WO2024258224A1 - Method for producing calcium hydroxide from limestone or calcium compound - Google Patents

Method for producing calcium hydroxide from limestone or calcium compound Download PDF

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WO2024258224A1
WO2024258224A1 PCT/KR2024/008175 KR2024008175W WO2024258224A1 WO 2024258224 A1 WO2024258224 A1 WO 2024258224A1 KR 2024008175 W KR2024008175 W KR 2024008175W WO 2024258224 A1 WO2024258224 A1 WO 2024258224A1
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calcium hydroxide
weight
parts
producing calcium
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Korean (ko)
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허남회
박희선
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Sogang University Research Foundation
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium

Definitions

  • Calcium hydroxide (Ca(OH) 2 ) is a strong alkaline substance that is environmentally friendly and harmless to the human body, and is therefore widely used in various industries such as construction, iron and steel, water treatment, agriculture, and food.
  • calcium hydroxide is used to safely treat industrial waste, and since direct landfill of acidic industrial waste can cause fatal environmental disasters by contaminating the soil, calcium hydroxide is used as a neutralizing agent in the treatment process of large amounts of waste acid generated in steelmaking and metal refining processes. Recently, it has been used as a neutralizing agent in high-concentration acidic waste water containing phosphoric acid ( H3PO4 ) or hydrofluoric acid (HF) in the treatment of semiconductor process waste water.
  • H3PO4 phosphoric acid
  • HF hydrofluoric acid
  • Calcium hydroxide with low purity is used as a neutralizing agent for acid wastewater, an inorganic coagulant in water and sewage treatment, and a purifying agent in improving the water quality of lakes and rivers. Meanwhile, calcium hydroxide fine particles with a purity of 90% or higher are used to reduce air pollution and play a significant role in reducing pollutants such as sulfur oxides (SO x ), nitrogen oxides (NO x ), and carbon monoxide, which are environmental pollutants.
  • High-grade calcium hydroxide with a purity of 95% or higher and good color and powder shape is used as a food additive; or for refining sugar or raw sugar.
  • the conventional method for manufacturing calcium hydroxide is a relatively easy process of reacting calcium oxide (CaO) and water, as shown in the following reaction formula 1.
  • CaO calcium oxide
  • the raw material for manufacturing calcium hydroxide is manufactured by heat-treating limestone (CaCO 3 ) at a high temperature of 900°C or higher, the energy cost is high.
  • the conventional method for manufacturing calcium hydroxide is a process that emits a large amount of carbon dioxide, as shown in the following reaction formula 2, and thus has the problem of large greenhouse gas emissions.
  • limestone the raw material ore of calcium hydroxide
  • Patent Document 1 Republic of Korea Patent Publication No. 10-2013-7025562.
  • the present invention provides a method for producing calcium hydroxide from limestone or a calcium compound.
  • the first aspect of the present invention provides a method for producing calcium hydroxide, comprising catalytically reacting limestone or a calcium compound; nitric acid; and hydrogen to obtain calcium hydroxide and an ammonia compound.
  • the second aspect of the present invention provides a ruthenium oxide catalyst, which is represented by the following chemical formula I and has a monoclinic crystal structure, and is used in the method for producing calcium hydroxide according to the first aspect:
  • the method for producing calcium hydroxide according to the embodiments of the present invention does not require a high-temperature heat treatment process to produce calcium oxide (CaO), and thus can be performed at a lower temperature than conventional calcium hydroxide production methods, thereby realizing an economical process with lower energy costs.
  • the method for producing calcium hydroxide according to the embodiments of the present invention can implement an environmentally friendly process that does not emit carbon dioxide compared to conventional methods.
  • the method for producing calcium hydroxide according to the embodiments of the present invention may produce expensive ammonia compounds as a side effect.
  • the yield of calcium hydroxide obtainable using the method for producing calcium hydroxide according to the embodiments of the present invention may be about 60% or more, about 70% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more, about 96% or more, or about 97% or more.
  • the catalyst used in the method for producing calcium hydroxide according to the embodiments of the present invention is economical because it does not melt or lose its structure during the reaction, so the reaction can be performed for a long time, and can be separated and recovered after the reaction and reused.
  • the catalyst used in the method for producing calcium hydroxide according to the embodiments of the present invention has excellent reaction activity and can produce calcium hydroxide in a high yield.
  • Figure 1 is a schematic diagram of a reaction in which nitric acid and hydrogen containing calcium carbonate (CaCO 3 ) are catalytically reacted to obtain calcium hydroxide (Ca(OH) 2 ) and an ammonia compound, in one embodiment of the present invention.
  • FIG. 2 is a powder X-ray diffraction (PXRD) graph of Ca(OH) 2 manufactured according to Example 1 of the present application.
  • Figure 3 is a powder X-ray diffraction analysis graph of NH 4 NO 3 manufactured according to Example 1 of the present invention.
  • Figure 4 is a powder X-ray diffraction analysis graph of limestone, a reactant of Example 5 of the present invention.
  • Figure 5 is a powder X-ray diffraction analysis graph of Ca(OH) 2 manufactured according to Example 5 of the present invention.
  • step of ⁇ or “step of ⁇ ” as used throughout this specification do not mean “step for ⁇ .”
  • the term "combination(s) thereof" included in the expressions in the Makushi format means one or more mixtures or combinations selected from the group consisting of the components described in the Makushi format, and means including one or more selected from the group consisting of said components.
  • references to “A and/or B” mean “A or B, or A and B.”
  • the first aspect of the present invention provides a method for producing calcium hydroxide, comprising catalytically reacting limestone or a calcium compound; nitric acid; and hydrogen to obtain calcium hydroxide and an ammonia compound.
  • the limestone is an ore containing calcium carbonate (CaCO 3 ) as its main component, and may contain other components, and the scope to which the present invention can be applied may be expanded.
  • the limestone may contain marble, calcite, feldspar, limestone, chalk, glacierite, seashells, egg shells, and coral containing calcium carbonate.
  • the calcium compound may include one or more selected from process by-products, wastes and salts containing calcium.
  • the process by-product or the waste may include at least one selected from slag and waste concrete.
  • the salt means a salt containing calcium, and may not be limited.
  • the salt may include at least one selected from a chloride, an oxide, a sulfate, a carbonate, a nitrate, a phosphate, a sulfate, a silicate, and a hydrate thereof containing calcium, and non-limiting examples thereof include a chloride (e.g., CaCl 2 ), a nitrate (e.g., Ca(NO 3 ) 2 ), an oxide (e.g., CaO), a silicate (e.g., calcium silicate), or a sulfur oxide (e.g., CaSO 4 ).
  • the concentration of the nitric acid may be from about 0.1 M to about 16 M, but may not be limited thereto. In one embodiment of the present invention, the concentration of the nitric acid is from about 0.1 M to about 16 M, from about 0.1 M to about 14 M, from about 0.1 M to about 12 M, from about 0.1 M to about 10 M, from about 0.1 M to about 8 M, from about 0.1 M to about 6 M, from about 0.1 M to about 5 M, from about 0.1 M to about 4 M, from about 0.1 M to about 3 M, from about 0.1 M to about 2 M, from about 0.1 M to about 1 M, from about 1 M to about 16 M, from about 1 M to about 14 M, from about 1 M to about 12 M, from about 1 M to about 10 M, from about 1 M to about 8 M, from about 1 M to about 6 M, from about 1 M to about 5 M, from about 1 M to about 4 M, from about 1 M to about 3 M, about 1 M to about 2 M, about
  • the concentration of the nitric acid when the concentration of the nitric acid is less than about 0.1 M, the production rate of calcium hydroxide may be slowed, and when the concentration of the nitric acid is more than about 16 M, the yield ratio of calcium hydroxide may be decreased due to the high acidity.
  • the catalyst may be selected from a metal, alloy or oxide including at least one selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), molybdenum (Mo), indium (In), tin (Sn), phosphorus (P), aluminum (Al), silicon (Si), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au).
  • the catalyst may include ruthenium oxide represented by the following chemical formula I:
  • the reaction activity may be enhanced, but may not be limited thereto.
  • the diameter of the particles of the catalyst may be about 10 nm or less, about 8 nm or less, about 6 nm or less, or about 4 nm or less.
  • the catalyst does not melt or its structure collapse during the reaction, so the reaction can be performed for a long period of time.
  • the catalyst can be separated and recovered after the reaction is completed and reused.
  • a catalyst comprising ruthenium oxide represented by the chemical formula I for the reaction, but another metal or metal salt may be additionally used as an auxiliary catalyst.
  • the catalyst may be used in an amount of about 0.1 to about 10 parts by weight based on 100 parts by weight of the limestone or the calcium compound. In one embodiment of the present invention, the catalyst is present in an amount of from about 0.1 part by weight to about 10 parts by weight, from about 0.1 part by weight to about 9 parts by weight, from about 0.1 part by weight to about 8 parts by weight, from about 0.1 part by weight to about 7 parts by weight, from about 0.1 part by weight to about 6 parts by weight, from about 0.1 part by weight to about 5 parts by weight, from about 0.1 part by weight to about 4 parts by weight, from about 0.1 part by weight to about 3 parts by weight, from about 0.1 part by weight to about 2 parts by weight, from about 0.1 part by weight to about 1 part by weight, from about 1 part by weight to about 10 parts by weight, from about 1 part by weight to about 9 parts by weight, from about 1 part by weight to about 8 parts by weight, from about 1 part by weight to about 7 parts by weight, from about 1 part by weight
  • the reaction time of the hydrogenation reaction may become longer and/or the reaction may not be completed, and when the catalyst is used in an amount of about 10 parts by weight or more with respect to 100 parts by weight of the limestone or the calcium compound, the speed of the hydrogenation reaction may become faster, but the separation efficiency may decrease in the process of separating the product and the catalyst.
  • the catalytic reaction may be performed at a temperature range of about 20°C to about 200°C. In one embodiment of the present invention, the catalytic reaction is performed at a temperature of about 20°C to about 200°C, about 20°C to about 190°C, about 20°C to about 180°C, about 20°C to about 170°C, about 20°C to about 160°C, about 20°C to about 150°C, about 20°C to about 140°C, about 20°C to about 130°C, about 30°C to about 200°C, about 30°C to about 190°C, about 30°C to about 180°C, about 30°C to about 170°C, about 30°C to about 160°C, about 30°C to about 150°C, about 30°C to about 140°C, about 30°C to about 130°C, about 40°C to about 200°C, about 40°C to about The catalytic reaction may be performed at a temperature range of about 190°C, about 40°C, about a temperature range
  • the catalytic reaction may be performed in a hydrothermal reactor.
  • the pressure of the hydrogen may be from about 0.1 MPa to about 10 MPa. In one embodiment of the present invention, the pressure of the hydrogen is from about 0.1 MPa to about 10 MPa, from about 0.1 MPa to about 9 MPa, from about 0.1 MPa to about 8 MPa, from about 0.1 MPa to about 7 MPa, from about 0.1 MPa to about 6 MPa, from about 0.1 MPa to about 5 MPa, from about 0.1 MPa to about 4 MPa, from about 0.1 MPa to about 3 MPa, from about 1 MPa to about 10 MPa, from about 1 MPa to about 9 MPa, from about 1 MPa to about 8 MPa, from about 1 MPa to about 7 MPa, from about 1 MPa to about 6 MPa, from about 1 MPa to about 5 MPa, from about 1 MPa to about 4 MPa, from about 1 MPa to about 3 MPa, from about 1.5 MPa to about 10 MPa, from about 1.5 MPa to about 9 MPa, about 1.5 MPa to about 8 MP
  • the reaction progress rate when the pressure of the hydrogen is about 0.1 MPa or lower, the reaction progress rate may be very slow, and when the pressure of the hydrogen is about 10 MPa or higher, the reaction may not progress smoothly. In one embodiment of the present disclosure, the pressure of the hydrogen may be most preferably about 2 MPa.
  • the calcium hydroxide may be obtained as a precipitate of the solution through filtration, but is not limited thereto.
  • the ammonia may be obtained in the form of an ammonia compound by adding carbon dioxide or an acid to the solution, but is not limited thereto.
  • separating the catalyst may be further included.
  • separating a precipitate including the catalyst and the calcium hydroxide may be further included.
  • the method may further include adding an inorganic acid to the product of the hydrogenation reaction to obtain an ammonium salt.
  • the inorganic acid may be, but is not limited to, sulfuric acid, nitric acid, hydrochloric acid, or acetic acid.
  • the ammonium salt may be ammonium sulfate ((NH 4 ) 2 SO 4 ), ammonium hydrogen sulfate (NH 4 HSO 4 ), ammonium nitrate (NH 4 NO 3 ), ammonium hydrochloride (NH 4 Cl), or ammonium acetate (NH 4 CH 3 CO 2 ), and the ammonium salt may vary depending on the type of the inorganic acid.
  • the yield of ammonium ion can be calculated through the weight of the ammonium salt obtained by additionally adding an inorganic acid, but this may be an additional value experimentally confirmed in the process of obtaining an ammonium salt for actual separation and use of ammonium ion after generating ammonia from nitrate ion.
  • the second aspect of the present invention provides a ruthenium oxide catalyst, which is represented by the following chemical formula I and has a monoclinic crystal structure, and is used in the method for producing calcium hydroxide according to the first aspect:
  • x (atomic ratio of hydrogen) is greater than 0 and less than or equal to 4, greater than 0 and less than or equal to about 3.5, greater than 0 and less than or equal to about 3, greater than 0 and less than or equal to about 2.5, greater than 0 and less than or equal to about 2, greater than 0 and less than or equal to about 1.5, greater than 0 and less than or equal to about 1.2, from about 0.1 to about 4, from about 0.1 to about 3.5, from about 0.1 to about 3, from about 0.1 to about 2.5, from about 0.1 to about 2, from about 0.1 to about 1.5, from about 0.1 to about 1.2, from about 0.2 to about 3.5, from about 0.2 to about 3, from about 0.2 to about 2.5, from about 0.2 to about 2, from about 0.2 to about 1.5, from about 0.2 to about 1.2, from about 0.3 to about 3.5, about 0.3 to about 3, about 0.3 to about 2.5, about 0.3 to about 2, about 0.3 to about 1.5, about 0.3 to about 0.3 to about 3.5, about 0.3 to about 3,
  • the ratio of hydrogen when the ratio of hydrogen is from about 0.6 to about 1.4, the monoclinic ruthenium oxide may be easier to produce.
  • x in the chemical formula I when x in the chemical formula I is 0, a structural transition into a tetragonal rutile structure ruthenium oxide may occur, so it is preferable to maintain the hydrogen content.
  • the atomic ratio of hydrogen included in the chemical formula I can be calculated by thermo-gravimetric analysis (TGA). Specifically, in the analysis using the thermo-gravimetric analysis, a solid sample can be placed in a platinum container and the weight change can be measured while increasing the temperature. All hydrogen included in the monoclinic ruthenium oxide (H x RuO 2 ) is removed and converted to tetragonal ruthenium oxide (RuO 2 ). The amount of hydrogen can be quantitatively analyzed from the weight change according to the temperature.
  • TGA thermo-gravimetric analysis
  • the ruthenium oxide catalyst has an incident angle (2 ⁇ ) determined by X-ray powder diffraction measurement (Cu K ⁇ line) of 18.38° ⁇ 2 ⁇ ⁇ 18.42°, 25.45° ⁇ 2 ⁇ ⁇ 25.51°, 26.26° ⁇ 2 ⁇ ⁇ 26.32°, 33.45° ⁇ 2 ⁇ ⁇ 33.51°, 35.28° ⁇ 2 ⁇ ⁇ 35.34°, 36.24° ⁇ 2 ⁇ ⁇ 36.30°, 37.32° ⁇ 2 ⁇ ⁇ 37.38°, 39.55° ⁇ 2 ⁇ ⁇ 39.61°, 40.61° ⁇ 2 ⁇ ⁇ 40.67°, 41.46° ⁇ 2 ⁇ ⁇ 41.52°, 49.17° ⁇ 2 ⁇ Diffraction peaks can be observed at each position of ⁇ 49.23°, 52.31° ⁇ 2 ⁇ ⁇ 52.37°, 54.03° ⁇ 2 ⁇ ⁇ 54.09°, 54.70° ⁇ 2 ⁇ ⁇ 54.76°, 55.95° ⁇ 2 ⁇
  • the ruthenium oxide catalyst may have diffraction peaks observed at positions where the incident angles (2 ⁇ ) determined by X-ray powder diffraction measurement (Cu K ⁇ line) are 18.40°, 25.48°, 26.29°, 33.48°, 35.31°, 36.27°, 37.35°, 39.58°, 40.64°, 41.49°, 49.20°, 52.34°, 54.06°, 54.73°, 55.98°, 58.00°, 60.43°, 61.95°, 63.97°, 65.82°, and 69.16°, respectively.
  • the ruthenium oxide catalyst may have a structure of a monoclinic space group P2 1 /c, C2/m, P2/c, C2/c, P2/m, or P2 1 /m, but may not be limited thereto.
  • the unit cell of the monoclinic crystal structure of the ruthenium oxide catalyst can be defined by lattice constants a to c and edge angle beta ( ⁇ ).
  • 5 ⁇ a ⁇ 6 ⁇ , 5 ⁇ b ⁇ 6 ⁇ , and 5 ⁇ c ⁇ 6 ⁇ , and the beta ( ⁇ ) angle may be about 110° to about 120°.
  • a to c are each about 5 ⁇ to about 6 ⁇ , about 5.1 ⁇ to about 6 ⁇ , about 5.2 ⁇ to about 6 ⁇ , about 5.3 ⁇ to about 6 ⁇ , about 5 ⁇ to about 5.8 ⁇ , about 5.1 ⁇ to about 5.8 ⁇ , about 5.2 ⁇ to about 5.8 ⁇ , about 5.3 ⁇ to about 5.8 ⁇ , about 5 ⁇ to about 5.6 ⁇ , about 5.1 ⁇ to about 5.6 ⁇ , about 5.2 ⁇ to about 5.6 ⁇ , about 5.3 ⁇ to about 5.6 ⁇ , about 5 ⁇ to about 5.4 ⁇ , about 5.1 ⁇ to about 5.4 ⁇ , about 5.2 ⁇ to about 5.4 ⁇ , about 5.3 ⁇ to about 5.4 ⁇ or about 5.35 ⁇ to about 5.4 ⁇ , wherein b can be about 5 ⁇ to about 6 ⁇ , about 5 ⁇ to about 5.8 ⁇ , about 5 ⁇ to about 5.6 ⁇ , about 5 ⁇ to about 5.4 ⁇ , about 5
  • a 5.3533 ⁇
  • b 5.0770 ⁇
  • c 5.3532 ⁇
  • the beta ( ⁇ ) angle may be 115.9074°, but may not be limited thereto.
  • the residual solution was analyzed by ultraviolet-visible spectroscopy, and nitrogen oxide ions (NO 3 - and NO 2 - ) were not detected, confirming that all nitrate ions were reduced to ammonia or nitrogen.
  • Nitric acid was added to the residual solution and evaporated to obtain crystals, which were confirmed to be ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction (Fig. 3).
  • the mass of the obtained NH 4 NO 3 is 0.301 g (3.76 mmol), and the yield calculated based on HNO 3 is 94.1%.
  • the hydrogenation reaction was performed in the same manner as in Example 1, except that the reaction was performed under a hydrogen pressure of 5.0 MPa.
  • the precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 through X-ray powder diffraction analysis.
  • the mass of the obtained Ca(OH) 2 was 0.139 g (1.88 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 93.8%.
  • nitric acid was added to the residual solution and evaporated to obtain crystals, which were identified as ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction.
  • the mass of the obtained NH 4 NO 3 was 0.313 g (3.91 mmol), and the yield calculated based on HNO 3 was 97.8%.
  • the hydrogenation reaction was performed in the same manner as in Example 1, except that 2 mL of distilled water was additionally added and the reaction was performed.
  • the precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 through X-ray powder diffraction analysis.
  • the mass of the obtained Ca(OH) 2 was 0.125 g (1.69 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 84.3%.
  • nitric acid was added to the residual solution and evaporated to obtain crystals, which were identified as ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction.
  • the mass of the obtained NH 4 NO 3 was 0.294 g (3.67 mmol), and the yield calculated based on HNO 3 was 91.9%.
  • the hydrogenation reaction was performed in the same manner as in Example 1, except that the reaction was performed at 60°C.
  • the precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 through X-ray powder diffraction analysis.
  • the mass of the obtained Ca(OH) 2 was 0.087 g (1.17 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 58.7%.
  • nitric acid was added to the residual solution and evaporated to obtain crystals, which were identified as ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction.
  • the mass of the obtained NH 4 NO 3 was 0.183 g (2.29 mmol), and the yield calculated based on HNO 3 was 57.2%.
  • the hydrogenation reaction was performed in the same manner as in Example 1, except that 0.2 g of commercial limestone (Fig. 4) was dissolved in nitric acid instead of calcium carbonate as a reactant, and the undissolved solid was separated and used for the reaction.
  • the precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 by X-ray powder diffraction analysis (Fig. 5).
  • the mass of the obtained Ca(OH) 2 is 0.107 g (1.44 mmol).
  • the reaction was carried out in the same manner as in Example 1, except that ruthenium powder (7.6 mg, 0.075 mmol) was used as a catalyst. After the reaction was completed, the yield of the obtained Ca(OH) 2 was less than 5%, so a very small amount was obtained.
  • the reaction was performed in the same manner as in Example 1, except that platinum powder (14.6 mg, 0.075 mmol) was used as a catalyst. After completion of the reaction, the mass of the obtained Ca(OH) 2 was 0.115 g (1.55 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 77.6%. The mass of the obtained NH 4 NO 3 was 0.232 g (2.88 mmol), and the yield calculated based on HNO 3 was 72.5%.
  • the reaction was performed in the same manner as in Example 1, except that palladium powder (8.0 mg, 0.075 mmol) was used as a catalyst. After completion of the reaction, the mass of the obtained Ca(OH) 2 was 0.120 g (1.62 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 81.0%. The mass of the obtained NH 4 NO 3 was 0.256 g (3.20 mmol), and the yield calculated based on HNO 3 was 80.0%.
  • the reaction was carried out in the same manner as in Example 1, except that nickel powder (7.1 mg, 0.075 mmol) was used as a catalyst. After the reaction was completed, the yield of the obtained Ca(OH) 2 was less than 5%, so a very small amount was obtained.

