Method for preparing sodium bicarbonate by utilizing catalytic reaction

Abstract

The invention relates to a method for preparing sodium bicarbonate by utilizing catalytic reaction. Compared with the existing Solvar process, the method for preparing sodium bicarbonate according to the embodiment of the invention can be used for preparing high-quality sodium bicarbonate in a short time.

Description

Technical Field

[0001] The present application relates to a method for preparing sodium bicarbonate by a catalytic reaction. Background Art

[0002] Sodium carbonate (Na2CO3) is a common compound, widely used as a raw material for manufacturing soaps, glass, paper, etc., and for removing water hardness. Sodium carbonate is industrially prepared by the Solvay process using sodium chloride (NaCl) and calcium carbonate (CaCO3) as raw materials. The Solvay process includes the following steps: saturating a high-concentration sodium chloride solution with ammonia, and then introducing carbon dioxide into the above solution to obtain a sodium bicarbonate precipitate; and heating the obtained sodium bicarbonate to obtain sodium carbonate. The above sodium chloride solution acts as an ammoniated brine solution and serves as a mother liquor.

[0003] The Solvay process is an energy-intensive process that requires a large amount of energy consumption, so the energy cost is relatively high. Especially in the decomposition process of calcining calcium carbonate at a temperature of about 1,000 °C to prepare carbon dioxide and calcium oxide (CaO), 2.2 GJ to 2.8 GJ of energy is required per ton of calcium carbonate. In addition, in a high-concentration sodium chloride solution (300 g / L), about 30% does not participate in the reaction and remains in the solution, and a large amount of calcium chloride (CaCl2) with little industrial use is generated as a by-product.

[0004] When ammonia is used as a catalyst in the Solvay process, although it can be regenerated and reused after the reaction, since a large amount of ammonia must be additionally supplemented for this purpose, the overall process cost increases. In addition, since the reaction time exceeds 10 hours, there is a disadvantage that the equipment must be enlarged for mass production of sodium bicarbonate. Therefore, it is necessary to develop a new sodium carbonate preparation process with low energy cost, less by-product generation, and fast production rate.

[0005] [Prior Art Documents]

[0006] U.S. Patent Publication No. 5,980,848. Summary of the Invention

[0007] Technical Problem

[0008] The present application provides a method for preparing sodium bicarbonate by a catalytic reaction.

[0009] However, the problems to be solved by the present application are not limited to the above problems, and those skilled in the art will clearly understand other problems not mentioned from the following description.

[0010] Solution to the Problem

[0011] The first aspect of the present application provides a method for preparing sodium bicarbonate, including: obtaining sodium bicarbonate by subjecting nitrate ions, sodium ions, carbon dioxide, and hydrogen to a catalytic reaction.

[0012] The second aspect of the present application provides a method for preparing sodium bicarbonate, including: obtaining sodium bicarbonate by subjecting a sodium-containing substance, nitric acid or nitrate, carbon dioxide, and hydrogen to a catalytic reaction.

[0013] The third aspect of the present application is for the method according to the first aspect; or the method according to the second aspect, and provides a ruthenium oxide catalyst represented by the following Chemical Formula I and having a monoclinic crystal structure:

[0014] [Chemical Formula I]

[0015] H x RuO2;

[0016] In the above Chemical Formula I, 0 < x ≤ 4.

[0017] Advantages of the Invention

[0018] Compared with the existing Solvay process, the method for preparing sodium bicarbonate according to the embodiments of the present application can prepare high-quality sodium bicarbonate in a short time.

[0019] The method for preparing sodium bicarbonate according to the embodiments of the present application can produce high-value ammonia in a short time.

[0020] Different from the Solvay process, the method for preparing sodium bicarbonate according to the embodiments of the present application does not use ammonia, and thus sodium bicarbonate can be prepared at low cost.

[0021] The yield of sodium bicarbonate obtained by using the method for preparing sodium bicarbonate according to the embodiments of the present application can be about 50% or more, 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 98% or more, or about 99% or more.

[0022] The catalyst used in the method for preparing sodium bicarbonate according to the embodiments of the present application will not melt or collapse in structure during the reaction, and thus a long-term reaction can be carried out.

[0023] The catalyst used in the method for preparing sodium bicarbonate according to the embodiments of the present application can be separated, recovered, and reused after the reaction is completed, thereby reducing the cost caused by the catalyst.

[0024] The method for preparing sodium bicarbonate according to the embodiments of the present application can continuously maintain a high yield and high selectivity close to atom economy.

[0025] Since the method for preparing sodium bicarbonate according to the embodiments of the present application only produces water as a by-product, an environmentally friendly process can be achieved.

[0026] The method for preparing sodium bicarbonate according to the embodiments of the present application uses the captured carbon dioxide as a reactant, so that more than about 20 million tons of carbon dioxide can be reduced globally every year. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic diagram of the reaction for preparing sodium carbonate and ammonia by the catalytic reaction of nitrate ions, sodium ions, carbon dioxide and hydrogen in an embodiment of the present application.

[0028] Figure 2 It is a powder X-ray diffraction (PXRD) pattern of sodium bicarbonate (NaHCO3) prepared according to Example 1-1 of the present application.

[0029] Figure 3 It is a PXRD pattern of sodium carbonate (Na2CO3) prepared according to Example 1-1 of the present application.

[0030] Figure 4 It is a PXRD pattern of ammonium sulfate ((NH4)2SO4) prepared according to Example 1-1 of the present application.

[0031] Figure 5 It is a PXRD pattern of ruthenium oxide (H x RuO2) catalyst according to an embodiment of the present application.

[0032] Figure 6 It is a PXRD pattern of sodium bicarbonate (NaHCO3) obtained according to Example 2-1 of the present application.

[0033] Figure 7 It is a PXRD pattern of barium sulfate (BaSO4) obtained according to Example 2-1 of the present application.

[0034] Figure 8 It is a PXRD pattern of ammonium bicarbonate (NH4HCO3) prepared according to Example 2-1 of the present application.

[0035] Figure 9 It is a PXRD pattern of the products (NaHCO3 and Na(NH4)SO4·2H2O) obtained according to Example 2-2 of the present application.

[0036] Figure 10 It is a PXRD pattern of sodium bicarbonate (NaHCO3) obtained according to Example 2-3 of the present application.

