Process for the production of a carbon dioxide capture shift catalyst

Abstract

The present invention relates to a manufacturing method of a carbon dioxide capture conversion catalyst which can remove carbon dioxide while resourceizing into other useful substances by capturing carbon dioxide in exhaust gas generated at the time of combustion of fossil fuel and converting into carbon resources, and a carbon dioxide capture conversion catalyst manufactured according to the manufacturing method, and the carbon dioxide capture conversion catalyst according to the present invention can reduce carbon dioxide by capturing carbon dioxide in exhaust gas generated at the time of combustion of fossil fuel, and can resourceize into other useful substances by resourceizing into sodium carbonate or sodium bicarbonate using the captured carbon dioxide carbon resources.

Description

TECHNICAL FIELD

[0001] The present application relates to a method of manufacturing a carbon dioxide capture conversion catalyst that can resource other useful substances while removing carbon dioxide by capturing and converting carbon dioxide in exhaust gas generated when fossil fuel is burned into a carbon resource. BACKGROUND

[0002] Climate change of the earth is periodically accompanied by changes in the orbit, the angle of the axis of rotation, the period of precession, and the amount of radiation of the sun, and presents an ice age and an interglacial period, and the temperature rise at the time of transition from an ice age to an interglacial period is 1°C per 100 years. However, in the last 100 years, the average rise is 0.74°C, which is 7 times higher than the temperature rise caused by natural phenomena, and this is a human phenomenon caused by human activities. Global warming causes global ecosystems to be disturbed, such as a rise in sea level, famine, outbreaks of diseases such as malaria, and changes in water resources due to a rise in the temperature of the earth.

[0003] In particular, carbon dioxide is considered to be a greenhouse gas that causes global warming, and although the global warming index of carbon dioxide is relatively low compared to other greenhouse gases, it is attracting much attention because it accounts for 80% of all greenhouse gas emissions and can be regulated. In this regard, the International Maritime Organization (IMO) has finally decided to apply the Energy Efficiency Design Index (EEDI) to new ships to be built in the future, and thus the amount of greenhouse gas emissions needs to be reduced by an average of 30% compared to the present until 2025.

[0004] Accordingly, as one of the climate change conventions for preventing global warming and the solutions for reducing carbon dioxide emissions, which accounts for most of the greenhouse gases that induce global warming, research activities related to carbon dioxide capture and storage (CSS) technology are actively being conducted.

[0005] Carbon dioxide capture and storage (CSS) technology is a technology of capturing and transporting greenhouse gases emitted when chemical fuels are burned and storing or converting them (immobilization). The technology can effectively reduce the amount of CO2 emissions, and thus is considered to be a realistic alternative solution that plays a bridging role before the economy of new renewable energy can be ensured.

[0006] Carbon dioxide capture and storage (CSS) is mainly used to reduce carbon dioxide generated in the process of power generation using coal and gas, but can also be applied to carbon dioxide-intensive industries such as cement, steel, petrochemical, oil and gas production. As a storage method, different methods such as underground storage, ocean storage or mineral storage are included. However, ocean storage has been banned because it can induce high environmental risks. Mineral storage is currently the main research topic, but there is still a need for development of technologies such as improved technologies for reducing energy use and large-scale emission reduction.

[0007] In addition, as the most effective method for removing carbon dioxide from a gas containing carbon dioxide such as a gas mixture generated in hydrogen, steel and cement production engineering, and combustion exhaust gas discharged from a power plant using fossil fuels and natural gas, a chemical absorption method using an aqueous amine solution can be exemplified. As a chemical absorbent, research related to an aqueous amine solution such as monoethanolamine (MEA) and diethanolamine (DEA) is most common because the amine absorbent can easily react with carbon dioxide and generate a stable carbamate compound, and the compound can be decomposed into carbon dioxide and amine upon heating, thereby regenerating the alcohol amine absorbent.

[0008] However, the above-described engineering also causes several serious problems at the same time, especially the generation of by-products due to impurities such as NOx, SOx and oxygen contained in the combustion exhaust gas, the decrease in absorbent performance due to decomposition, and the device corrosion problem due to this, the problem of requiring a regeneration temperature of 120°C or more due to the high thermochemical stability of the carbamate generated by the reaction with carbon dioxide and thus requiring excessive regeneration energy, the problem of excessive volatilization loss of the alcohol amine due to the high regeneration temperature and thus the problem of absorbent replenishment, the problem of the separated carbon dioxide being contaminated during the regeneration process due to the low vapor pressure of the absorbent, and the like.