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Abstract

The present application relates to a method for producing calcium hydroxide from limestone or a calcium compound. The method for producing calcium hydroxide according to embodiments of the present application can implement an eco-friendly process that does not discharge carbon dioxide compared to a conventional method. Also, the method can implement an economical process with low energy costs since the method does not employ a high-temperature heat treatment process for producing calcium oxide (CaO) and thus is performed at a low temperature compared to a conventional method for producing calcium hydroxide.

Description

석회석 또는 칼슘 화합물로부터 수산화 칼슘을 제조하는 방법Method for producing calcium hydroxide from limestone or calcium compounds

본원은 석회석 또는 칼슘 화합물로부터 수산화 칼슘을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing calcium hydroxide from limestone or a calcium compound.

수산화 칼슘(Ca(OH)2)은 강한 염기성을 띠는 염기성 물질로서, 친환경적이고 인체에 무해한 원소이기 때문에 건축, 제철, 수처리, 농업, 식품 등 산업계 전반에서 다양하게 사용되고 있다. 일례로서, 수산화 칼슘은 산업폐기물을 안전하게 처리하기 위해서 사용되며, 산성의 산업 폐기물을 직접 매립할 경우 토양을 오염시키는 치명적인 환경 재해를 일으키기 때문에, 수산화 칼슘은 제강 및 금속 제련 공정에서 발생하는 대량의 폐산수 처리 공정의 중화제로서 사용된다. 최근에는 반도체 공정 폐수 처리시, 인산(H3PO4) 또는 불산(HF)을 포함하는 고농도 산성 폐수의 중화제로서 사용되고 있다.Calcium hydroxide (Ca(OH) 2 ) is a strong alkaline substance that is environmentally friendly and harmless to the human body, and is therefore widely used in various industries such as construction, iron and steel, water treatment, agriculture, and food. For example, calcium hydroxide is used to safely treat industrial waste, and since direct landfill of acidic industrial waste can cause fatal environmental disasters by contaminating the soil, calcium hydroxide is used as a neutralizing agent in the treatment process of large amounts of waste acid generated in steelmaking and metal refining processes. Recently, it has been used as a neutralizing agent in high-concentration acidic waste water containing phosphoric acid ( H3PO4 ) or hydrofluoric acid (HF) in the treatment of semiconductor process waste water.