[0037] Figure 11It is the PXRD pattern of silver chloride (AgCl) obtained according to Example 2-3 of the present application.

[0038] Figure 12 It is the PXRD pattern of the products (NaHCO3, NH4Cl, NaCl) obtained according to Example 2-4 of the present application.

[0039] Figure 13 It is the PXRD pattern of the products (NaHCO3 and NaNO3) obtained according to Example 2-5 of the present application.

[0040] Figure 14 It is the PXRD pattern of the precipitate (SiO2 and H x RuO2) obtained according to Example 2-5 of the present application.

[0041] Figure 15 It is the PXRD pattern of the products (NaHCO3, Na2CO3·H2O and Na3H(CO3)2·(H2O)2) obtained according to Example 2-6 of the present application.

[0042] Figure 16 It is the PXRD pattern of the precipitate ((NH)2MoO4 and H x RuO2) obtained according to Example 2-6 of the present application. Detailed implementation manners

[0043] Hereinafter, the implementation manners and examples of the present application will be described in detail with reference to the accompanying drawings, so that those of ordinary skill in the art to which the present invention pertains can easily implement it. However, the present invention can be implemented in various different forms and is not limited to the implementation manners and examples described herein. And, in order to clearly illustrate the present invention in the drawings, parts irrelevant to the description are omitted, and similar parts are denoted by similar reference numerals throughout the specification.

[0044] Throughout this specification, when a part is "connected" to another part, this includes not only the case of "direct connection", but also the case of "electrically connected" with other elements interposed therebetween.

[0045] Throughout this specification, when a component is "on" another component, this includes not only the case where one component is in contact with the other component, but also the case where there are other components between the two components.

[0046] Throughout this specification, when a part "includes" a certain component, unless otherwise specifically stated to the contrary, this means that other components can be included, rather than excluding other components.

[0047] Degree terms such as "about" and "substantially" used in this specification, when referring to a meaning with an inherent manufacturing and material tolerance, are used to represent that value or a value close to it, and are used to prevent infringers from unfairly using the exact or absolute values mentioned in the disclosure to help understand this application.

[0048] The degree terms "perform the step of ~" or "the step of ~" used in this specification do not mean "the step for ~".

[0049] In this specification, the term "combinations thereof" included in a Markush format expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush format expression, that is, it means including one or more selected from the group consisting of the said components.

[0050] Throughout this specification, the meaning of "A and / or B" is "A or B, or A and B".

[0051] The embodiments of this application will be described in detail below, but this application is not limited thereto.

[0052] The first aspect of this application provides a method for preparing sodium bicarbonate, comprising: obtaining sodium bicarbonate by subjecting nitrate ions, sodium ions, carbon dioxide and hydrogen to a catalytic reaction.

[0053] In one embodiment of this application, the catalyst may be selected from metals, alloys or oxides, and the metals, alloys or oxides include at least one selected from the following: 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). In one embodiment of this application, the catalyst may be ruthenium powder, platinum powder, palladium powder or ruthenium oxide.

[0054] In one embodiment of this application, the catalyst may include ruthenium oxide represented by the following Chemical Formula I, but is not limited thereto:

[0055] [Chemical Formula I]

[0056] H x RuO2;

[0057] In the above Chemical Formula I, 0 < x ≤ 4.

[0058] In one embodiment of the present application, when the particle size of the catalyst is about 10 nm or less, the reaction activity can be improved.

[0059] In one embodiment of the present application, the catalyst does not melt or its structure collapse during the reaction, so a long-term reaction can be carried out.

[0060] In one embodiment of the present application, the catalyst can be separated, recovered, and reused after the reaction is completed.

[0061] In one embodiment of the present application, considering from the aspects of activity and / or stability, it is preferred to use a catalyst including ruthenium oxide represented by Chemical Formula I for the reaction, but other metals can also be included as co-catalysts.

[0062] In one embodiment of the present application, the catalytic reaction can be carried out in a hydrothermal reactor, but it is not limited thereto.

[0063] In one embodiment of the present application, as a reactant of the catalytic reaction, a solvent can also be included, but it is not limited thereto. In one embodiment of the present application, the solvent can be selected from distilled water, methanol, and ethanol, but it is not limited thereto. In one embodiment of the present application, the solvent can be distilled water.

[0064] In one embodiment of the present application, when sodium nitrate and a solvent are included as reactants, the weight ratio of the solvent to sodium nitrate can be about 0:10 to about 100:1, but it is not limited thereto.

[0065] In one embodiment of the present application, when sodium nitrate is included as a reactant, the molar ratio of the catalyst to sodium nitrate (catalyst:sodium nitrate) can be about 1:5 to about 1:500, but it is not limited thereto. In one embodiment of the present application, when the molar ratio of the catalyst to sodium nitrate is about 1:500 or more, the reaction time may increase and the reaction may not be completed completely, while when the molar ratio of the catalyst to sodium nitrate is less than about 1:5, the reaction rate may increase, but a large amount of catalyst may be required, which may be uneconomical.

[0066] In one embodiment of the present application, the pressure ratio of carbon dioxide to hydrogen (carbon dioxide:hydrogen) can be about 1:1 to about 1:50, about 1:1 to about 1:40, about 1:1 to about 1:30, about 1:1 to about 1:20, about 1:1 to about 1:10, about 1:1 to about 1:5, or about 1:1 to about 1:4, but it is not limited thereto. In one embodiment of the present application, the pressure ratio of carbon dioxide to hydrogen can be about 1:4.

[0067] In one embodiment of the present application, the total pressure of the hydrothermal reactor for the catalytic reaction can be from about 0.1 MPa to about 20 MPa, but is not limited thereto. The total pressure of the hydrothermal reactor can be from about 0.1 MPa to about 20 MPa, from about 0.1 MPa to about 15 MPa, from about 0.1 MPa to about 10 MPa, from about 0.1 MPa to about 5 MPa, from about 1 MPa to about 20 MPa, from about 1 MPa to about 15 MPa, from about 1 MPa to about 10 MPa, from about 1 MPa to about 5 MPa, from about 2 MPa to about 20 MPa, from about 2 MPa to about 15 MPa, from about 2 MPa to about 10 MPa, or from about 2 MPa to about 5 MPa, but is not limited thereto. In one embodiment of the present application, the total pressure of the hydrothermal reactor can be about 2.5 MPa.