[0009] Therefore, there is a need to develop a stable catalyst for removing carbon dioxide which is not affected by impurities other than carbon dioxide contained in the combustion exhaust gas and does not require excessive regeneration energy. SUMMARY

[0010] The present application provides a method for manufacturing a carbon dioxide capture conversion catalyst that can capture carbon dioxide in exhaust gas generated when fossil fuels are burned and convert it into a carbon resource, thereby removing carbon dioxide while being recycled into other useful substances.

[0011] To solve the problems as described above, an embodiment of the present application provides a method for manufacturing a carbon dioxide capture conversion catalyst, comprising: (a) a step of manufacturing oxide fine powder and metal fine powder by micronizing an oxide powder and a metal powder, respectively; (b) a step of manufacturing a crystallized synthetic zeolite by charging an alumina-based raw material, a silica-based raw material, and sodium hydroxide into a reaction furnace; (c) a step of mixing a first alkaline solution after charging the oxide fine powder into the crystallized synthetic zeolite at a certain time interval and stirring; (d) a step of charging the metal fine powder into the mixture of the step (c) at a certain time interval and stirring after mixing a second alkaline solution; and (e) a step of obtaining a carbon dioxide capture conversion catalyst by stabilizing after mixing a third alkaline solution into the mixture of the step (d) and extracting only a liquid portion.

[0012] The average size of the oxide fine powder and the metal fine powder can be 0.5 to 5 μm.

[0013] In the step (b), the crystallized synthetic zeolite can be manufactured by stirring at 30 to 70°C for 1 to 10 hours after charging the alumina-based raw material, the silica-based raw material, and sodium hydroxide into the reaction furnace.

[0014] When charging at a certain time interval in the steps (c) and (d), a prescribed charging amount can be charged in intervals of 1 to 10 minutes.

[0015] In the step (e), the separation into a liquid composition and a precipitated powder composition can be performed by naturally cooling after mixing the third alkaline solution and stabilizing for 40 to 50 hours.

[0016] The oxide powder can include one or more selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O, and P2O3.

[0017] The metal powder can include one or more selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd, and Pb.

[0018] The alumina-based raw material can be sodium tetrakis hydroxy aluminate (NaAl(OH)4), and the silica-based raw material can be sodium silicate (Na2SiO3).

[0019] The first, second, and third basic solutions can each independently include one or more selected from the group consisting of potassium hydroxide (KOH), sodium tetraborate (Na2B4O7·10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), hydrogen peroxide (H2O2), and combinations thereof.

[0020] Further, in an embodiment of the present application, there is provided a carbon dioxide capture conversion catalyst manufactured according to a manufacturing method of the carbon dioxide capture conversion catalyst, including: one or more oxides selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O, and P2O3; one or more metals selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd, and Pb; a crystallized synthetic zeolite manufactured using an alumina-based raw material, a silica-based raw material, and sodium hydroxide; and one or more basic solutions selected from the group consisting of potassium hydroxide (KOH), sodium tetraborate (Na2B4O7·10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), hydrogen peroxide (H2O2), and combinations thereof.

[0021] The oxides can include SiO2 15 to 90 parts by weight, Al2O3 15 to 100 parts by weight, Fe2O3 10 to 50 parts by weight, TiO2 5 to 15 parts by weight, MgO 20 to 150 parts by weight, MnO 10 to 20 parts by weight, CaO 20 to 200 parts by weight, Na2O 15 to 45 parts by weight, K2O 20 to 50 parts by weight, and P2O3 5 to 20 parts by weight, the metals can include Li 0.0035 to 0.009 parts by weight, Cr 0.005 to 0.01 parts by weight, Co 0.001 to 0.005 parts by weight, Ni 0.006 to 0.015 parts by weight, Cu 0.018 to 0.03 parts by weight, Zn 0.035 to 0.05 parts by weight, Ga 0.04 to 0.08 parts by weight, Sr 0.02 to 0.05 parts by weight, Cd 0.002 to 0.01 parts by weight, and Pb 0.003 to 0.005 parts by weight, the zeolite can include 75 to 420 parts by weight, and the basic solution can include potassium hydroxide (KOH) 15 to 120 parts by weight, sodium tetraborate (Na2B4O7·10H2O) 20 to 130 parts by weight, sodium hydroxide (NaOH) 15 to 120 parts by weight, sodium silicate (Na2SiO3) 50 to 250 parts by weight, and hydrogen peroxide (H2O2) 10 to 50 parts by weight.