순도가 낮은 수산화 칼슘은 산성 폐수의 중화 처리제, 상하수 처리 시 무기 응집제, 및 호수나 강물의 수질환경 개선 시 정화제로서 사용된다. 한편, 순도가 90% 이상인 수산화 칼슘 미립자 분말은 대기오염 저감용으로 사용되며, 환경오염 물질인 황산화물(SOx), 질소산화물(NOx), 일산화탄소 등 공해물질을 현저히 감소시키는 역할을 한다. 순도가 95% 이상이며, 색도 및 분말 형상이 좋은 고품위 수산화 칼슘은 식품 첨가물; 또는 제당 또는 원당 정제용으로 사용되고 있다.Calcium hydroxide with low purity is used as a neutralizing agent for acid wastewater, an inorganic coagulant in water and sewage treatment, and a purifying agent in improving the water quality of lakes and rivers. Meanwhile, calcium hydroxide fine particles with a purity of 90% or higher are used to reduce air pollution and play a significant role in reducing pollutants such as sulfur oxides (SO x ), nitrogen oxides (NO x ), and carbon monoxide, which are environmental pollutants. High-grade calcium hydroxide with a purity of 95% or higher and good color and powder shape is used as a food additive; or for refining sugar or raw sugar.

종래의 수산화 칼슘의 제조 방법은, 하기 반응식 1과 같이, 산화 칼슘(CaO)과 물을 반응시키는 비교적 용이한 공정이나, 수산화 칼슘의 제조 원료인 산화 칼슘은 석회석(CaCO3)을 900℃ 이상의 고온에서 열처리하여 제조되기 때문에, 에너지 비용이 크다. 또한, 종래의 수산화 칼슘의 제조 방법은 하기 반응식 2와 같이 다량의 이산화탄소를 배출하는 공정이므로 온실 가스의 배출량이 크다는 문제점을 가지고 있다. The conventional method for manufacturing calcium hydroxide is a relatively easy process of reacting calcium oxide (CaO) and water, as shown in the following reaction formula 1. However, since calcium oxide, the raw material for manufacturing calcium hydroxide, is manufactured by heat-treating limestone (CaCO 3 ) at a high temperature of 900°C or higher, the energy cost is high. In addition, the conventional method for manufacturing calcium hydroxide is a process that emits a large amount of carbon dioxide, as shown in the following reaction formula 2, and thus has the problem of large greenhouse gas emissions.

[반응식 1][Reaction Formula 1]

CaO + H2O → Ca(OH)2 CaO + H 2 O → Ca(OH) 2

[반응식 2][Reaction Formula 2]

CaCO3 → CaO + CO2 CaCO 3 → CaO + CO 2

또한, 수산화 칼슘의 원료 광석인 석회석은 탄산칼슘(CaCO3) 이외에 다른 불순물을 포함하고 있다. 따라서, 석회석을 분쇄하여 분리 과정 없이 그대로 사용하는 종래의 수산화 칼슘 제조 공정의 경우, 생성물로서 불순물이 포함된 순도가 낮은 산화 칼슘이 수득된다. 수산화 칼슘 제조시 물을 첨가하더라도 부산물로 생성된 불순물은 잔류하기 때문에, 고품위 수산화 칼슘을 제조하기 위해서는 불순물을 제거하는 추가적인 공정이 반드시 필요하다.In addition, limestone, the raw material ore of calcium hydroxide, contains impurities other than calcium carbonate (CaCO 3 ). Therefore, in the case of the conventional calcium hydroxide manufacturing process in which limestone is crushed and used as is without a separation process, low-purity calcium oxide containing impurities is obtained as a product. Even if water is added during the manufacturing of calcium hydroxide, the impurities generated as byproducts remain, so an additional process for removing impurities is absolutely necessary to manufacture high-quality calcium hydroxide.

따라서, 고온의 열처리 과정을 거치지 않고 고순도의 수산화 칼슘을 제조하는 경제적이고 친환경적인 저온 제조 공정 기술의 개발이 필요한 실정이다. Therefore, there is a need to develop an economical and environmentally friendly low-temperature manufacturing process technology for producing high-purity calcium hydroxide without going through a high-temperature heat treatment process.

[선행기술문헌][Prior art literature]

(특허문헌 1) 대한민국공개특허공보 제10-2013-7025562호.(Patent Document 1) Republic of Korea Patent Publication No. 10-2013-7025562.

본원은 석회석 또는 칼슘 화합물로부터 수산화 칼슘을 제조하는 방법을 제공하고자 한다.The present invention provides a method for producing calcium hydroxide from limestone or a calcium compound.

그러나, 본원이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다.However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

본원의 제 1 측면은, 석회석 또는 칼슘 화합물; 질산; 및 수소를 촉매 반응시켜 수산화 칼슘 및 암모니아 화합물을 수득하는 것을 포함하는, 수산화 칼슘의 제조 방법을 제공한다.The first aspect of the present invention provides a method for producing calcium hydroxide, comprising catalytically reacting limestone or a calcium compound; nitric acid; and hydrogen to obtain calcium hydroxide and an ammonia compound.

본원의 제 2 측면은, 하기 화학식 Ⅰ로서 표시되며, 단사정계 구조를 갖는, 루테늄 산화물 촉매로서, 제 1 측면에 따른 수산화 칼슘의 제조 방법에 사용되는, 루테늄 산화물 촉매를 제공한다:The second aspect of the present invention provides a ruthenium oxide catalyst, which is represented by the following chemical formula Ⅰ and has a monoclinic crystal structure, and is used in the method for producing calcium hydroxide according to the first aspect:

[화학식 Ⅰ][Chemical Formula I]

HxRuO2;H x RuO 2 ;

상기 화학식 Ⅰ에서, 0< x ≤4임.In the above chemical formula I, 0< x ≤4.

본원의 구현예들에 따른 수산화 칼슘의 제조 방법은 산화칼슘(CaO)을 생성하기 위한 고온의 열처리 공정을 거치지 않으므로 종래의 수산화 칼슘 제조 방법과 비교하여 낮은 온도에서 수행되어 에너지 비용이 적은 경제적인 공정을 구현할 수 있다.The method for producing calcium hydroxide according to the embodiments of the present invention does not require a high-temperature heat treatment process to produce calcium oxide (CaO), and thus can be performed at a lower temperature than conventional calcium hydroxide production methods, thereby realizing an economical process with lower energy costs.

본원의 구현예들에 따른 수산화 칼슘의 제조 방법은 종래의 방법과 비교하여 이산화탄소를 배출하지 않는 친환경적인 공정을 구현할 수 있다.The method for producing calcium hydroxide according to the embodiments of the present invention can implement an environmentally friendly process that does not emit carbon dioxide compared to conventional methods.

본원의 구현예들에 따른 수산화 칼슘의 제조 방법은 부수적으로 고가의 암모니아 화합물을 제조할 수 있다.The method for producing calcium hydroxide according to the embodiments of the present invention may produce expensive ammonia compounds as a side effect.

본원의 구현예들에 따른 수산화 칼슘의 제조 방법을 이용하여 수득할 수 있는 수산화 칼슘의 수득 비율은 약 60% 이상, 약 70% 이상, 약 80% 이상, 약 85% 이상, 약 90% 이상, 약 95% 이상, 약 96% 이상, 또는 약 97% 이상일 수 있다.The yield of calcium hydroxide obtainable using the method for producing calcium hydroxide according to the embodiments of the present invention may be about 60% or more, about 70% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more, about 96% or more, or about 97% or more.

본원의 구현예들에 따른 수산화 칼슘의 제조 방법에 사용되는 촉매는 반응 중 녹거나 구조가 붕괴되지 않아, 장시간 반응이 수행될 수 있고, 반응 후 분리 및 회수되어 재사용될 수 있으므로, 경제적이다.The catalyst used in the method for producing calcium hydroxide according to the embodiments of the present invention is economical because it does not melt or lose its structure during the reaction, so the reaction can be performed for a long time, and can be separated and recovered after the reaction and reused.

본원의 구현예들에 따른 수산화 칼슘의 제조 방법에 사용되는 촉매는 반응 활성이 우수하고, 높은 수율로 수산화 칼슘을 제조할 수 있다.The catalyst used in the method for producing calcium hydroxide according to the embodiments of the present invention has excellent reaction activity and can produce calcium hydroxide in a high yield.

도 1은, 본원의 일 실시예에 있어서, 탄산칼슘(CaCO3)을 포함하는 질산 및 수소를 촉매 반응시켜 수산화 칼슘(Ca(OH)2) 및 암모니아 화합물을 수득하는 반응의 모식도이다.Figure 1 is a schematic diagram of a reaction in which nitric acid and hydrogen containing calcium carbonate (CaCO 3 ) are catalytically reacted to obtain calcium hydroxide (Ca(OH) 2 ) and an ammonia compound, in one embodiment of the present invention.

도 2는, 본원의 실시예 1에 따라 제조된 Ca(OH)2의 분말 X-선 회절 분석(powder X-ray diffraction; PXRD) 그래프이다.FIG. 2 is a powder X-ray diffraction (PXRD) graph of Ca(OH) 2 manufactured according to Example 1 of the present application.

도 3은, 본원의 실시예 1에 따라 제조된 NH4NO3의 분말 X-선 회절분석 그래프이다.Figure 3 is a powder X-ray diffraction analysis graph of NH 4 NO 3 manufactured according to Example 1 of the present invention.

도 4는, 본원의 실시예 5의 반응물인 석회석의 분말 X-선 회절 분석 그래프이다.Figure 4 is a powder X-ray diffraction analysis graph of limestone, a reactant of Example 5 of the present invention.

도 5는, 본원의 실시예 5에 따라 제조된 Ca(OH)2의 분말 X-선 회절 분석 그래프이다.Figure 5 is a powder X-ray diffraction analysis graph of Ca(OH) 2 manufactured according to Example 5 of the present invention.

이하, 첨부한 도면을 참조하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본원의 구현예 및 실시예를 상세히 설명한다. 그러나 본원은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 구현예 및 실시예에 한정되지 않는다. 그리고 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.Hereinafter, with reference to the attached drawings, the implementation examples and embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the present invention may be implemented in various different forms and is not limited to the implementation examples and embodiments described herein. In addition, in order to clearly explain the present invention in the drawings, parts that are not related to the description are omitted, and similar parts are assigned similar drawing reference numerals throughout the specification.

본원 명세서 전체에서, 어떤 부분이 다른 부분과 "연결"되어 있다고 할 때, 이는 "직접적으로 연결"되어 있는 경우뿐 아니라, 그 중간에 다른 소자를 사이에 두고 "전기적으로 연결"되어 있는 경우도 포함한다.Throughout this specification, when a part is said to be "connected" to another part, this includes not only the case where it is "directly connected" but also the case where it is "electrically connected" with another element in between.

본원 명세서 전체에서, 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.Throughout this specification, when it is said that an element is "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where there is another element between the two elements.

본원 명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

본 명세서에서 사용되는 정도의 용어 "약", "실질적으로" 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본원의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다.The terms “about,” “substantially,” and the like, as used in this specification, are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings stated are presented, and are used to prevent unscrupulous infringers from unfairly utilizing the disclosure in which exact or absolute values are stated to aid the understanding of the present application.

본원 명세서 전체에서 사용되는 정도의 용어 “~ 하는 단계” 또는 “~의 단계”는 “~를 위한 단계”를 의미하지 않는다.The terms “step of ~” or “step of ~” as used throughout this specification do not mean “step for ~.”

본원 명세서 전체에서, 마쿠시 형식의 표현에 포함된 "이들의 조합(들)"의 용어는 마쿠시 형식의 표현에 기재된 구성 요소들로 이루어진 군에서 선택되는 하나 이상의 혼합 또는 조합을 의미하는 것으로서, 상기 구성 요소들로 이루어진 군에서 선택되는 하나 이상을 포함하는 것을 의미한다.Throughout this specification, the term "combination(s) thereof" included in the expressions in the Makushi format means one or more mixtures or combinations selected from the group consisting of the components described in the Makushi format, and means including one or more selected from the group consisting of said components.

본원 명세서 전체에서, "A 및/또는 B"의 기재는, "A 또는 B, 또는 A 및 B"를 의미한다.Throughout this specification, references to “A and/or B” mean “A or B, or A and B.”

이하, 본원의 구현예를 상세히 설명하였으나, 본원이 이에 제한되지 않을 수 있다.Below, the implementation examples of the present invention are described in detail, but the present invention may not be limited thereto.

본원의 제 1 측면은, 석회석 또는 칼슘 화합물; 질산; 및 수소를 촉매 반응시켜 수산화 칼슘 및 암모니아 화합물을 수득하는 것을 포함하는, 수산화 칼슘의 제조 방법을 제공한다.The first aspect of the present invention provides a method for producing calcium hydroxide, comprising catalytically reacting limestone or a calcium compound; nitric acid; and hydrogen to obtain calcium hydroxide and an ammonia compound.