[0068] In one embodiment of the present application, the catalytic reaction can be carried out in a temperature range of about 20 °C to about 200 °C, but is not limited thereto. In one embodiment of the present application, the catalytic reaction can be carried out in a temperature range of about 20 °C to about 200 °C, about 20 °C to about 170 °C, about 20 °C to about 150 °C, about 20 °C to about 130 °C, about 20 °C to about 110 °C, about 20 °C to about 90 °C, about 40 °C to about 200 °C, about 40 °C to about 170 °C, about 40 °C to about 150 °C, about 40 °C to about 130 °C, about 40 °C to about 110 °C, about 40 °C to about 90 °C, about 60 °C to about 200 °C, about 60 °C to about 170 °C, about 60 °C to about 150 °C, about 60 °C to about 130 °C, about 60 °C to about 110 °C, or about 60 °C to about 90 °C, but is not limited thereto.

[0069] In one embodiment of the present application, when sodium nitrate is included as a reactant, the reaction time can vary according to the molar ratio of the catalyst to sodium nitrate. In one embodiment of the present application, when sodium nitrate is included as a reactant, when the molar ratio of the catalyst to sodium nitrate is about 1:10 or less, the reaction can be completed in about 1 hour, but is not limited thereto. In one embodiment of the present application, when sodium nitrate is included as a reactant, when the molar ratio of the catalyst to sodium nitrate is about 1:100 or more, the reaction may take about 1 hour or longer to complete, but is not limited thereto.

[0070] In one embodiment of the present application, as a reactant for the catalytic reaction, additives can also be included, but are not limited thereto.

[0071] In one embodiment of the present application, the additive may be at least one selected from NaOH, KOH, LiOH, Ba(OH)₂, Ca(OH)₂, RbOH, CsOH, Sr(OH)₂, CH₃NH₂, C₂H₅NH₂, Mg(OH)₂, and Al(OH)₃. In one embodiment of the present application, the additive may be NaOH.

[0072] In one embodiment of the present application, when nitric acid is included as a reactant, the pH value is increased by adding a basic additive, so that nitrate ions can be generated better.

[0073] In one embodiment of the present application, when sodium nitrate and an additive are included as reactants, the molar ratio of the additive to sodium nitrate may be about 1:1, but it is not limited thereto.

[0074] In one embodiment of the present application, the yield of sodium bicarbonate obtained through the catalytic reaction may be about 90% or more. In one embodiment of the present application, the yield of sodium bicarbonate obtained through the catalytic reaction may be about 50% or more, 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 98% or more, or about 99% or more.

[0075] In one embodiment of the present application, the obtained sodium bicarbonate can be heat-treated to prepare sodium carbonate.

[0076] In one embodiment of the present application, the heat treatment can be carried out in air, but it is not limited thereto.

[0077] In one embodiment of the present application, the heat treatment can be carried out in the temperature range of about 250 °C to about 350 °C. In one embodiment of the present application, the heat treatment can be carried out in the temperature range of about 250 °C to about 350 °C, about 250 °C to about 330 °C, about 250 °C to about 310 °C, about 250 °C to about 290 °C, about 250 °C to about 270 °C, about 270 °C to about 350 °C, about 270 °C to about 330 °C, about 270 °C to about 310 °C, about 270 °C to about 290 °C, about 290 °C to about 350 °C, about 290 °C to about 330 °C, about 290 °C to about 310 °C, about 310 °C to about 350 °C, about 310 °C to about 330 °C, or about 330 °C to about 350 °C, but it is not limited thereto.

[0078] In one embodiment of the present application, ammonia and / or ammonium compounds can also be produced by the method for preparing sodium bicarbonate. In one embodiment of the present application, after the catalytic reaction is completed, an acid can be added to the residual solution to obtain an ammonium compound corresponding to the type of the acid. In one embodiment of the present application, the acid can be selected from sulfuric acid (H2SO4), nitric acid (HNO3), hydrochloric acid (HCl), acetic acid (CH3COOH), carbonic acid (H2CO3), and formic acid (HCOOH), but is not limited thereto. In one embodiment of the present application, the acid can be a weak acid or a strong acid. In one embodiment of the present application, the acid can be sulfuric acid. In one embodiment of the present application, after the catalytic reaction is completed, sulfuric acid can be added to the residual solution to obtain ammonium sulfate. In one embodiment of the present application, the ammonium compound can be selected from at least one of (NH4)2SO4, NH4NO3, NH4Cl, CH3COONH4, (NH4)2CO3, and NH4HCO2, but is not limited thereto.

[0079] In one embodiment of the present application, an ammonium compound can be obtained by injecting carbon dioxide into the residual solution. In one embodiment of the present application, the ammonium compound can be NH4HCO3, but is not limited thereto.

[0080] According to the method for preparing sodium bicarbonate of one embodiment of the present application, water may be produced as a by-product.

[0081] A second aspect of the present application provides a method for preparing sodium bicarbonate, comprising: obtaining sodium bicarbonate by subjecting a sodium-containing substance, nitric acid or nitrate, carbon dioxide, and hydrogen to a catalytic reaction.

[0082] The detailed description of the part repeated with the first aspect of the present application has been omitted. However, even if the description of the second aspect of the present application is omitted, the content described for the first aspect of the present application can be equally applied.

[0083] In one embodiment of the present application, the sodium-containing substance can include at least one selected from sodium salts, sodium-containing composite oxides, and sodium-containing ores, but is not limited thereto.

[0084] In one embodiment of the present application, the solubility of the sodium salt in water can be unrestricted.

[0085] In one embodiment of the present application, the sodium salt can include at least one selected from Na2SO4 and NaCl, and the sodium-containing composite oxide and / or the sodium-containing ore can include at least one selected from Na2SiO3, Na2MoO4, and Na3VO4, but is not limited thereto.

[0086] In one embodiment of the present application, the nitrate may include at least one selected from Ba(NO3)2, Pb(NO3)2, and AgNO3, but is not limited thereto.

[0087] In one embodiment of the present application, the catalyst may be selected from metals, alloys, or oxides, and the metals, alloys, or oxides include at least one selected from the following: 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).