[0022] 0.3 to 0.5 kg / h of carbon dioxide can be captured per 1 kg of the carbon dioxide capture conversion catalyst.

[0023] The pH of the carbon dioxide capture conversion catalyst can be pH 12 to pH 14.

[0024] The present application belongs to a manufacturing method of a carbon dioxide capture conversion catalyst which can capture carbon dioxide while converting it into sodium carbonate or sodium bicarbonate, thereby removing carbon dioxide, using a carbon dioxide capture conversion catalyst in a solution state.

[0025] According to the carbon dioxide capture conversion catalyst of the present application, carbon dioxide can be reduced by capturing carbon dioxide in exhaust gas generated when fossil fuel is burned, and can be carbon resourceized into sodium carbonate or sodium bicarbonate using the captured carbon dioxide, and can be resourceized into other useful substances.

[0026] Further, according to the carbon dioxide capture conversion catalyst of the present application, sodium carbonate or sodium bicarbonate manufactured using captured carbon dioxide can be used as a desulfurizer for capturing sulfur oxides in exhaust gas generated when chemical fuel is burned, and thus carbon dioxide and sulfur oxides can be removed simultaneously using one catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0027] FIG. 1(a) is a schematic diagram illustrating the results of a carbon dioxide capture test of a carbon dioxide capture conversion catalyst according to the present embodiment (scrubber data before carbon dioxide capture).

[0028] FIG. 1(b) is a schematic diagram illustrating the results of a carbon dioxide capture test of a carbon dioxide capture conversion catalyst according to the present embodiment (scrubber data after carbon dioxide capture).

[0029] FIG. 1(c) is a schematic diagram illustrating the results of a carbon dioxide capture saturation test of a carbon dioxide capture conversion catalyst according to the present embodiment.

[0030] Figure 2 is a schematic diagram illustrating the results of a carbon dioxide capture test of Comparative Example 1 and Comparative Example 2 in the present embodiment. DETAILED DESCRIPTION

[0031] The present application can be modified in various ways and has various embodiments, and specific embodiments will be illustrated in the accompanying drawings and specifically described in the detailed description below.

[0032] However, this is not intended to limit the present application to specific embodiments, but should be understood to include all modifications, equivalents, and alternatives within the scope of the idea and technical range of the present application.

[0033] In the present application, terms such as "comprise" or "have" are used to indicate that the features, numbers, steps, actions, components, parts or combinations thereof described in the specification exist, and should not be understood as excluding the possibility of existence or addition of one or more other features, numbers, steps, actions, components, parts or combinations thereof.

[0034] Next, the present application will be specifically described.

[0035] The present application provides a manufacturing method of a carbon dioxide capture conversion catalyst, comprising: (a) a step of manufacturing an oxide fine powder and a metal fine powder by respectively performing micronization on an oxide powder and a metal powder; (b) a step of manufacturing a crystallized synthetic zeolite by inputting an alumina-based raw material, a silica-based raw material and sodium hydroxide into a reaction furnace; (c) a step of mixing a first alkaline solution after inputting the oxide fine powder into the crystallized synthetic zeolite at a certain time interval and performing stirring; (d) a step of inputting the metal fine powder into the mixture of the step (c) at a certain time interval and performing stirring after mixing a second alkaline solution; and (e) a step of obtaining a carbon dioxide capture conversion catalyst by performing stabilization and extracting only a liquid portion after mixing a third alkaline solution into the mixture of the step (d).

[0036] The carbon dioxide capture conversion catalyst manufactured according to the manufacturing method of the present application can reduce carbon dioxide by capturing carbon dioxide in exhaust gas generated when fossil fuel is burned, and can be carbon resourceized into sodium carbonate or sodium bicarbonate using the captured carbon dioxide, and can be resourceized into other useful substances.

[0037] In addition, the carbon dioxide capture conversion catalyst according to the present application can use sodium carbonate or sodium bicarbonate manufactured using the captured carbon dioxide as a desulfurizer for capturing sulfur oxides in exhaust gas generated when chemical fuel is burned, and thus can simultaneously remove carbon dioxide and sulfur oxides using one catalyst.