본원의 일 구현예에 있어서, 상기 석회석은 탄산 칼슘(CaCO3)을 주성분으로 하는 광석으로서 다른 성분들이 포함될 수 있고, 본 발명이 적용될 수 있는 범위에서 확장될 수 있다. 예를 들어, 상기 석회석은 탄산 칼슘을 포함하는 대리석, 방해석, 선석, 석회석, 백악, 빙주석, 조개껍데기, 난각(egg shell), 및 산호가 포함될 수 있다.In one embodiment of the present invention, the limestone is an ore containing calcium carbonate (CaCO 3 ) as its main component, and may contain other components, and the scope to which the present invention can be applied may be expanded. For example, the limestone may contain marble, calcite, feldspar, limestone, chalk, glacierite, seashells, egg shells, and coral containing calcium carbonate.

본원의 일 구현예에 있어서, 상기 칼슘 화합물은 칼슘을 포함하는 공정 부산물, 폐기물 및 염에서 선택되는 하나 이상을 포함하는 것일 수 있다.In one embodiment of the present invention, the calcium compound may include one or more selected from process by-products, wastes and salts containing calcium.

본원의 일 구현예에 있어서, 상기 공정 부산물 또는 상기 폐기물은 슬래그 및 폐콘크리트에서 선택되는 하나 이상을 포함하는 것일 수 있다.In one embodiment of the present invention, the process by-product or the waste may include at least one selected from slag and waste concrete.

본원의 일 구현예에 있어서, 본 발명이 적용될 수 있는 한, 상기 염은 칼슘을 포함하는 염을 의미하며, 제한되지 않을 수 있다. 본원의 일 구현예에 있어서, 상기 염은, 칼슘을 포함하는, 염화염, 산화염, 황화염, 탄산염, 질산염, 인산염, 황산염, 규산염 및 이들의 수화물에서 선택되는 하나 이상을 포함하는 것일 수 있으며, 비제한적인 예로서 염화물(예. CaCl2), 질산화물(예. Ca(NO3)2), 산화물(예. CaO), 규산화물(예. 규산칼슘), 또는 황산화물(예. CaSO4) 일 수 있다.In one embodiment of the present invention, as far as the present invention can be applied, the salt means a salt containing calcium, and may not be limited. In one embodiment of the present invention, the salt may include at least one selected from a chloride, an oxide, a sulfate, a carbonate, a nitrate, a phosphate, a sulfate, a silicate, and a hydrate thereof containing calcium, and non-limiting examples thereof include a chloride (e.g., CaCl 2 ), a nitrate (e.g., Ca(NO 3 ) 2 ), an oxide (e.g., CaO), a silicate (e.g., calcium silicate), or a sulfur oxide (e.g., CaSO 4 ).

본원의 일 구현예에 있어서, 상기 질산의 농도는 약 0.1 M 내지 약 16 M인 것일 수 있으나, 이에 제한되지 않을 수 있다. 본원의 일 구현예에 있어서, 상기 질산의 농도는 약 0.1 M 내지 약 16 M, 약 0.1 M 내지 약 14 M, 약 0.1 M 내지 약 12 M, 약 0.1 M 내지 약 10 M, 약 0.1 M 내지 약 8 M, 약 0.1 M 내지 약 6 M, 약 0.1 M 내지 약 5 M, 약 0.1 M 내지 약 4 M, 약 0.1 M 내지 약 3 M, 약 0.1 M 내지 약 2 M, 약 0.1 M 내지 약 1 M, 약 1 M 내지 약 16 M, 약 1 M 내지 약 14 M, 약 1 M 내지 약 12 M, 약 1 M 내지 약 10 M, 약 1 M 내지 약 8 M, 약 1 M 내지 약 6 M, 약 1 M 내지 약 5 M, 약 1 M 내지 약 4 M, 약 1 M 내지 약 3 M, 약 1 M 내지 약 2 M, 약 2 M 내지 약 16 M, 약 2 M 내지 약 14 M, 약 2 M 내지 약 12 M, 약 2 M 내지 약 10 M, 약 2 M 내지 약 8 M, 약 2 M 내지 약 6 M, 약 2 M 내지 약 5 M, 약 2 M 내지 약 4 M, 약 2 M 내지 약 3 M, 약 3 M 내지 약 16 M, 약 3 M 내지 약 14 M, 약 3 M 내지 약 12 M, 약 3 M 내지 약 10 M, 약 3 M 내지 약 8 M, 약 3 M 내지 약 6 M, 약 3 M 내지 약 5 M, 약 3 M 내지 약 4 M, 약 4 M 내지 약 16 M, 약 4 M 내지 약 14 M, 약 4 M 내지 약 12 M, 약 4 M 내지 약 10 M, 약 4 M 내지 약 8 M, 약 4 M 내지 약 6 M, 약 4 M 내지 약 5 M, 약 5 M 내지 약 16 M, 약 5 M 내지 약 14 M, 약 5 M 내지 약 12 M, 약 5 M 내지 약 10 M, 약 5 M 내지 약 8 M, 약 5 M 내지 약 6 M, 약 6 M 내지 약 16 M, 약 6 M 내지 약 14 M, 약 6 M 내지 약 10 M, 약 6 M 내지 약 8 M, 약 6 M 내지 약 7 M, 약 8 M 내지 약 16 M, 약 8 M 내지 약 14 M, 약 8 M 내지 약 12 M, 약 8 M 내지 약 10 M, 약 10 M 내지 약 16 M, 약 10 M 내지 약 14 M, 약 10 M 내지 약 12 M, 약 12 M 내지 약 16 M, 약 12 M 내지 약 14 M, 또는 약 14 M 내지 약 16 M인 것일 수 있다. 본원의 일 구현예에 있어서, 상기 질산의 농도가 약 0.1 M 미만인 경우에는 수산화 칼슘의 생성 속도가 느려지고, 상기 질산의 농도가 약 16 M 초과인 경우에는 높은 산성도로 인하여 수산화 칼슘의 수득 비율이 감소할 수 있다.In one embodiment of the present invention, the concentration of the nitric acid may be from about 0.1 M to about 16 M, but may not be limited thereto. In one embodiment of the present invention, the concentration of the nitric acid is from about 0.1 M to about 16 M, from about 0.1 M to about 14 M, from about 0.1 M to about 12 M, from about 0.1 M to about 10 M, from about 0.1 M to about 8 M, from about 0.1 M to about 6 M, from about 0.1 M to about 5 M, from about 0.1 M to about 4 M, from about 0.1 M to about 3 M, from about 0.1 M to about 2 M, from about 0.1 M to about 1 M, from about 1 M to about 16 M, from about 1 M to about 14 M, from about 1 M to about 12 M, from about 1 M to about 10 M, from about 1 M to about 8 M, from about 1 M to about 6 M, from about 1 M to about 5 M, from about 1 M to about 4 M, from about 1 M to about 3 M, about 1 M to about 2 M, about 2 M to about 16 M, about 2 M to about 14 M, about 2 M to about 12 M, about 2 M to about 10 M, about 2 M to about 8 M, about 2 M to about 6 M, about 2 M to about 5 M, about 2 M to about 4 M, about 2 M to about 3 M, about 3 M to about 16 M, about 3 M to about 14 M, about 3 M to about 12 M, about 3 M to about 10 M, about 3 M to about 8 M, about 3 M to about 6 M, about 3 M to about 5 M, about 3 M to about 4 M, about 4 M to about 16 M, about 4 M to about 14 M, about 4 M to about 12 M, about 4 M to about 10 M, about 4 M to about 8 M, about 4 M to about 6 M, about 4 M to about 5 M, about 5 M to about 16 M, about 5 M to about 14 M, about 5 M to about 12 M, about 5 M to about 10 M, about 5 M to about 8 M, about 5 M to about 6 M, about 6 M to about 16 M, about 6 M to about 14 M, about 6 M to about 10 M, about 6 M to about 8 M, about 6 M to about 7 M, about 8 M to about 16 M, about 8 M to about 14 M, about 8 M to about 12 M, about 8 M to about 10 M, about 10 M to about 16 M, about 10 M to about 14 M, about 10 M to about 12 M, about 12 M to about 16 M, about 12 M to about 14 M, or about 14 M It may be about 16 M. In one embodiment of the present invention, when the concentration of the nitric acid is less than about 0.1 M, the production rate of calcium hydroxide may be slowed, and when the concentration of the nitric acid is more than about 16 M, the yield ratio of calcium hydroxide may be decreased due to the high acidity.

본원의 일 구현예에 있어서, 촉매는 타이타늄(Ti), 바나듐(V), 크로뮴(Cr), 망가니즈(Mn), 철(Fe), 코발트(Co), 니켈(Ni), 구리(Cu), 아연(Zn), 몰리브데넘(Mo), 인듐(In), 주석(Sn), 인(P), 알루미늄(Al), 실리콘(Si), 루테늄(Ru), 로듐(Rh), 팔라듐(Pd), 은(Ag), 텅스텐(W), 레늄(Re), 오스뮴(Os), 이리듐(Ir), 백금(Pt), 및 금(Au)에서 선택되는 하나 이상을 포함하는 금속, 합금 또는 산화물에서 선택되는 것일 수 있다.In one embodiment of the present invention, the catalyst may be selected from a metal, alloy or oxide including at least one selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), molybdenum (Mo), indium (In), tin (Sn), phosphorus (P), aluminum (Al), silicon (Si), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au).

본원의 일 구현예에 있어서, 상기 촉매는 하기 화학식 Ⅰ로서 표시되는 루테늄 산화물을 포함하는 것일 수 있다:In one embodiment of the present invention, the catalyst may include ruthenium oxide represented by the following chemical formula I:

[화학식 Ⅰ][Chemical Formula I]

HxRuO2; H x RuO 2;

상기 화학식 Ⅰ에서, 0< x ≤4임.In the above chemical formula I, 0< x ≤4.

본원의 일 구현예에 있어서, 상기 촉매의 입자의 직경이 약 10 nm 이하인 경우, 반응 활성이 증진될 수 있으나, 이에 제한되지 않을 수 있다. 본원의 일 구현예에 있어서, 상기 촉매의 입자의 직경은 약 10 nm 이하, 약 8 nm 이하, 약 6 nm 이하, 또는 약 4 nm 이하일 수 있다.In one embodiment of the present invention, when the diameter of the particles of the catalyst is about 10 nm or less, the reaction activity may be enhanced, but may not be limited thereto. In one embodiment of the present invention, the diameter of the particles of the catalyst may be about 10 nm or less, about 8 nm or less, about 6 nm or less, or about 4 nm or less.

본원의 일 구현예에 있어서, 상기 촉매는 반응 중 녹거나 구조가 붕괴되지 않아, 장시간 동안 반응이 수행될 수 있다.In one embodiment of the present invention, the catalyst does not melt or its structure collapse during the reaction, so the reaction can be performed for a long period of time.

본원의 일 구현예에 있어서, 상기 촉매는 반응이 완료된 후 분리 및 회수되어 재사용될 수 있다.In one embodiment of the present invention, the catalyst can be separated and recovered after the reaction is completed and reused.

본원의 일 구현예에 있어서, 상기 반응은 상기 화학식 I로서 표시되는 루테늄 산화물을 포함하는 촉매를 사용하는 것이 활성 및/또는 안정성 측면에서 바람직하나, 보조 촉매로서 다른 금속 또는 금속염을 추가적으로 사용할 수 있다.In one embodiment of the present invention, it is preferable in terms of activity and/or stability to use a catalyst comprising ruthenium oxide represented by the chemical formula I for the reaction, but another metal or metal salt may be additionally used as an auxiliary catalyst.

