin copolymer, polybutene, aromatic ester, hindered ester, dibasic ester, paraffinic mineral oil, and naphthenic mineral oil as a non-hydrophilic solvent.

12. In paragraph 1, A method for manufacturing a lithium ceramic pebble, characterized in that the cation is at least one of calcium, magnesium, sodium, and potassium.

13. In paragraph 1, The above drying is performed at 60 to 80°C for 12 to 24 hours, A method for manufacturing lithium ceramic pebbles, characterized in that the above sintering is performed at 900 to 1200°C for 1 to 5 hours.

14. A fluid system for manufacturing the lithium ceramic pebble of paragraph 1.

15. In paragraph 12, The above fluid system, The length of the channel is 50 to 100 mm, the height is 0.1 to 5 mm, The interior of the fluid system includes a channel into which a dispersed phase for the core is injected, a channel into which a dispersed phase for the shell is injected, and a channel into which a continuous phase is injected. The width of the channel into which the dispersed phase for the core is injected is 0.5 to 1.5 mm, The width of the channel into which the dispersion phase for the above shell is injected is 1.0 to 3 mm, A fluid system, characterized in that the width of the channel into which the continuous phase is injected is 1 to 4 m.

16. A lithium ceramic pebble formed by drying and sintering core-shell droplets formed by reacting with cations in a fluid system to form a core-shell gel, a core comprising a first oxide containing lithium; and A lithium ceramic pebble comprising a shell comprising a second oxide comprising lithium, which is different from the first oxide and is provided on the surface of the core.

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