[0038] Specifically, the manufacturing method of the carbon dioxide capture conversion catalyst of the present application, in the step (a), can manufacture an oxide fine powder after dissolving the oxide powder in a melting furnace at 3 to 12 bar and 600 to 1,500°C for 0.5 to 10 hours, cooling at room temperature and performing micronization using a micronizer.

[0039] The oxide powder can include one or more selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O and P2O3.

[0040] The metal powder can include one or more selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd, and Pb. The metal powder can be micronized using a micronizer after being mixed, thereby manufacturing a metal micropowder.

[0041] The average size of the oxide micropowder and the metal micropowder can be 0.5 to 5 μm. For example, the average size of the oxide micropowder and the metal micropowder can be 0.5 to 4 μm, 0.5 to 3 μm, 0.5 to 2 μm, 0.5 to 1 μm, 1 to 5 μm, 2 to 5 μm, 3 to 5 μm, or 1 to 2 μm. When the oxide micropowder and the metal micropowder are micronized, micronization can be sufficiently performed until the size is satisfied.

[0042] In the step (b), the crystallized synthetic zeolite can be manufactured by stirring for 1 to 10 hours at 30 to 70°C after the water, the alumina-based raw material, the silica-based raw material, and the sodium hydroxide are charged into a reaction furnace.

[0043] The alumina-based raw material can be sodium tetrakis hydroxy aluminate (NaAl(OH)4), and the silica-based raw material can be sodium silicate (Na2SiO3).

[0044] In the step (c), the first basic solution can be mixed after the oxide micropowder is charged into the crystallized synthetic zeolite in units of 100 kg at a certain time interval and stirred.

[0045] When charged at a certain time interval in the step (c), a prescribed amount of charge can be charged in intervals of 1 to 10 minutes and stirred. For example, the time interval can be 5 minutes.

[0046] In the step (d), the metal micropowder yttrium can be charged in units of 20 g at a certain time interval and stirred after a second basic solution is mixed with the mixture of the step (c).

[0047] When charged at a certain time interval in the step (d), a prescribed amount of charge can be charged in intervals of 1 to 10 minutes and stirred. For example, the time interval can be 3 minutes.

[0048] In the step (e), the mixture can be naturally cooled and stabilized for 40 to 50 hours after a third basic solution is mixed with the mixture of the step (d), thereby being separated into a liquid composition and a precipitated powder composition, and a carbon dioxide capture conversion catalyst can be obtained by extracting only a supernatant, that is, the liquid composition part.

[0049] The first, second, and third basic solutions can each independently include one or more selected from the group consisting of potassium hydroxide (KOH), sodium tetraborate (Na2B4O7·10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), hydrogen peroxide (H2O2), and combinations thereof.

[0050] For example, the first basic solution can include potassium hydroxide (KOH), sodium tetraborate (Na2B4O7·10H2O), and sodium hydroxide (NaOH).

[0051] For example, the second basic solution can include sodium silicate (Na2SiO3).

[0052] For example, the third basic solution can include hydrogen peroxide (H2O2).

[0053] Further, provided is a carbon dioxide capture conversion catalyst manufactured according to a manufacturing method of the carbon dioxide capture conversion catalyst, including: one or more oxides selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O, and P2O3; one or more metals selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd, and Pb; a crystallized synthetic zeolite manufactured using an alumina-based raw material, a silica-based raw material, and sodium hydroxide; and one or more basic solutions selected from the group consisting of potassium hydroxide (KOH), sodium tetraborate (Na2B4O7·10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), hydrogen peroxide (H2O2), and combinations thereof.

[0054] The carbon dioxide capture conversion catalyst can improve the carbon dioxide capture efficiency by including the potassium hydroxide (KOH) as a basic solution. For example, by including potassium hydroxide in the carbon dioxide capture conversion catalyst, about 2.5 to 4 times the carbon dioxide capture efficiency can be exhibited compared to a case where potassium hydroxide is not included.