본원의 일 구현예에 있어서, 상기 촉매는 상기 석회석 또는 상기 칼슘 화합물 100 중량부에 대하여 약 0.1 중량부 내지 약 10 중량부로 사용되는 것일 수 있다. 본원의 일 구현예에 있어서, 상기 촉매는 상기 석회석 또는 상기 칼슘 화합물 100 중량부에 대하여 약 0.1 중량부 내지 약 10 중량부, 약 0.1 중량부 내지 약 9 중량부, 약 0.1 중량부 내지 약 8 중량부, 약 0.1 중량부 내지 약 7 중량부, 약 0.1 중량부 내지 약 6 중량부, 약 0.1 중량부 내지 약 5 중량부, 약 0.1 중량부 내지 약 4 중량부, 약 0.1 중량부 내지 약 3 중량부, 약 0.1 중량부 내지 약 2 중량부, 약 0.1 중량부 내지 약 1 중량부, 약 1 중량부 내지 약 10 중량부, 약 1 중량부 내지 약 9 중량부, 약 1 중량부 내지 약 8 중량부, 약 1 중량부 내지 약 7 중량부, 약 1 중량부 내지 약 6 중량부, 약 1 중량부 내지 약 5 중량부, 약 1 중량부 내지 약 4 중량부, 약 1 중량부 내지 약 3 중량부, 약 1 중량부 내지 약 2 중량부, 약 2 중량부 내지 약 10 중량부, 약 2 중량부 내지 약 9 중량부, 약 2 중량부 내지 약 8 중량부, 약 2 중량부 내지 약 7 중량부, 약 2 중량부 내지 약 6 중량부, 약 2 중량부 내지 약 5 중량부, 약 2 중량부 내지 약 4 중량부, 약 2 중량부 내지 약 3 중량부, 약 3 중량부 내지 약 10 중량부, 약 3 중량부 내지 약 9 중량부, 약 3 중량부 내지 약 8 중량부, 약 3 중량부 내지 약 7 중량부, 약 3 중량부 내지 약 6 중량부, 약 3 중량부 내지 약 5 중량부, 약 3 중량부 내지 약 4 중량부, 약 4 중량부 내지 약 10 중량부, 약 4 중량부 내지 약 9 중량부, 약 4 중량부 내지 약 8 중량부, 약 4 중량부 내지 약 7 중량부, 약 4 중량부 내지 약 6 중량부, 약 4 중량부 내지 약 5 중량부, 약 5 중량부 내지 약 10 중량부, 약 5 중량부 내지 약 9 중량부, 약 5 중량부 내지 약 8 중량부, 약 5 중량부 내지 약 7 중량부, 약 5 중량부 내지 약 6 중량부, 약 6 중량부 내지 약 10 중량부, 약 6 중량부 내지 약 9 중량부, 약 6 중량부 내지 약 8 중량부, 약 6 중량부 내지 약 7 중량부, 약 7 중량부 내지 약 10 중량부, 약 7 중량부 내지 약 9 중량부, 약 7 중량부 내지 약 8 중량부, 약 8 중량부 내지 약 10 중량부, 약 8 중량부 내지 약 9 중량부, 또는 약 9 중량부 내지 약 10 중량부로 사용되는 것일 수 있다. 본원의 일 구현예에 있어서, 상기 석회석 또는 상기 칼슘 화합물 100 중량부에 대하여 상기 촉매가 약 0.1 중량부 이하로 사용되는 경우, 상기 수소화 반응의 반응 시간이 길어지거나 및/또는 반응이 완결되지 않을 수 있고, 상기 석회석 또는 상기 칼슘 화합물 100 중량부에 대하여 상기 촉매가 약 10 중량부 이상으로 사용되는 경우, 상기 수소화 반응의 속도가 빨라질 수 있으나, 생성물과 촉매를 분리하는 과정에서 분리 효율이 감소할 수 있다.In one embodiment of the present invention, the catalyst may be used in an amount of about 0.1 to about 10 parts by weight based on 100 parts by weight of the limestone or the calcium compound. In one embodiment of the present invention, the catalyst is present in an amount of from about 0.1 part by weight to about 10 parts by weight, from about 0.1 part by weight to about 9 parts by weight, from about 0.1 part by weight to about 8 parts by weight, from about 0.1 part by weight to about 7 parts by weight, from about 0.1 part by weight to about 6 parts by weight, from about 0.1 part by weight to about 5 parts by weight, from about 0.1 part by weight to about 4 parts by weight, from about 0.1 part by weight to about 3 parts by weight, from about 0.1 part by weight to about 2 parts by weight, from about 0.1 part by weight to about 1 part by weight, from about 1 part by weight to about 10 parts by weight, from about 1 part by weight to about 9 parts by weight, from about 1 part by weight to about 8 parts by weight, from about 1 part by weight to about 7 parts by weight, from about 1 part by weight to about 6 parts by weight, from about 1 part by weight to about 5 parts by weight, or about 1 About 4 parts by weight, about 1 part by weight to about 3 parts by weight, about 1 part by weight to about 2 parts by weight, about 2 parts by weight to about 10 parts by weight, about 2 parts by weight to about 9 parts by weight, about 2 parts by weight to about 8 parts by weight, about 2 parts by weight to about 7 parts by weight, about 2 parts by weight to about 6 parts by weight, about 2 parts by weight to about 5 parts by weight, about 2 parts by weight to about 4 parts by weight, about 2 parts by weight to about 3 parts by weight, about 3 parts by weight to about 10 parts by weight, about 3 parts by weight to about 9 parts by weight, about 3 parts by weight to about 8 parts by weight, about 3 parts by weight to about 7 parts by weight, about 3 parts by weight to about 6 parts by weight, about 3 parts by weight to about 5 parts by weight, about 3 parts by weight to about 4 parts by weight, about 4 parts by weight to about 10 parts by weight, about 4 parts by weight to about 9 parts by weight, about 4 parts by weight to About 8 parts by weight, about 4 parts by weight to about 7 parts by weight, about 4 parts by weight to about 6 parts by weight, about 4 parts by weight to about 5 parts by weight, about 5 parts by weight to about 10 parts by weight, about 5 parts by weight to about 9 parts by weight, about 5 parts by weight to about 8 parts by weight, about 5 parts by weight to about 7 parts by weight, about 5 parts by weight to about 6 parts by weight, about 6 parts by weight to about 10 parts by weight, about 6 parts by weight to about 9 parts by weight, about 6 parts by weight to about 8 parts by weight, about 6 parts by weight to about 7 parts by weight, about 7 parts by weight to about 10 parts by weight, about 7 parts by weight to about 9 parts by weight, about 7 parts by weight to about 8 parts by weight, about 8 parts by weight to about 9 parts by weight, or about 9 parts by weight to about 10 parts by weight. In one embodiment of the present invention, when the catalyst is used in an amount of about 0.1 parts by weight or less with respect to 100 parts by weight of the limestone or the calcium compound, the reaction time of the hydrogenation reaction may become longer and/or the reaction may not be completed, and when the catalyst is used in an amount of about 10 parts by weight or more with respect to 100 parts by weight of the limestone or the calcium compound, the speed of the hydrogenation reaction may become faster, but the separation efficiency may decrease in the process of separating the product and the catalyst.

본원의 일 구현예에 있어서, 상기 촉매 반응은 약 20℃ 내지 약 200℃의 온도 범위에서 수행되는 것일 수 있다. 본원의 일 구현예에 있어서, 상기 촉매 반응은 약 20℃ 내지 약 200℃, 약 20℃ 내지 약 190℃, 약 20℃ 내지 약 180℃, 약 20℃내지 약 170℃, 약 20℃ 내지 약 160℃, 약 20℃ 내지 약 150℃, 약 20℃ 내지 약 140℃, 약 20℃ 내지 약 130℃, 약 30℃ 내지 약 200℃, 약 30℃ 내지 약 190℃, 약 30℃ 내지 약 180℃, 약 30℃ 내지 약 170℃, 약 30℃ 내지 약 160℃, 약 30℃내지 약 150℃, 약 30℃ 내지 약 140℃, 약 30℃ 내지 약 130℃, 약 40℃ 내지 약 200℃, 약 40℃ 내지 약 190℃, 약 40℃ 내지 약 180℃, 약 40℃ 내지 약 170℃, 약 40℃ 내지 약 160℃, 약 40℃ 내지 약 150℃, 약 40℃ 내지 약 140℃, 약 40℃ 내지 약 130℃, 약 50℃ 내지 약 200℃, 약 50℃ 내지 약 190℃, 약 50℃ 내지 약 180℃, 약 50℃ 내지 약 170℃, 약 50℃ 내지 약 160℃, 약 50℃ 내지 약 150℃, 약 50℃ 내지 약 140℃ 또는 약 50℃ 내지 약 130℃의 온도 범위에서 수행되는 것일 수 있다. 본원의 일 구현예에 있어서, 상기 촉매 반응은 약 60℃ 내지 약 120℃의 온도 범위에서 수행되는 것이 가장 바람직할 수 있다.In one embodiment of the present invention, the catalytic reaction may be performed at a temperature range of about 20°C to about 200°C. In one embodiment of the present invention, the catalytic reaction is performed at a temperature of about 20°C to about 200°C, about 20°C to about 190°C, about 20°C to about 180°C, about 20°C to about 170°C, about 20°C to about 160°C, about 20°C to about 150°C, about 20°C to about 140°C, about 20°C to about 130°C, about 30°C to about 200°C, about 30°C to about 190°C, about 30°C to about 180°C, about 30°C to about 170°C, about 30°C to about 160°C, about 30°C to about 150°C, about 30°C to about 140°C, about 30°C to about 130°C, about 40°C to about 200°C, about 40°C to about The catalytic reaction may be performed at a temperature range of about 190°C, about 40°C to about 180°C, about 40°C to about 170°C, about 40°C to about 160°C, about 40°C to about 150°C, about 40°C to about 140°C, about 40°C to about 130°C, about 50°C to about 200°C, about 50°C to about 190°C, about 50°C to about 180°C, about 50°C to about 170°C, about 50°C to about 160°C, about 50°C to about 150°C, about 50°C to about 140°C, or about 50°C to about 130°C. In one embodiment of the present disclosure, it is most preferable that the catalytic reaction is performed at a temperature range of about 60°C to about 120°C.

본원의 일 구현예에 있어서, 상기 촉매 반응은 수열반응기에서 수행되는 것일 수 있다.In one embodiment of the present invention, the catalytic reaction may be performed in a hydrothermal reactor.

본원의 일 구현예에 있어서, 상기 수소의 압력은 약 0.1 MPa 내지 약 10 MPa인 것일 수 있다. 본원의 일 구현예에 있어서, 상기 수소의 압력은 약 0.1 MPa 내지 약 10 MPa, 약 0.1 MPa 내지 약 9 MPa, 약 0.1 MPa 내지 약 8 MPa, 약 0.1 MPa 내지 약 7 MPa, 약 0.1 MPa 내지 약 6 MPa, 약 0.1 MPa 내지 약 5 MPa, 약 0.1 MPa 내지 약 4 MPa, 약 0.1 MPa 내지 약 3 MPa, 약 1 MPa 내지 약 10 MPa, 약 1 MPa 내지 약 9 MPa, 약 1 MPa 내지 약 8 MPa, 약 1 MPa 내지 약 7 MPa, 약 1 MPa 내지 약 6 MPa, 약 1 MPa 내지 약 5 MPa, 약 1 MPa 내지 약 4 MPa, 약 1 MPa 내지 약 3 MPa, 약 1.5 MPa 내지 약 10 MPa, 약 1.5 MPa 내지 약 9 MPa, 약 1.5 MPa 내지 약 8 MPa, 약 1.5 MPa 내지 약 7 MPa, 약 1.5 MPa 내지 약 6 MPa, 약 1.5 MPa 내지 약 5 MPa, 약 1.5 MPa 내지 약 4 MPa, 또는 약 1.5 MPa 내지 약 3 MPa인 것일 수 있다. 본원의 일 구현예에 있어서, 상기 수소의 압력이 약 0.1 MPa 이하인 경우에는 반응 진행 속도가 매우 느릴 수 있고, 상기 수소의 압력이 약 10 MPa 이상에서는 반응이 원활하게 진행되지 않을 수 있다. 본원의 일 구현예에 있어서, 상기 수소의 압력은 약 2 MPa인 것이 가장 바람직할 수 있다.In one embodiment of the present invention, the pressure of the hydrogen may be from about 0.1 MPa to about 10 MPa. In one embodiment of the present invention, the pressure of the hydrogen is from about 0.1 MPa to about 10 MPa, from about 0.1 MPa to about 9 MPa, from about 0.1 MPa to about 8 MPa, from about 0.1 MPa to about 7 MPa, from about 0.1 MPa to about 6 MPa, from about 0.1 MPa to about 5 MPa, from about 0.1 MPa to about 4 MPa, from about 0.1 MPa to about 3 MPa, from about 1 MPa to about 10 MPa, from about 1 MPa to about 9 MPa, from about 1 MPa to about 8 MPa, from about 1 MPa to about 7 MPa, from about 1 MPa to about 6 MPa, from about 1 MPa to about 5 MPa, from about 1 MPa to about 4 MPa, from about 1 MPa to about 3 MPa, from about 1.5 MPa to about 10 MPa, from about 1.5 MPa to about 9 MPa, about 1.5 MPa to about 8 MPa, about 1.5 MPa to about 7 MPa, about 1.5 MPa to about 6 MPa, about 1.5 MPa to about 5 MPa, about 1.5 MPa to about 4 MPa, or about 1.5 MPa to about 3 MPa. In one embodiment of the present disclosure, when the pressure of the hydrogen is about 0.1 MPa or lower, the reaction progress rate may be very slow, and when the pressure of the hydrogen is about 10 MPa or higher, the reaction may not progress smoothly. In one embodiment of the present disclosure, the pressure of the hydrogen may be most preferably about 2 MPa.