[0088] In one embodiment of the present application, the catalyst may include ruthenium oxide represented by the following Chemical Formula I, but is not limited thereto:

[0089] [Chemical Formula I]

[0090] H x RuO2;

[0091] In the above Chemical Formula I, 0 < x ≤ 4.

[0092] In one embodiment of the present application, when the particle size of the catalyst is about 10 nm or less, the reaction activity can be improved.

[0093] In one embodiment of the present application, the catalyst does not melt or its structure collapses during the reaction, so a long-term reaction can be carried out.

[0094] In one embodiment of the present application, the catalyst can be separated, recovered, and reused after the reaction is completed.

[0095] In one embodiment of the present application, considering from the aspects of activity and / or stability, it is preferred to use a catalyst including ruthenium oxide represented by Chemical Formula I for the reaction, but other metals can also be included as co-catalysts.

[0096] In one embodiment of the present application, the catalytic reaction can be carried out in a hydrothermal reactor, but is not limited thereto.

[0097] In one embodiment of the present application, as a reactant for the catalytic reaction, a solvent may also be included, but is not limited thereto. In one embodiment of the present application, the solvent may be selected from distilled water, methanol, and ethanol, but is not limited thereto. In one embodiment of the present application, the solvent may be distilled water.

[0098] In one embodiment of the present application, the weight ratio of the solvent to the sodium-containing substance (solvent:sodium-containing substance) can be from about 0:10 to about 100:1, but is not limited thereto.

[0099] In one embodiment of the present application, the molar ratio of the catalyst to the sodium-containing substance (catalyst:sodium-containing substance) can be from about 1:5 to about 1:500, but is not limited thereto. In one embodiment of the present application, when the molar ratio of the catalyst to the sodium-containing substance is more than about 1:500, the reaction time may increase and the reaction may not proceed completely, while when the molar ratio of the catalyst to the sodium-containing substance is less than about 1:5, the reaction rate may increase, but a large amount of catalyst may be required, which may be uneconomical.

[0100] In one embodiment of the present application, the pressure ratio of carbon dioxide to hydrogen (carbon dioxide:hydrogen) can be from about 1:1 to about 1:50, about 1:1 to about 1:40, about 1:1 to about 1:30, about 1:1 to about 1:20, about 1:1 to about 1:10, about 1:1 to about 1:5 or about 1:1 to about 1:4, but is not limited thereto. In one embodiment of the present application, the pressure ratio of carbon dioxide to hydrogen can be about 1:4.

[0101] In one embodiment of the present application, the total pressure of the hydrothermal reactor for carrying out the catalytic reaction can be from about 0.1 MPa to about 20 MPa, but is not limited thereto. The total pressure of the hydrothermal reactor can be from about 0.1 MPa to about 20 MPa, about 0.1 MPa to about 15 MPa, about 0.1 MPa to about 10 MPa, about 0.1 MPa to about 5 MPa, about 1 MPa to about 20 MPa, about 1 MPa to about 15 MPa, about 1 MPa to about 10 MPa, about 1 MPa to about 5 MPa, about 2 MPa to about 20 MPa, about 2 MPa to about 15 MPa, about 2 MPa to about 10 MPa, or about 2 MPa to about 5 MPa, but is not limited thereto.

[0102] In one embodiment of the present application, the catalytic reaction can be carried out in a temperature range of about 20°C to about 200°C, but it is not limited thereto. In one embodiment of the present application, the catalytic reaction is carried out in a temperature range of about 20°C to about 200°C, about 20°C to about 170°C, about 20°C to about 150°C, about 20°C to about 130°C, about 20°C to about 110°C, about 20°C to about 90°C, about 40°C to about 200°C, about 40°C to about 170°C, about 40°C to about 150°C, about 40°C to about 130°C, about 40°C to about 110°C, about 40°C to about 90°C, about 60°C to about 200°C, about 60°C to about 170°C, about 60°C to about 150°C, about 60°C to about 130°C, about 60°C to about 110°C, or about 60°C to about 90°C, but it is not limited thereto.

[0103] In one embodiment of the present application, the reaction time can vary according to the molar ratio of the catalyst and the sodium-containing substance. In one embodiment of the present application, when the molar ratio of the catalyst to the sodium-containing substance is about 1:10 or less, the reaction can be completed in about 6 hours, but it is not limited thereto. In one embodiment of the present application, when the molar ratio of the catalyst to the sodium-containing substance is about 1:100 or more, the reaction may take about 1 hour or longer to complete, but it is not limited thereto.

[0104] In one embodiment of the present application, as a reactant for the catalytic reaction, an additive may also be included, but it is not limited thereto.

[0105] In one embodiment of the present application, the additive may be at least one selected from NaOH, KOH, LiOH, Ba(OH)2, Ca(OH)2, RbOH, CsOH, Sr(OH)2, CH3NH2, C2H5NH2, Mg(OH)2, Al(OH)3. In one embodiment of the present application, the additive may be NaOH.

[0106] In one embodiment of the present application, when a sodium-containing substance and an additive are included as reactants, the molar ratio of the additive to the sodium-containing substance may be about 1:1, but it is not limited thereto.

[0107] In one embodiment of the present application, the yield of sodium bicarbonate obtained through the catalytic reaction may be about 90% or more. In one embodiment of the present application, the yield of sodium bicarbonate obtained through the catalytic reaction may be about 50% or more, 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 98% or more, or about 99% or more.

[0108] In one embodiment of the present application, the obtained sodium bicarbonate can be heat-treated to prepare sodium carbonate.

[0109] In one embodiment of the present application, the heat treatment can be carried out in air, but is not limited thereto.

[0110] In one embodiment of the present application, the heat treatment can be carried out in a temperature range of about 250 °C to about 350 °C. In one embodiment of the present application, the heat treatment can be carried out in a temperature range of about 250 °C to about 350 °C, about 250 °C to about 330 °C, about 250 °C to about 310 °C, about 250 °C to about 290 °C, about 250 °C to about 270 °C, about 270 °C to about 350 °C, about 270 °C to about 330 °C, about 270 °C to about 310 °C, about 270 °C to about 290 °C, about 290 °C to about 350 °C, about 290 °C to about 330 °C, about 290 °C to about 310 °C, about 310 °C to about 350 °C, about 310 °C to about 330 °C or about 330 °C to about 350 °C, but is not limited thereto.