[0055] The oxide can include SiO215 to 90 parts by weight, Al2O315 to 100 parts by weight, Fe2O310 to 50 parts by weight, TiO25 to 15 parts by weight, MgO 20 to 150 parts by weight, MnO 10 to 20 parts by weight, CaO 20 to 200 parts by weight, Na2O 15 to 45 parts by weight, K2O 20 to 50 parts by weight, and P2O35 to 20 parts by weight, the metal can include Li 0.0035 to 0.009 parts by weight, Cr 0.005 to 0.01 parts by weight, Co 0.001 to 0.005 parts by weight, Ni 0.006 to 0.015 parts by weight, Cu 0.018 to 0.03 parts by weight, Zn 0.035 to 0.05 parts by weight, Ga 0.04 to 0.08 parts by weight, Sr 0.02 to 0.05 parts by weight, Cd 0.002 to 0.01 parts by weight, and Pb 0.003 to 0.005 parts by weight, the zeolite can include 75 to 420 parts by weight, and the alkaline solution can include potassium hydroxide (KOH) 15 to 120 parts by weight, sodium tetraborate (Na2B4O7·10H2O) 20 to 130 parts by weight, sodium hydroxide (NaOH) 15 to 120 parts by weight, sodium silicate (Na2SiO3) 50 to 250 parts by weight, and hydrogen peroxide (H2O2) 10 to 50 parts by weight.

[0056] The zeolite can be a crystallized synthetic zeolite manufactured using sodium tetrahydroxyaluminate (NaAl(OH)4) 30 to 120 parts by weight, sodium silicate (Na2SiO3) 30 to 200 parts by weight, and sodium hydroxide 15 to 100 parts by weight.

[0057] The carbon dioxide capture conversion catalyst can function as a positive catalyst in the following chemical formula by forming an over metal oxide from the oxide, the metal, and the alkaline solution, thus having a carbon dioxide capture effect.

[0058] Specifically, since the metal includes an over metal, the over metal can be allowed to react with the oxide in a reaction furnace and form an over metal oxide. The carbon dioxide capture conversion catalyst can be the over metal oxide, which functions as a positive catalyst, and can capture carbon dioxide since it includes NaOH and KOH, which can react with carbon dioxide.

[0059] The NaOH and KOH contained in the carbon dioxide capture conversion catalyst can react according to the following reaction formula. The following reaction formula 1 (1-1, 1-2) and reaction formula 2 can occur in parallel, and can be converted into a substance for realizing carbon resource by forming NaHCO3 and K2CO3 as final reaction products.

[0060] That is, the carbon dioxide capture conversion catalyst of the present application can convert carbon dioxide into sodium carbonate and sodium bicarbonate while inactivating the carbon dioxide, thereby removing the carbon dioxide and realizing carbon resourceization.

[0061]

Reaction Formula 1-1

[0062]

Reaction Formula 1-2

[0063]

Reaction Formula 2

[0064] The carbon dioxide capture conversion catalyst can capture 0.3 to 0.5 kg / h of carbon dioxide per 1 kg of the carbon dioxide capture conversion catalyst. For example, the carbon dioxide capture conversion catalyst can capture 0.3 to 0.45 kg / h, 0.3 to 0.4 kg / h, 0.3 to 0.35 kg / h, 0.35 to 0.5 kg / h, 0.4 to 0.5 kg / h, 0.45 to 0.5 kg / h, or 0.38 to 0.4 kg / h of carbon dioxide per 1 kg of the carbon dioxide capture conversion catalyst.

[0065] The carbon dioxide capture conversion catalyst can be an alkaline solution, and the average pH thereof can be pH 12 to pH 14. For example, the carbon dioxide capture catalyst can be pH 12 to 13.5, pH 12 to 13, pH 12 to 12.5, pH 12 to 12.2, pH 12.2 to 14, pH 12.5 to 14, pH 13 to 14, or pH 13.5 to 14. The pH of the carbon dioxide capture conversion catalyst can be an important index for determining the amount of catalyst to be added. Specifically, as the carbon dioxide capture conversion catalyst captures carbon dioxide, the pH thereof will gradually decrease, and thus the carbon dioxide capture conversion catalyst can be additionally added when the pH decreases to a certain reference value or less.

[0066] The carbon dioxide capture conversion catalyst can be used in combination with water. When the carbon dioxide capture conversion catalyst and water are mixed, the higher the ratio of the catalyst, the higher the carbon dioxide capture rate will be, but the mixing ratio with water can be adjusted in consideration of the cost.

[0067] The carbon dioxide capture conversion catalyst and water can be mixed at a ratio of 1:1 to 1:5. For example, the alkaline alkali solution and water can be mixed at a ratio of 1:1 to 1:4, 1:1 to 1:3, 1:1 to 1:2, 1:2 to 1:5, 1:2 to 1:3, or 1:3 to 1:5.

[0068] The carbon dioxide capture conversion catalyst according to the present application can be used for removal of carbon dioxide from exhaust gas emitted from a ship such as a boiler, incinerator, and engine, and from exhaust gas emitted from a thermal power plant, liquefied natural gas (LNG), liquefied petroleum gas (LPG), or a fuel cell facility, etc.