본원의 일 구현예에 있어서, 상기 수산화 칼슘은 상기 용액의 침전물로서 여과를 통하여 수득되는 것일 수 있으나, 이에 제한되는 것은 아니다. 본원의 일 구현예에 있어서, 상기 암모니아는 상기 용액에 이산화탄소 또는 산을 첨가하여 암모니아 화합물 형태로 수득되는 것일 수 있으나, 이에 제한되는 것은 아니다.In one embodiment of the present invention, the calcium hydroxide may be obtained as a precipitate of the solution through filtration, but is not limited thereto. In one embodiment of the present invention, the ammonia may be obtained in the form of an ammonia compound by adding carbon dioxide or an acid to the solution, but is not limited thereto.

본원의 일 구현예에 있어서, 상기 수산화 칼슘의 제조 반응 후, 상기 촉매를 분리하는 것을 추가 포함할 수 있다. 본원의 일 구현예에 있어서, 상기 수소화 반응 후 상기 촉매 및 상기 수산화 칼슘을 포함하는 침전물을 분리하는 것을 추가 포함할 수 있다.In one embodiment of the present invention, after the manufacturing reaction of the calcium hydroxide, separating the catalyst may be further included. In one embodiment of the present invention, after the hydrogenation reaction, separating a precipitate including the catalyst and the calcium hydroxide may be further included.

본원의 일 구현예에 있어서, 상기 수소화 반응의 생성물에 무기산을 첨가하여 암모늄염을 수득하는 것을 추가 포함하는 것일 수 있다. 본원의 일 구현예에 있어서, 상기 무기산은 황산, 질산, 염산, 또는 아세트산일 수 있으나, 이에 제한되지 않을 수 있다. 본원의 일 구현예에 있어서, 상기 암모늄염은 황산암모늄 ((NH4)2SO4), 황산수소암모늄 (NH4HSO4), 질산암모늄 (NH4NO3), 염산암모늄 (NH4Cl), 또는 아세트산암모늄 (NH4CH3CO2)일 수 있으며, 상기 암모늄염은 상기 무기산의 종류에 따라 달라지는 것일 수 있다. 여기서, 추가적으로 무기산을 첨가하여 수득되는 상기 암모늄염의 무게를 통하여 암모늄 이온의 수득률을 계산할 수 있으나, 이는 질산 이온에서 암모니아를 생성한 후에 실제 암모늄 이온의 분리 및 사용을 위한 암모늄염을 수득하는 과정에서 실험적으로 확인되는 부가적인 수치인 것일 수 있다.In one embodiment of the present invention, the method may further include adding an inorganic acid to the product of the hydrogenation reaction to obtain an ammonium salt. In one embodiment of the present invention, the inorganic acid may be, but is not limited to, sulfuric acid, nitric acid, hydrochloric acid, or acetic acid. In one embodiment of the present invention, the ammonium salt may be ammonium sulfate ((NH 4 ) 2 SO 4 ), ammonium hydrogen sulfate (NH 4 HSO 4 ), ammonium nitrate (NH 4 NO 3 ), ammonium hydrochloride (NH 4 Cl), or ammonium acetate (NH 4 CH 3 CO 2 ), and the ammonium salt may vary depending on the type of the inorganic acid. Here, the yield of ammonium ion can be calculated through the weight of the ammonium salt obtained by additionally adding an inorganic acid, but this may be an additional value experimentally confirmed in the process of obtaining an ammonium salt for actual separation and use of ammonium ion after generating ammonia from nitrate ion.

본원의 제 2 측면은, 하기 화학식 Ⅰ로서 표시되며, 단사정계 구조를 갖는, 루테늄 산화물 촉매로서, 제 1 측면에 따른 수산화 칼슘의 제조 방법에 사용되는, 루테늄 산화물 촉매를 제공한다:The second aspect of the present invention provides a ruthenium oxide catalyst, which is represented by the following chemical formula Ⅰ and has a monoclinic crystal structure, and is used in the method for producing calcium hydroxide according to the first aspect:

[화학식 Ⅰ][Chemical Formula I]

HxRuO2;H x RuO 2 ;

상기 화학식 Ⅰ에서, 0< x ≤4임.In the above chemical formula I, 0< x ≤4.

본원의 제 1 측면과 중복되는 부분들에 대해서는 상세한 설명을 생략하였으나, 본원의 제 1 측면에 대해 설명한 내용은 본원의 제 2 측면에서 그 설명이 생략되었더라도 동일하게 적용될 수 있다.Although detailed descriptions of parts that overlap with the first aspect of the present application have been omitted, the contents described for the first aspect of the present application may be equally applied even if the description is omitted in the second aspect of the present application.

본원의 일 구현예에 있어서, 상기 화학식 I에서, x (수소의 원자비)는 0 초과 4 이하, 0 초과 약 3.5 이하, 0 초과 약 3 이하, 0 초과 약 2.5 이하, 0 초과 약 2 이하, 0 초과 약 1.5 이하, 0 초과 약 1.2 이하, 약 0.1 내지 약 4, 약 0.1 내지 약 3.5, 약 0.1 내지 약 3, 약 0.1 내지 약 2.5, 약 0.1 내지 약 2, 약 0.1 내지 약 1.5, 약 0.1 내지 약 1.2, 약 0.2 내지 약 3.5, 약 0.2 내지 약 3, 약 0.2 내지 약 2.5, 약 0.2 내지 약 2, 약 0.2 내지 약 1.5, 약 0.2 내 지 약 1.2, 약 0.3 내지 약 3.5, 약 0.3 내지 약 3, 약 0.3 내지 약 2.5, 약 0.3 내지 약 2, 약 0.3 내지 약 1.5, 약 0.3 내지 약 1.2, 약 0.4 내지 약 3.5, 약 0.4 내지 약 3, 약 0.4 내지 약 2.5, 약 0.4 내지 약 2, 약 0.4 내지 약 1.5, 또는 약 0.4 내지 약 1.2일 수 있으나, 이에 제한되지 않을 수 있다. 본원의 일 구현예에 있어서, 상기 화학식 Ⅰ에서, x는 약 0.4 내지 약 1.2 일 수 있다.In one embodiment of the present invention, in the chemical formula I, x (atomic ratio of hydrogen) is greater than 0 and less than or equal to 4, greater than 0 and less than or equal to about 3.5, greater than 0 and less than or equal to about 3, greater than 0 and less than or equal to about 2.5, greater than 0 and less than or equal to about 2, greater than 0 and less than or equal to about 1.5, greater than 0 and less than or equal to about 1.2, from about 0.1 to about 4, from about 0.1 to about 3.5, from about 0.1 to about 3, from about 0.1 to about 2.5, from about 0.1 to about 2, from about 0.1 to about 1.5, from about 0.1 to about 1.2, from about 0.2 to about 3.5, from about 0.2 to about 3, from about 0.2 to about 2.5, from about 0.2 to about 2, from about 0.2 to about 1.5, from about 0.2 to about 1.2, from about 0.3 to about 3.5, about 0.3 to about 3, about 0.3 to about 2.5, about 0.3 to about 2, about 0.3 to about 1.5, about 0.3 to about 1.2, about 0.4 to about 3.5, about 0.4 to about 3, about 0.4 to about 2.5, about 0.4 to about 2, about 0.4 to about 1.5, or about 0.4 to about 1.2, but may not be limited thereto. In one embodiment of the present disclosure, in the chemical formula I, x may be about 0.4 to about 1.2.

본원의 일 구현예에 있어서, 상기 화학식 I에서, x (수소의 원자비)가 약 1에 가까울수록 상기 단사정계 구조의 루테늄 산화물을 생성하기 용이할 수 있다. 구체적으로, 상기 화학식 I에서, 상기 수소의 비율이 약 0.6 내지 약 1.4이면, 상기 단사정계 구조의 루테늄 산화물을 생성하기 더 용이할 수 있다. 여기에서, 상기 화학식 I에서 x가 0이면, 정방정계 금홍석 (rutile) 구조의 루테늄 산화물로의 구조 전이가 일어날 수 있어, 수소 함량을 유지하는 것이 바람직하다.In one embodiment of the present invention, in the chemical formula I, the closer x (atomic ratio of hydrogen) is to about 1, the easier it is to produce the monoclinic ruthenium oxide. Specifically, in the chemical formula I, when the ratio of hydrogen is from about 0.6 to about 1.4, the monoclinic ruthenium oxide may be easier to produce. Here, when x in the chemical formula I is 0, a structural transition into a tetragonal rutile structure ruthenium oxide may occur, so it is preferable to maintain the hydrogen content.

본원의 일 구현예에 있어서, 상기 화학식 I에 포함된 수소의 원자비는 열 무게 분석(thermo-gravimetric analysis; TGA)에 의해 계산될 수 있다. 구체적으로, 상기 열 무게 분석을 이용한 분석에서, 고체 시료를 백금 용기에 넣은 후 온도를 올려주면서 무게 변화를 측정할 수 있다. 상기 단사정계 루테늄 산화물 (HxRuO2)에 포함된 수소는 모두 제거되고, 정방정계 루테늄 산화물 (RuO2)로 전환된다. 온도에 따른 무게 변화로부터 수소의 양을 정량적으로 분석할 수 있다.In one embodiment of the present invention, the atomic ratio of hydrogen included in the chemical formula I can be calculated by thermo-gravimetric analysis (TGA). Specifically, in the analysis using the thermo-gravimetric analysis, a solid sample can be placed in a platinum container and the weight change can be measured while increasing the temperature. All hydrogen included in the monoclinic ruthenium oxide (H x RuO 2 ) is removed and converted to tetragonal ruthenium oxide (RuO 2 ). The amount of hydrogen can be quantitatively analyzed from the weight change according to the temperature.

본원의 일 구현예에 있어서, 상기 루테늄 산화물 촉매는 X-선 분말 회절 측정 (Cu Kα 선)에 의해 결정되는 입사각 (2θ)이 18.38°< 2θ <18.42°, 25.45°< 2θ <25.51°, 26.26°< 2θ <26.32°, 33.45°< 2θ <33.51°, 35.28°< 2θ <35.34°, 36.24°< 2θ <36.30°, 37.32°< 2θ <37.38°, 39.55°< 2θ <39.61°, 40.61°< 2θ <40.67°, 41.46°< 2θ <41.52°, 49.17°< 2θ <49.23°, 52.31°< 2θ <52.37°, 54.03°< 2θ <54.09°, 54.70°< 2θ <54.76°, 55.95°< 2θ <56.01°, 59.97°< 2θ <60.03°, 60.40°< 2θ <60.46°, 61.92°< 2θ <61.98°, 63.94°< 2θ <64.00°, 65.79°< 2θ <65.85° 및 69.13°< 2θ <69.19°인 각 위치에서 회절 피크가 관측되는 것일 수 있다. 본원의 일 구현예에 있어서, 상기 루테늄 산화물 촉매는 X-선 분말 회절 측정 (Cu Kα 선)에 의해 결정되는 입사각 (2θ)은 18.40°, 25.48°, 26.29°, 33.48°, 35.31°, 36.27°, 37.35°, 39.58°, 40.64°, 41.49°, 49.20°, 52.34°, 54.06°, 54.73°, 55.98°, 58.00°, 60.43°, 61.95°, 63.97°, 65.82° 및 69.16°인 각 위치에서 회절 피크가 관측되는 것일 수 있다.In one embodiment of the present invention, the ruthenium oxide catalyst has an incident angle (2θ) determined by X-ray powder diffraction measurement (Cu Kα line) of 18.38°<2θ <18.42°, 25.45°<2θ <25.51°, 26.26°<2θ <26.32°, 33.45°<2θ <33.51°, 35.28°<2θ <35.34°, 36.24°<2θ <36.30°, 37.32°<2θ <37.38°, 39.55°<2θ <39.61°, 40.61°<2θ <40.67°, 41.46°<2θ <41.52°, 49.17°<2θ Diffraction peaks can be observed at each position of <49.23°, 52.31°< 2θ <52.37°, 54.03°< 2θ <54.09°, 54.70°< 2θ <54.76°, 55.95°< 2θ <56.01°, 59.97°< 2θ <60.03°, 60.40°< 2θ <60.46°, 61.92°< 2θ <61.98°, 63.94°< 2θ <64.00°, 65.79°< 2θ <65.85°, and 69.13°< 2θ <69.19°. In one embodiment of the present invention, the ruthenium oxide catalyst may have diffraction peaks observed at positions where the incident angles (2θ) determined by X-ray powder diffraction measurement (Cu Kα line) are 18.40°, 25.48°, 26.29°, 33.48°, 35.31°, 36.27°, 37.35°, 39.58°, 40.64°, 41.49°, 49.20°, 52.34°, 54.06°, 54.73°, 55.98°, 58.00°, 60.43°, 61.95°, 63.97°, 65.82°, and 69.16°, respectively.