[0111] In one embodiment of the present application, compared with the existing Solvay process, the method for preparing sodium bicarbonate can prepare high-quality sodium bicarbonate and valuable useful compounds as by-products at low cost and in a short time. In one embodiment of the present application, the by-products can include at least one selected from BaSO4, AgCl, NaCl, NaNO3, SiO2, ammonia and ammonium compounds, but are not limited thereto. In one embodiment of the present application, the ammonium compounds can include at least one selected from NH4HCO3, Na(NH4)SO4·2H2O, NH4Cl and (NH4)2MoO4, but are not limited thereto.

[0112] In one embodiment of the present application, after the catalytic reaction is completed, ammonia and / or ammonium compounds can be obtained from the residual solution. In one embodiment of the present application, the ammonium compound can be an ammonium salt, but is not limited thereto.

[0113] The third aspect of the present application is for the method according to the first aspect; or for the method according to the second aspect, and provides a ruthenium oxide catalyst represented by the following Chemical Formula I and having a monoclinic crystal structure:

[0114] [Chemical Formula I]

[0115] H x RuO2;

[0116] In the above Chemical Formula I, 0 < x ≤ 4.

[0117] Although the detailed description of the parts that are repeated with the first aspect and the second aspect of the present application is omitted, even if the description is omitted in the third aspect of the present application, the content described for the first aspect and the second aspect of the present application can be equally applied.

[0118] In one embodiment of the present application, for the above chemical formula I, x (atomic ratio of hydrogen) can be greater than 0 and less than or equal to 4, about 0.1 to about 3.5, about 0.1 to about 3, about 0.1 to about 2.5, about 0.1 to about 2, about 0.1 to about 1.5, about 0.1 to about 1.2, about 0.2 to about 3.5, about 0.2 to about 3, about 0.2 to about 2.5, about 0.2 to about 2, about 0.2 to about 1.5, about 0.2 to about 1.2, 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 is not limited thereto.

[0119] In one embodiment of the present application, for chemical formula I, the closer x (atomic ratio of hydrogen atoms) is to about 1, the easier it is to form ruthenium oxide with a monoclinic crystal structure. Specifically, when the proportion of hydrogen is about 0.6 to about 1.4, it is easier to form ruthenium oxide with a monoclinic crystal structure. Here, if x in chemical formula I is 0, a structural transformation to ruthenium oxide with a tetragonal rutile structure will occur, so it is preferred to maintain the hydrogen content.

[0120] In one embodiment of the present application, the atomic ratio of hydrogen contained in chemical formula I can be calculated by thermogravimetric analysis (TGA). Specifically, in the analysis using the above thermogravimetric analysis method, a solid sample can be placed in a platinum container, and the weight change can be measured while raising the temperature. All the hydrogen contained in the above monoclinic ruthenium oxide (H x RuO2) is removed and converted into tetragonal ruthenium oxide (RuO2). According to the change in weight with temperature, the amount of hydrogen gas can be quantitatively analyzed.

[0121] In one embodiment of the present application, ruthenium oxide is measured by X-ray powder diffraction (Cu Kα line) at 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°, 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°, and diffraction peaks are observed at each position. In one embodiment of the present application, ruthenium oxide is determined by X-ray powder diffraction (Cu Kα line) to have diffraction peaks observed at each position with incident angles (2θ) of 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°.

[0122] In one embodiment of the present application, the ruthenium oxide may have a structure with a monoclinic space group of P21 / c, C2 / m, P2 / c, C2 / c, P2 / m, or P21 / m, but is not limited thereto.

[0123] In one embodiment of the present application, the unit cell () of the monoclinic crystal structure of monoclinic ruthenium oxide may be represented as shown in the following figure and may be defined according to the lattice constants a to c and the angle β between the corners.

[0124] In one embodiment of the present application, in the monoclinic structure, and and the β angle may be from about 110° to about 120°. For example, a to c are each independently from about to about about to about about to about about to about about to about about to about about to about about to about about to about about to about about to about about to about about to about about to about about to about about to about or about to about wherein b can be about to about about to about about to about about to about about to about or about to about and wherein the 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 116°.

[0125] In one embodiment of the present application, in the monoclinic crystal structure, and the β angle can be 115.9074°, but is not limited thereto.

[0126] Embodiments of the invention

[0127] [Examples]

[0128] Example 1-1( Figure 1 )

[0129] 10 mg (0.075 mmol) of H xRuO2, 0.15 g (1.76 mmol) of sodium nitrate, and 0.5 mL of distilled water were added to a hydrothermal reactor. Then, a carbon dioxide pressure of 0.5 Mpa and a hydrogen pressure of 2.0 Mpa were charged into the hydrothermal reactor, and the reaction was carried out at 100 °C for 1 h. After the reaction was completed, the hydrothermal reactor was cooled to room temperature, and the generated precipitate was separated from the residual solution.

[0130] Reference Figure 2 For illustration, the precipitate of the RuO2 catalyst was confirmed to be sodium bicarbonate (NaHCO3) by X-ray powder diffraction analysis (PXRD). The amount of sodium bicarbonate obtained was 0.142 g (1.69 mmol), and the yield of sodium bicarbonate calculated based on sodium nitrate was 96.0%. The above sodium bicarbonate powder was heat-treated at 300 °C to be converted into sodium carbonate, and it was confirmed by X-ray powder diffraction analysis (reference x ) that the yield of sodium carbonate was over 99%. Figure 3 )

[0131] The result of analyzing the above residual solution by ultraviolet-visible spectroscopy (UV-vis) showed that nitrate ions (NO3 - and NO2 - ) were not confirmed, thus confirming that all the nitrate ions of the reactants had been converted into ammonia or nitrogen. Sulfuric acid and acetone were added to the residual solution, followed by separation and drying to obtain a white powder, which was confirmed to be ammonium sulfate ((NH4)2SO4) by X-ray powder diffraction analysis (reference Figure 4 ). The amount of ammonium sulfate obtained was 0.095 g (0.72 mmol), and the yield of ammonium sulfate calculated based on sodium nitrate was 81.7%.