본원의 일 구현예에 있어서, 상기 루테늄 산화물 촉매는 단사정계의 공간군 P21/c, C2/m, P2/c, C2/c, P2/m, 또는 P21/m의 구조일 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present invention, the ruthenium oxide catalyst may have a structure of a monoclinic space group P2 1 /c, C2/m, P2/c, C2/c, P2/m, or P2 1 /m, but may not be limited thereto.

본원의 일 구현예에 있어서, 상기 루테늄 산화물 촉매의 단사정계 결정 구조의 단위 격자 (unit cell)는 격자 상수 a 내지 c, 및 모서리 각도 베타(β)로서 정의될 수 있다.In one embodiment of the present invention, the unit cell of the monoclinic crystal structure of the ruthenium oxide catalyst can be defined by lattice constants a to c and edge angle beta (β).

본원의 일 구현예에 있어서, 상기 단사정계 구조에서, 5 Å≤ a ≤6 Å, 5 Å≤ b ≤6 Å, 및 5 Å≤ c ≤6 Å이고, 베타(β) 각은 약 110° 내지 약 120°인 것일 수 있다. 예를 들어, 상기 a 내지 c는 각각, 약 5 Å 내지 약 6 Å, 약 5.1 Å 내지 약 6 Å, 약 5.2 Å 내지 약 6 Å, 약 5.3 Å 내지 약 6 Å, 약 5 Å 내지 약 5.8 Å, 약 5.1 Å 내지 약 5.8 Å, 약 5.2 Å 내지 약 5.8 Å, 약 5.3 Å 내지 약 5.8 Å, 약 5 Å 내지 약 5.6 Å, 약 5.1 Å 내지 약 5.6 Å, 약 5.2 Å 내지 약 5.6 Å, 약 5.3 Å 내지 약 5.6 Å, 약 5 Å 내지 약 5.4 Å, 약 5.1 Å 내지 약 5.4 Å, 약 5.2 Å 내지 약 5.4 Å, 약 5.3 Å 내지 약 5.4 Å 또는 약 5.35 Å 내지 약 5.4 Å일 수 있으며, 상기 b는 약 5 Å 내지 약 6 Å, 약 5 Å 내지 약 5.8 Å, 약 5 Å 내지 약 5.6 Å, 약 5 Å 내지 약 5.4 Å, 약 5 Å 내지 약 5.2 Å 또는 약 5 Å 내지 약 5.1 Å일 수 있으며, 상기 베타(β) 각은 약 110° 내지 약 120°, 약 112° 내지 약 120°, 약 114° 내지 약 120°, 약 110° 내지 약 118°, 약 112 ° 내지 약 118°, 약 114° 내지 약 118°, 약 110° 내지 약 116°, 약 112° 내지 약 116° 또는 약 114° 내지 약 116°일 수 있다.In one embodiment of the present invention, in the monoclinic structure, 5 Å≤ a ≤6 Å, 5 Å≤ b ≤6 Å, and 5 Å≤ c ≤6 Å, and the beta (β) angle may be about 110° to about 120°. For example, a to c are each about 5 Å to about 6 Å, about 5.1 Å to about 6 Å, about 5.2 Å to about 6 Å, about 5.3 Å to about 6 Å, about 5 Å to about 5.8 Å, about 5.1 Å to about 5.8 Å, about 5.2 Å to about 5.8 Å, about 5.3 Å to about 5.8 Å, about 5 Å to about 5.6 Å, about 5.1 Å to about 5.6 Å, about 5.2 Å to about 5.6 Å, about 5.3 Å to about 5.6 Å, about 5 Å to about 5.4 Å, about 5.1 Å to about 5.4 Å, about 5.2 Å to about 5.4 Å, about 5.3 Å to about 5.4 Å or about 5.35 Å to about 5.4 Å, wherein b can be about 5 Å to about 6 Å, about 5 Å to about 5.8 Å, about 5 Å to about 5.6 Å, about 5 Å to about 5.4 Å, about 5 Å to about 5.2 Å or about 5 Å to about 5.1 Å, and wherein the beta (β) angle is about 110° to about 120°, about 112° to about 120°, about 114° to about 120°, about 110° to about 118°, about 112° to about 118°, about 114° to about 118°, about 110° to about 116°, about 112° to about 116° or about 114° to about It could be 116°.

본원의 일 구현예에 있어서, 상기 단사정계 구조에서, a=5.3533 Å, b=5.0770 Å, c=5.3532 Å이고, 베타(β) 각은 115.9074°일 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present invention, in the monoclinic structure, a = 5.3533 Å, b = 5.0770 Å, c = 5.3532 Å, and the beta (β) angle may be 115.9074°, but may not be limited thereto.

이하, 본원에 대하여 실시예를 이용하여 좀더 구체적으로 설명하지만, 하기 실시예는 본원의 이해를 돕기 위하여 예시하는 것일 뿐, 본원의 내용이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail using examples. However, the following examples are provided only to help understand the present invention, and the contents of the present invention are not limited to the following examples.

실시예 1Example 1

0.2 g의 CaCO3 (2.00 mmol), 20 mg의 HxRuO2 (0.15 mmol), 및 2.0 M의 HNO3 2 mL를 수열반응기에 넣고, 상기 수열반응기의 내부를 2.0 MPa의 수소 압력으로 채운 후, 100℃에서 10 시간 동안 반응을 진행하였다. 반응이 완료된 후, 상기 수열반응기를 상온으로 냉각하고 생성된 침전물과 잔류 용액을 분리하였다.0.2 g of CaCO 3 (2.00 mmol), 20 mg of H x RuO 2 (0.15 mmol), and 2 mL of 2.0 M HNO 3 were placed in a hydrothermal reactor, and the inside of the hydrothermal reactor was filled with a hydrogen pressure of 2.0 MPa, and the reaction was performed at 100°C for 10 hours. After the reaction was completed, the hydrothermal reactor was cooled to room temperature, and the generated precipitate and residual solution were separated.

상기 침전물은 건조된 후, X-선 분말 회절 분석법을 통하여 수산화 칼슘(Ca(OH)2)으로 확인되었다 (도 2). 수득된 Ca(OH)2의 질량은 0.145 g(1.96 mmol)이며, CaCO3를 기준으로 계산한 Ca(OH)2의 수득 비율은 97.9%이다.After drying, the above precipitate was confirmed to be calcium hydroxide (Ca(OH) 2 ) through X-ray powder diffraction analysis (Fig. 2). The mass of the obtained Ca(OH) 2 was 0.145 g (1.96 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 97.9%.

반응 후 잔류 용액을 자외선 가시광선 분광법(ultraviolet-visible spectroscopy)으로 분석한 결과, 질소 산화물 이온(NO3 - 및 NO2 -)은 확인되지 않았으며, 이를 통하여 질산 이온은 모두 암모니아 또는 질소로 환원된 것을 확인하였다. 상기 잔류 용액에 질산을 첨가하고 증발시켜 결정을 수득하였으며, 상기 결정은 X-선 분말 회절법을 통하여 질산암모늄(NH4NO3)으로 확인되었다 (도 3). 상기 수득한 NH4NO3의 질량은 0.301 g(3.76 mmol)이며, HNO3를 기준으로 계산한 수득 비율은 94.1%이다.After the reaction, the residual solution was analyzed by ultraviolet-visible spectroscopy, and nitrogen oxide ions (NO 3 - and NO 2 - ) were not detected, confirming that all nitrate ions were reduced to ammonia or nitrogen. Nitric acid was added to the residual solution and evaporated to obtain crystals, which were confirmed to be ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction (Fig. 3). The mass of the obtained NH 4 NO 3 is 0.301 g (3.76 mmol), and the yield calculated based on HNO 3 is 94.1%.

실시예 2Example 2

5.0 MPa의 수소 압력에서 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 수소화 반응을 수행하였다. 반응 후 생성된 침전물은 건조된 후, X-선 분말 회절 분석법을 통하여 Ca(OH)2으로 확인되었다. 수득된 Ca(OH)2의 질량은 0.139 g(1.88 mmol)이며, CaCO3를 기준으로 계산한 Ca(OH)2의 수득 비율은 93.8%이다.The hydrogenation reaction was performed in the same manner as in Example 1, except that the reaction was performed under a hydrogen pressure of 5.0 MPa. The precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 through X-ray powder diffraction analysis. The mass of the obtained Ca(OH) 2 was 0.139 g (1.88 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 93.8%.

반응 후 잔류 용액에 질산을 첨가하고 증발시켜 결정을 수득하였으며, 상기 결정은 X-선 분말 회절법을 통하여 질산암모늄(NH4NO3)으로 확인되었다. 수득된 NH4NO3의 질량은 0.313 g(3.91 mmol)이며, HNO3를 기준으로 계산한 수득 비율은 97.8%이다.After the reaction, nitric acid was added to the residual solution and evaporated to obtain crystals, which were identified as ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction. The mass of the obtained NH 4 NO 3 was 0.313 g (3.91 mmol), and the yield calculated based on HNO 3 was 97.8%.

실시예 3Example 3

증류수 2 mL를 추가로 넣고 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 수소화 반응을 수행하였다. 반응 후 생성된 침전물은 건조된 후, X-선 분말 회절 분석법을 통하여 Ca(OH)2으로 확인되었다. 수득된 Ca(OH)2의 질량은 0.125 g(1.69 mmol)이며, CaCO3를 기준으로 계산한 Ca(OH)2의 수득 비율은 84.3%이다.The hydrogenation reaction was performed in the same manner as in Example 1, except that 2 mL of distilled water was additionally added and the reaction was performed. The precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 through X-ray powder diffraction analysis. The mass of the obtained Ca(OH) 2 was 0.125 g (1.69 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 84.3%.

반응 후 잔류 용액에 질산을 첨가하고 증발시켜 결정을 수득하였으며, 상기 결정은 X-선 분말 회절법을 통하여 질산암모늄(NH4NO3)으로 확인되었다. 수득된 NH4NO3의 질량은 0.294 g(3.67 mmol)이며, HNO3를 기준으로 계산한 수득 비율은 91.9%이다.After the reaction, nitric acid was added to the residual solution and evaporated to obtain crystals, which were identified as ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction. The mass of the obtained NH 4 NO 3 was 0.294 g (3.67 mmol), and the yield calculated based on HNO 3 was 91.9%.

실시예 4Example 4

60℃에서 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 수소화 반응을 수행하였다. 반응 후 생성된 침전물은 건조된 후, X-선 분말 회절 분석법을 통하여 Ca(OH)2으로 확인되었다. 수득된 Ca(OH)2의 질량은 0.087 g(1.17 mmol)이며, CaCO3를 기준으로 계산한 Ca(OH)2의 수득 비율은 58.7%이다.The hydrogenation reaction was performed in the same manner as in Example 1, except that the reaction was performed at 60°C. The precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 through X-ray powder diffraction analysis. The mass of the obtained Ca(OH) 2 was 0.087 g (1.17 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 58.7%.

반응 후 잔류 용액에 질산을 첨가하고 증발시켜 결정을 수득하였으며, 상기 결정은 X-선 분말 회절법을 통하여 질산암모늄(NH4NO3)으로 확인되었다. 수득된 NH4NO3의 질량은 0.183 g(2.29 mmol)이며, HNO3를 기준으로 계산한 수득 비율은 57.2%이다.After the reaction, nitric acid was added to the residual solution and evaporated to obtain crystals, which were identified as ammonium nitrate (NH 4 NO 3 ) through X-ray powder diffraction. The mass of the obtained NH 4 NO 3 was 0.183 g (2.29 mmol), and the yield calculated based on HNO 3 was 57.2%.