[0132] <Hydrogen Pressure Regulation>

[0133] Example 1-2

[0134] The reaction was carried out in the same manner as in Example 1-1 except that the reaction was carried out at a hydrogen pressure of 1.0 Mpa. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis. The solids precipitated from the precipitate and the residual solution were confirmed to be sodium bicarbonate and sodium nitrate. The yield of sodium bicarbonate calculated based on sodium nitrate was 51.1%. Sulfuric acid and acetone were added to the above residual solution, followed by separation and drying to obtain a small amount of white ammonium sulfate powder.

[0135] Example 1-3

[0136] The reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out under a hydrogen pressure of 3.0 MPa. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis, and the solid precipitated from the precipitate and the residual solution was confirmed to be sodium bicarbonate. The yield of sodium bicarbonate calculated based on sodium nitrate was 89.1%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out to obtain a small amount of white ammonium sulfate powder.

[0137] <Reaction temperature adjustment>

[0138] Example 1-4

[0139] The reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at 80 °C. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis, and the solid precipitated from the precipitate and the residual solution was confirmed to be sodium bicarbonate and sodium nitrate. The yield of sodium bicarbonate calculated based on sodium nitrate was 71.1%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out to obtain a small amount of white ammonium sulfate powder.

[0140] Example 1-5

[0141] The reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at 120 °C. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis, and the solid precipitated from the precipitate and the residual solution was confirmed to be sodium bicarbonate. The yield of sodium bicarbonate calculated based on sodium nitrate was 91.5%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out to obtain a small amount of white ammonium sulfate powder.

[0142] <Volume adjustment of solvent>

[0143] Example 1-6

[0144] The reaction was carried out in the same manner as in Example 1-1, except that 0.1 mL of distilled water was used as the solvent for the reaction. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis, and the solid precipitated from the precipitate and the residual solution was confirmed to be sodium bicarbonate and sodium nitrate. The yield of sodium bicarbonate calculated based on sodium nitrate was 80.1%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out to obtain a small amount of white ammonium sulfate powder.

[0145] Example 1-7

[0146] Except for using 2.5 mL of distilled water as the solvent for the reaction, the reaction was carried out in the same manner as in Example 1-1. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis. The solids precipitated from the precipitate and the residual solution were confirmed to be sodium bicarbonate and sodium nitrate. The yield of sodium bicarbonate calculated based on sodium nitrate was 10.5%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out to obtain a small amount of white ammonium sulfate powder.

[0147] <Catalyst type change>

[0148] Example 1-8

[0149] Except for using ruthenium powder (7.6 mg, 0.075 mmol) as the catalyst for the reaction, the reaction was carried out in the same manner as in Example 1-1. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis. The solids precipitated from the precipitate and the residual solution were confirmed to be sodium bicarbonate and sodium nitrate. The yield of sodium bicarbonate calculated based on sodium nitrate was 25.1%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out to obtain a small amount of white ammonium sulfate powder.

[0150] Example 1-9

[0151] Except for using platinum powder (14.6 mg, 0.075 mmol) as the catalyst for the reaction, the reaction was carried out in the same manner as in Example 1-1. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis. The solids precipitated from the precipitate and the residual solution were confirmed to be sodium bicarbonate and sodium nitrate. The yield of sodium bicarbonate calculated based on sodium nitrate was less than 1.0%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out, but almost no white powder was obtained.

[0152] Example 1-10

[0153] Except for using palladium powder (8.0 mg, 0.075 mmol) as the catalyst for the reaction, the reaction was carried out in the same manner as in Example 1-1. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis. The solids precipitated from the precipitate and the residual solution were confirmed to be sodium bicarbonate and sodium nitrate. The yield of sodium bicarbonate calculated based on sodium nitrate was 7.1%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out, but almost no white powder was obtained.

[0154] <Additive addition>

[0155] Example 1-11

[0156] Except for adding 0.5 mL of 1 M NaOH solution as an additive for the reaction, it was carried out in the same manner as in Example 1-1. After the reaction was completed, the crystal structure was confirmed by X-ray powder diffraction analysis. The solid precipitated from the precipitate and the residual solution was confirmed to be sodium bicarbonate. The yield of sodium bicarbonate calculated based on sodium nitrate was 88.7%. After adding sulfuric acid and acetone to the above residual solution, separation and drying were carried out to obtain white ammonium sulfate powder.

[0157] Example 2-1

[0158] 0.284 g (2.00 mmol) of sodium sulfate (Na2SO4), 0.523 g (2.00 mmol) of barium nitrate (Ba(NO3)2), 20 mg (0.15 mmol) of H x RuO2, and 4 mL of distilled water were added together to a hydrothermal reactor. Then, a carbon dioxide pressure of 1.0 Mpa and a hydrogen pressure of 4.0 Mpa were charged into the interior of the hydrothermal reactor, and the reaction was carried out at 100 °C for 6 hours. After the reaction was completed, the hydrothermal reactor was cooled to room temperature, and the generated precipitate was separated from the residual solution.

[0159] The crystal obtained by drying the above residual solution was confirmed to be NaHCO3 by X-ray powder diffraction analysis (PXRD) (reference Figure 6 ). The mass of the obtained NaHCO3 was 0.334 g (3.98 mmol), and the yield of NaHCO3 calculated based on Na2SO4 was 99.4%.

[0160] By X-ray powder diffraction analysis method, it was confirmed that the above precipitate was barium sulfate (BaSO4) (reference Figure 7 ). The mass of the obtained BaSO4 was 0.448 g (1.92 mmol), and the yield of BaSO4 calculated based on Ba(NO3)2 was 96.0%.

[0161] The result of analyzing the residual solution after the reaction by ultraviolet-visible spectroscopy (UV-vis) showed that no nitrate ions (NO3 - and NO2 - ) were confirmed. Thus, it was confirmed that all the nitrate ions in the reactants were reduced to ammonia or nitrogen. After adding acetone to the above residual solution, the generated precipitate was separated and dried to obtain a white powder. The above white powder was confirmed to be ammonium bicarbonate (NH4HCO3) by X-ray powder diffraction analysis (reference Figure 8 ).

[0162] Example 2-2

[0163] The reaction was carried out in the same manner as in Example 2-1, except that 4 mL of 1.0 M nitric acid was used as a reactant. After the reaction was completed, the above hydrothermal reactor was cooled to room temperature, the catalyst and the product were separated, and the above product was confirmed to be NaHCO3 and Na(NH4)SO4·2H2O by X-ray powder diffraction analysis (reference Figure 9 ).

[0164] Example 2-3

[0165] The reaction was carried out in the same manner as in Example 2-1, except that 0.234 g (4.00 mmol) of sodium chloride (NaCl) and 0.679 g (4.00 mmol) of silver nitrate (AgNO3) were used as reactants. After the reaction was completed, the above hydrothermal reactor was cooled to room temperature, and the precipitate and the residual solution were separated.

[0166] The crystals obtained by drying the above residual solution were confirmed to be NaHCO3 by X-ray powder diffraction analysis (reference Figure 10 ). The mass of the obtained NaHCO3 was 0.332 g (3.95 mmol), and the yield of NaHCO3 calculated based on NaCl was 98.8%.

[0167] By X-ray powder diffraction analysis, the above precipitate was confirmed to be silver chloride (AgCl) (reference Figure 11 ). The mass of the obtained AgCl was 0.548 g (3.82 mmol), and the yield of AgCl calculated based on AgNO3 was 95.6%.

[0168] Example 2-4

[0169] The reaction was carried out in the same manner as in Example 2-3, except that 4 mL of 1.0 M nitric acid was used as a reactant. After the reaction was completed, the hydrothermal reactor was cooled to room temperature, the catalyst and the product were separated, and the above product was confirmed to be NaHCO3, NH4Cl, and NaCl by X-ray powder diffraction analysis (reference Figure 12 ).

[0170] Example 2-5

[0171] The reaction was carried out in the same manner as in Example 2-1, except that 0.568 g (2.00 mmol) of sodium silicate (Na2SiO3·9H2O) and 4 mL of 1.0 M nitric acid were used as reactants. After the reaction was completed, the hydrothermal reactor was cooled to room temperature, and the precipitate and the residual solution were separated.

[0172] The crystals obtained by drying the above residual solution were confirmed to be NaHCO3 and NaNO3 by X-ray powder diffraction analysis (referenceFigure 13 )。The mass of the obtained crystal was 0.339 g, the yield of sodium was greater than 99%, and the yield of NaHCO3 was 25.0%.

[0173] Through X-ray powder diffraction analysis, it was confirmed that the above precipitate was amorphous SiO2 and H x RuO2 catalyst. The mass of the above precipitate was 0.140 g, and the yield was 99.9% (reference Figure 14 ).

[0174] Examples 2-6

[0175] The reaction was carried out in the same manner as in Example 2-1, except that 0.484 g (2.00 mmol) of sodium molybdate (Na2MoO4·2H2O) and 4 mL of 1.0 M nitric acid were used as reactants. After the reaction was completed, the above hydrothermal reactor was cooled to room temperature, and the precipitate and the residual solution were separated.

[0176] The crystal obtained by drying the above residual solution was confirmed to be sodium carbonate (NaHCO3, Na2CO3H2O, and Na3H(CO3)2(H2O)2) by X-ray powder diffraction analysis (reference Figure 15 ). The mass of the obtained crystal was 0.319 g, and the yield of sodium was over 99%.

[0177] Through X-ray powder diffraction analysis, it was confirmed that the above precipitate was amorphous (NH4)2MoO4 and H x RuO2 catalyst. The mass of the above precipitate was 0.388 g, and the yield was 99.0% (reference Figure 16 ).

[0178] <Reaction gas pressure regulation>

[0179] Example 2-7

[0180] The reaction was carried out in the same manner as in Example 2-1, except that the reaction was carried out under a carbon dioxide pressure of 0.5 MPa and a hydrogen pressure of 2.0 MPa. The yield of NaHCO3 obtained after the reaction was 68.7%.

[0181] Example 2-8

[0182] The reaction was carried out in the same manner as in Example 2-1, except that the reaction was carried out under a carbon dioxide pressure of 2.0 MPa and a hydrogen pressure of 3.0 MPa. The yield of NaHCO3 obtained after the reaction was 98.6%.

[0183] <Reaction temperature regulation>

[0184] Example 2-9

[0185] The reaction was carried out in the same manner as in Example 2-1, except that the reaction was carried out at 80 °C. The yield of NaHCO3 obtained after the reaction was 60.8%.

[0186] Example 2-10

[0187] The reaction was carried out in the same manner as in Example 2-1, except that the reaction was carried out at 120 °C. The yield of NaHCO3 obtained after the reaction was 99.1%.

[0188] <Volume adjustment of solvent>

[0189] Example 2-11

[0190] The reaction was carried out in the same manner as in Example 2-1, except that 2.0 mL of distilled water was used as the solvent for the reaction. The yield of NaHCO3 obtained after the reaction was 88.0%.

[0191] Example 2-12

[0192] The reaction was carried out in the same manner as in Example 2-1, except that 8.0 mL of distilled water was used as the solvent for the reaction. The yield of NaHCO3 obtained after the reaction was 71.4%.

[0193] <Change of catalyst type>

[0194] Example 2-13

[0195] The reaction was carried out in the same manner as in Example 2-1, except that ruthenium powder (15.2 mg, 0.15 mmol) was used as the catalyst for the reaction. The yield of NaHCO3 obtained after the reaction was less than 5%, so the amount obtained was very small.

[0196] Example 2-14

[0197] The reaction was carried out in the same manner as in Example 2-1, except that platinum powder (29.3 mg, 0.15 mmol) was used as the catalyst for the reaction. The yield of NaHCO3 obtained after the reaction was less than 5%, so the amount obtained was very small.

[0198] Example 2-15

[0199] The reaction was carried out in the same manner as in Example 2-1, except that palladium powder (16.0 mg, 0.15 mmol) was used as the catalyst for the reaction. The yield of NaHCO3 obtained after the reaction was 11.8%.

[0200] The above description of the present application is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains should understand that it can be easily modified into other specific forms without changing the technical idea or basic features of the present application. Therefore, it should be understood that the above embodiments are exemplary in all aspects and not restrictive. For example, each component described as a single entity can be implemented in a distributed manner, and similarly, components described as distributed can be implemented in a combined manner.

[0201] The scope of the present application is represented by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included within the scope of the present application.

Claims

1. A method for preparing sodium bicarbonate, comprising: Obtaining sodium bicarbonate by subjecting nitrate ions, sodium ions, carbon dioxide, and hydrogen to a catalytic reaction.