실시예 5Example 5

반응물로서 탄산 칼슘 대신 상용 석회석 (도 4) 0.2 g을 질산에 용해시킨 후, 용해되지 않은 고체를 분리한 용액을 사용하여 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 수소화 반응을 수행하였다. 반응 후 생성된 침전물은 건조된 후, X-선 분말 회절 분석법을 통하여 Ca(OH)2으로 확인되었다 (도 5). 수득된 Ca(OH)2의 질량은 0.107 g(1.44 mmol)이다.The hydrogenation reaction was performed in the same manner as in Example 1, except that 0.2 g of commercial limestone (Fig. 4) was dissolved in nitric acid instead of calcium carbonate as a reactant, and the undissolved solid was separated and used for the reaction. The precipitate formed after the reaction was dried and confirmed to be Ca(OH) 2 by X-ray powder diffraction analysis (Fig. 5). The mass of the obtained Ca(OH) 2 is 0.107 g (1.44 mmol).

실시예 6Example 6

촉매로서 루테늄 분말(7.6 mg, 0.075 mmol)을 사용하여 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 반응을 수행하였다. 반응이 완료된 후, 수득된 Ca(OH)2의 수득 비율은 5% 미만으로서, 매우 소량이 수득되었다.The reaction was carried out in the same manner as in Example 1, except that ruthenium powder (7.6 mg, 0.075 mmol) was used as a catalyst. After the reaction was completed, the yield of the obtained Ca(OH) 2 was less than 5%, so a very small amount was obtained.

실시예 7Example 7

촉매로서 백금 분말(14.6 mg, 0.075 mmol)을 사용하여 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 반응을 수행하였다. 반응이 완료된 후, 수득된 Ca(OH)2의 질량은 0.115 g(1.55 mmol)이며, CaCO3를 기준으로 계산한 Ca(OH)2의 수득 비율은 77.6%이다. 수득된 NH4NO3의 질량은 0.232 g(2.88 mmol)이며, HNO3를 기준으로 계산한 수득 비율은 72.5%이다.The reaction was performed in the same manner as in Example 1, except that platinum powder (14.6 mg, 0.075 mmol) was used as a catalyst. After completion of the reaction, the mass of the obtained Ca(OH) 2 was 0.115 g (1.55 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 77.6%. The mass of the obtained NH 4 NO 3 was 0.232 g (2.88 mmol), and the yield calculated based on HNO 3 was 72.5%.

실시예 8Example 8

촉매로서 팔라듐 분말(8.0 mg, 0.075 mmol)을 사용하여 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 반응을 수행하였다. 반응이 완료된 후, 수득된 Ca(OH)2의 질량은 0.120 g(1.62 mmol)이며, CaCO3를 기준으로 계산한 Ca(OH)2의 수득 비율은 81.0%이다. 수득된 NH4NO3의 질량은 0.256 g(3.20 mmol)이며, HNO3를 기준으로 계산한 수득 비율은 80.0%이다.The reaction was performed in the same manner as in Example 1, except that palladium powder (8.0 mg, 0.075 mmol) was used as a catalyst. After completion of the reaction, the mass of the obtained Ca(OH) 2 was 0.120 g (1.62 mmol), and the yield of Ca(OH) 2 calculated based on CaCO 3 was 81.0%. The mass of the obtained NH 4 NO 3 was 0.256 g (3.20 mmol), and the yield calculated based on HNO 3 was 80.0%.

실시예 9Example 9

촉매로서 니켈 분말(7.1 mg, 0.075 mmol)을 사용하여 반응시킨 것 이외에는 상기 실시예 1과 동일한 방법으로 반응을 수행하였다. 반응이 완료된 후, 수득된 Ca(OH)2의 수득 비율은 5% 미만으로서, 매우 소량이 수득되었다.The reaction was carried out in the same manner as in Example 1, except that nickel powder (7.1 mg, 0.075 mmol) was used as a catalyst. After the reaction was completed, the yield of the obtained Ca(OH) 2 was less than 5%, so a very small amount was obtained.

전술한 본원의 설명은 예시를 위한 것이며, 본원이 속하는 기술분야의 통상의 지식을 가진 자는 본원의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수도 있다.The above description of the present invention is for illustrative purposes only, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single component may be implemented in a distributed manner, and likewise, components described as distributed may be implemented in a combined manner.

Claims (18)

석회석 또는 칼슘 화합물; 질산; 및 수소를 촉매 반응시켜 수산화 칼슘 및 암모니아 화합물을 수득하는 것을 포함하는,Comprising a process for producing calcium hydroxide and an ammonia compound by catalytically reacting limestone or a calcium compound; nitric acid; and hydrogen. 수산화 칼슘의 제조 방법.Method for producing calcium hydroxide. 제 1 항에 있어서, In paragraph 1, 상기 석회석은 탄산 칼슘을 포함하는 대리석, 방해석, 선석, 석회석, 백악, 빙주석, 조개껍데기, 난각(egg shell), 및 산호를 포함하는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the limestone includes marble, calcite, feldspar, limestone, chalk, glacierite, seashells, egg shells, and coral containing calcium carbonate. 제 1 항에 있어서,In paragraph 1, 상기 칼슘 화합물은 칼슘을 포함하는 공정 부산물, 폐기물 및 염에서 선택되는 하나 이상을 포함하는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the calcium compound comprises at least one selected from process by-products, wastes and salts containing calcium. 제 3 항에 있어서, In the third paragraph, 상기 공정 부산물 또는 상기 폐기물은 슬래그 및 폐콘크리트에서 선택되는 하나 이상을 포함하는 것이고,The above process by-product or the above waste comprises at least one selected from slag and waste concrete, 상기 염은 칼슘을 포함하는, 염화염, 산화염, 황화염, 탄산염, 질산염, 인산염, 황산염, 규산염 및 이들의 수화물에서 선택되는 하나 이상을 포함하는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the salt comprises at least one selected from chlorides, oxides, sulfates, carbonates, nitrates, phosphates, sulfates, silicates and hydrates thereof, which contain calcium. 제 1 항에 있어서,In paragraph 1, 상기 촉매는 타이타늄(Ti), 바나듐(V), 크로뮴(Cr), 망가니즈(Mn), 철(Fe), 코발트(Co), 니켈(Ni), 구리(Cu), 아연(Zn), 몰리브데넘(Mo), 인듐(In), 주석(Sn), 인(P), 알루미늄(Al), 실리콘(Si), 루테늄(Ru), 로듐(Rh), 팔라듐(Pd), 은(Ag), 텅스텐(W), 레늄(Re), 오스뮴(Os), 이리듐(Ir), 백금(Pt), 및 금(Au)에서 선택되는 하나 이상을 포함하는 금속, 합금 또는 산화물에서 선택되는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the catalyst is selected from a metal, alloy or oxide including at least one selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), molybdenum (Mo), indium (In), tin (Sn), phosphorus (P), aluminum (Al), silicon (Si), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au). 제 5 항에 있어서,In paragraph 5, 상기 촉매는 하기 화학식 Ⅰ로서 표시되는 루테늄 산화물을 포함하는 것인, 수산화 칼슘의 제조 방법:A method for producing calcium hydroxide, wherein the catalyst comprises ruthenium oxide represented by the following chemical formula Ⅰ: [화학식 Ⅰ][Chemical Formula I] HxRuO2;H x RuO 2 ; 상기 화학식 Ⅰ에서, 0< x ≤4임.In the above chemical formula I, 0< x ≤4. 제 1 항에 있어서, In paragraph 1, 상기 촉매는 상기 석회석 또는 상기 칼슘 화합물 100 중량부에 대하여 0.1 중량부 내지 10 중량부로 사용되는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the catalyst is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the limestone or the calcium compound. 제 1 항에 있어서, In paragraph 1, 상기 촉매 반응은 20℃ 내지 200℃의 온도 범위에서 수행되는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the above catalytic reaction is performed at a temperature range of 20°C to 200°C. 제 1 항에 있어서,In paragraph 1, 상기 촉매 반응은 수열반응기에서 수행되는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the above catalytic reaction is performed in a hydrothermal reactor. 제 1 항에 있어서,In paragraph 1, 상기 수소의 압력은 0.1 MPa 내지 10 MPa인 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the pressure of the hydrogen is 0.1 MPa to 10 MPa. 제 1항에 있어서,In paragraph 1, 상기 질산의 농도는 0.1 M 내지 16 M인 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the concentration of the nitric acid is 0.1 M to 16 M. 제 1 항에 있어서,In paragraph 1, 상기 촉매 반응은 용매를 포함하는 용액 조건에서 수행되는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the above catalytic reaction is performed under solution conditions containing a solvent. 제 12 항에 있어서,In Article 12, 상기 용매는 증류수, 메탄올, 및 에탄올에서 선택되는 것인, 수산화 칼슘의 제조 방법.A method for producing calcium hydroxide, wherein the solvent is selected from distilled water, methanol, and ethanol. 하기 화학식 Ⅰ로서 표시되며, It is represented by the following chemical formula I, 단사정계 구조를 갖는, 루테늄 산화물 촉매로서,As a ruthenium oxide catalyst having a monoclinic structure, 제 1 항에 따른 수산화 칼슘의 제조 방법에 사용되는, 루테늄 산화물 촉매:Ruthenium oxide catalyst used in the method for producing calcium hydroxide according to claim 1: [화학식 Ⅰ][Chemical Formula I] HxRuO2;H x RuO 2 ; 상기 화학식 Ⅰ에서, 0< x ≤4임.In the above chemical formula I, 0< x ≤4. 제 14 항에 있어서,In Article 14, 상기 루테늄 산화물 촉매는 X-선 분말 회절 측정 (Cu Kα 선)에 의해 입사각 (2θ)이 18.38°< 2θ <18.42°, 25.45°< 2θ <25.51°, 26.26°< 2θ <26.32°, 33.45°< 2θ <33.51°, 35.28°< 2θ <35.34°, 36.24°< 2θ <36.30°, 37.32°< 2θ <37.38°, 39.55°< 2θ <39.61°, 40.61°< 2θ <40.67°, 41.46°< 2θ <41.52°, 49.17°< 2θ <49.23°, 52.31°< 2θ <52.37°, 54.03°< 2θ <54.09°, 54.70°< 2θ <54.76°, 55.95°< 2θ <56.01°, 59.97°< 2θ <60.03°, 60.40°< 2θ <60.46°, 61.92°< 2θ <61.98°, 63.94°< 2θ <64.00°, 65.79°< 2θ <65.85° 및 69.13°< 2θ <69.19°인 각 위치에서 회절 피크가 관측되는 것인, 루테늄 산화물 촉매.The above ruthenium oxide catalyst was measured by X-ray powder diffraction (Cu Kα line) and had incident angles (2θ) of 18.38°<2θ <18.42°, 25.45°<2θ <25.51°, 26.26°<2θ <26.32°, 33.45°<2θ <33.51°, 35.28°<2θ <35.34°, 36.24°<2θ <36.30°, 37.32°<2θ <37.38°, 39.55°<2θ <39.61°, 40.61°<2θ <40.67°, 41.46°<2θ <41.52°, 49.17°<2θ <49.23°, A ruthenium oxide catalyst, wherein diffraction peaks are observed at respective positions of 52.31°<2θ <52.37°, 54.03°<2θ <54.09°, 54.70°<2θ <54.76°, 55.95°<2θ <56.01°, 59.97°<2θ <60.03°, 60.40°<2θ <60.46°, 61.92°<2θ <61.98°, 63.94°<2θ <64.00°, 65.79°<2θ <65.85°, and 69.13°<2θ <69.19°. 제 14 항에 있어서,In Article 14, 상기 루테늄 산화물 촉매는 단사정계의 공간군 P21/c, C2/m, P2/c, C2/c, P2/m, 또는 P21/m의 구조인 것인, 루테늄 산화물 촉매.The above ruthenium oxide catalyst is a ruthenium oxide catalyst having a structure of a monoclinic space group P2 1 /c, C2/m, P2/c, C2/c, P2/m, or P2 1 /m. 제 14 항에 있어서,In Article 14, 상기 단사정계 구조에서,In the above monoclinic structure, 5 Å≤ a ≤6 Å, 5 Å≤ b ≤6 Å 및 5 Å≤ c ≤6 Å이고,5 Å≤ a ≤6 Å, 5 Å≤ b ≤6 Å, and 5 Å≤ c ≤6 Å, 베타(β) 각은 110° 내지 120°인 것인, 루테늄 산화물 촉매.A ruthenium oxide catalyst having a beta (β) angle of 110° to 120°. 제 14 항에 있어서,In Article 14, 상기 단사정계 구조에서,In the above monoclinic structure, a=5.3533 Å, b=5.0770 Å, c=5.3532 Å이고, 베타(β) 각은 115.9074° 인 것인, 루테늄 산화물 촉매.A ruthenium oxide catalyst having a=5.3533 Å, b=5.0770 Å, c=5.3532 Å, and the beta (β) angle is 115.9074°.
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