2. The method for preparing sodium bicarbonate according to claim 1, wherein The catalyst is selected from metals, alloys, or oxides, and the metals, alloys, or oxides include at least one selected from the following: 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).

3. The method for preparing sodium bicarbonate according to claim 2, wherein The catalyst comprises ruthenium oxide represented by the following Chemical Formula I: [Chemical Formula I] H x RuO2; In the Chemical Formula I, 0 < x ≤ 4.

4. The method for preparing sodium bicarbonate according to claim 1, wherein The catalytic reaction is carried out in a hydrothermal reactor.

5. The method for preparing sodium bicarbonate according to claim 1, wherein As a reactant for the catalytic reaction, a solvent is further included.

6. The method for preparing sodium bicarbonate according to claim 5, wherein The solvent is selected from distilled water, methanol, and ethanol.

7. The method for preparing sodium bicarbonate according to claim 1, wherein The pressure ratio of carbon dioxide to hydrogen (carbon dioxide: hydrogen) is 1:1 to 1:

50.

8. The method for preparing sodium bicarbonate according to claim 1, wherein The catalytic reaction is carried out in a temperature range of 20°C to 200°C.

9. The method for preparing sodium bicarbonate according to claim 1, wherein As a reactant for the catalytic reaction, an additive is further included.

10. The method for preparing sodium bicarbonate according to claim 9, wherein The additive is at least one selected from NaOH, KOH, LiOH, Ba(OH)₂, Ca(OH)₂, RbOH, CsOH, Sr(OH)₂, CH₃NH₂, C₂H₅NH₂, Mg(OH)₂, and Al(OH)₃.

11. The method for preparing sodium bicarbonate according to claim 1, wherein Ammonia and / or ammonium compounds are also prepared by the method for preparing sodium bicarbonate.

12. The method for preparing sodium bicarbonate according to claim 11, wherein The ammonium compound includes at least one selected from NH₄HCO₃, (NH₄)₂SO₄, NH₄NO₃, NH₄Cl, CH₃COONH₄, (NH₄)₂CO₃, and NH₄HCO₂.

13. A method for preparing sodium bicarbonate, comprising: Obtaining sodium bicarbonate by subjecting a sodium-containing substance, nitric acid or nitrate, carbon dioxide, and hydrogen to a catalytic reaction.

14. The method for preparing sodium bicarbonate according to claim 13, wherein The sodium-containing substance includes at least one selected from sodium salts, sodium-containing composite oxides, and sodium-containing ores.

15. The method for preparing sodium bicarbonate according to claim 14, wherein, the sodium salt includes at least one selected from Na2SO4 and NaCl, the sodium-containing composite oxide and / or the sodium-containing ore includes at least one selected from Na2SiO3, Na2MoO4 and Na3VO4.

16. The method for preparing sodium bicarbonate according to claim 13, wherein, the nitrate includes at least one selected from Ba(NO3)2, Pb(NO3)2 and AgNO3.

17. The method for preparing sodium bicarbonate according to claim 13, wherein, the catalyst is selected from metals, alloys or oxides, and the metals, alloys or oxides include at least one selected from the following: 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).

18. The method for preparing sodium bicarbonate according to claim 17, wherein, the catalyst includes ruthenium oxide represented by the following chemical formula I: [Chemical formula I] H x RuO2; In the chemical formula I, 0 < x ≤ 4.

19. The method for preparing sodium bicarbonate according to claim 13, wherein, the catalytic reaction is carried out in a hydrothermal reactor.

20. The method for preparing sodium bicarbonate according to claim 13, wherein, as a reactant of the catalytic reaction, a solvent is further included.

21. The method for preparing sodium bicarbonate according to claim 20, wherein, the solvent is selected from distilled water, methanol and ethanol.

22. The method for preparing sodium bicarbonate according to claim 13, wherein, the pressure ratio of carbon dioxide to hydrogen (carbon dioxide: hydrogen) is 1:1 to 1:

50.

23. The method for preparing sodium bicarbonate according to claim 13, wherein, the catalytic reaction is carried out in a temperature range of 20°C to 200°C.

24. The method for preparing sodium bicarbonate according to claim 13, wherein, as a reactant of the catalytic reaction, an additive is further included.

25. The method for preparing sodium bicarbonate according to claim 24, wherein, the additive is at least one selected from NaOH, KOH, LiOH, Ba(OH)2, Ca(OH)2, RbOH, CsOH, Sr(OH)2, CH3NH2, C2H5NH2, Mg(OH)2 and Al(OH)3.

26. The method for preparing sodium bicarbonate according to claim 13, wherein, by the method for preparing sodium bicarbonate, in addition to preparing sodium bicarbonate, a by-product is also prepared.

27. The method for preparing sodium bicarbonate according to claim 26, wherein, the by-product includes at least one selected from BaSO4, AgCl, NaCl, NaNO3, SiO2, ammonia and ammonium compounds.

28. The method for preparing sodium bicarbonate according to claim 27, wherein, the ammonium compound includes at least one selected from NH4HCO3, Na(NH4)SO4·2H2O, NH4Cl, and (NH4)2MoO4.

29. A ruthenium oxide catalyst, which is used in the method according to claim 1 or 13, the ruthenium oxide catalyst is represented by the following Chemical Formula I and has a monoclinic crystal structure: [Chemical Formula I] H x RuO2; In the Chemical Formula I, 0 < x ≤ 4.

30. The ruthenium oxide catalyst according to claim 29, wherein, the ruthenium oxide catalyst observes diffraction peaks at respective positions where the incident angle (2θ) is 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°, and 69.13° < 2θ < 69.19° by X-ray powder diffraction measurement (Cu Kα line).

31. The ruthenium oxide catalyst according to claim 29, wherein, the ruthenium oxide catalyst has a structure of the space group P21 / c, C2 / m, P2 / c, C2 / c, P2 / m, or P21 / m of the monoclinic crystal system.

32. The ruthenium oxide catalyst according to claim 31, wherein, in the monoclinic crystal structure, and the β angle is 110° to 120°.

33. The ruthenium oxide catalyst according to claim 31, wherein, in the monoclinic crystal structure, And the β angle is 115.9074°.

Images