[0069] Next, the present application will be described in more detail with reference to examples according to the present application, but the scope of the present application is not limited by the following described examples.

[0070] <Example>

[0071] To manufacture the carbon dioxide capture conversion catalyst according to the present application, first, SiO2 150 kg, Al2O3 150 kg, Fe2O3 100 kg, TiO2 50 kg, MgO 200 kg, MnO 100 kg, CaO 200 kg, Na2O 150 kg, K2O 200 kg, and P2O3 50 kg as oxides are mixed and dissolved in a melting furnace at 3 to 12 bar and 600 to 1,500°C for 0.5 to 10 hours, and then cooled at room temperature. Next, a fine powder is manufactured by fine powdering using a micro powderizer.

[0072] A metal fine powder is manufactured by mixing Li 35 g, Cr 50 g, Co 10 g, Ni 60 g, Cu 180 g, Zn 350 g, Ga 400 g, Sr 200 g, Cd 20 g, and Pb 30 g as metals and fine powdering using a micro powderizer.

[0073] Fine powdering is repeated until the particle size of the oxide fine powder and the metal fine powder reaches 1 to 2 μm.

[0074] A crystallized synthetic zeolite is manufactured by stirring for 1 to 10 hours at a temperature of 30 to 70°C after putting water 3,000 kg, sodium tetrakis hydroxy aluminate (NaAl(OH)4) 40 kg, NaSi3 40 kg, and sodium hydroxide (NaOH) 25 kg into the reactant.

[0075] The oxide fine powder micronized in the above process was fed into the reaction furnace in units of 100 kg and at intervals of 5 minutes and stirred for 2 hours or more, and then sodium tetraborate (Na2B4O7-10H2O) 50 kg, sodium hydroxide (NaOH) 25 kg, and potassium hydroxide (KOH) 50 kg were simultaneously fed and stirred for 30 minutes. While stirring, the temperature was raised to 40 to 80°C, and then sodium silicate (Na2SiO3) 100 kg was fed. After stirring for 30 minutes, the metal fine powder micronized in the above process was fed in units of 20 g and at intervals of 3 minutes and stirred.

[0076] After stirring for 1 hour, hydrogen peroxide (H2O2) 30 kg was fed and stirring was continued for 30 minutes, and then natural cooling was performed for 1 hour. By performing stabilization for 48 hours after cooling, a liquid composition and a precipitated powder composition were separated. By obtaining only the liquid composition, a carbon dioxide electrochemical conversion catalyst (designated as KLC) was manufactured.

[0077] In the manufacturing method of the carbon dioxide capture conversion catalyst according to the present application (Example, KLC-20), Comparative Example 1 (KLC-11) and Comparative Example 2 (KLC-18) not containing potassium hydroxide (KOH) were manufactured.

[0078] <Test Example: Carbon Dioxide Capture Test>

[0079] The manufactured Example (KLC-20) and Comparative Examples 1 (KLC-11) and 2 (KLC-18) were filled into a K-scrubber (K-Scrubber) tank, and an exhaust gas pipe of a boiler (Miura GZ-300 boiler) using liquefied petroleum gas (LPG) as fuel was connected to the K-scrubber. By passing the exhaust gas discharged after combustion in the liquefied petroleum gas (LPG) boiler through the K-scrubber, a carbon dioxide capture test was performed.

[0080] The specifications of the K-scrubber are as follows.

[0081] - Power used: 1.3 KW

[0082] - Residence time: 4 seconds

[0083] - Solution used: KLC-20 stock solution 105.48 kg (specific gravity: 1.466) = 72 L

[0084] - Scrubber operation time: 1 hour 35 minutes

[0085] The results of the carbon dioxide capture test are shown in FIG. 1,Figure 2 and shown in Table 1.

[0086] Figure 1 is a graph of the carbon dioxide capture test results of the carbon dioxide capture conversion catalyst according to the example, with data from a gas meter. (a) Scrubber data before carbon dioxide capture, (b) Scrubber data after carbon dioxide capture and (c) Carbon dioxide capture saturation test results

[0087] Referring to Figure 1, the carbon dioxide capture test results of the example are shown below.

[0088] 1) CO2 capture efficiency of the example: approximately 20% (area comparison)

[0089] Solution used: Example 105.48 kg (specific gravity: 1.466) = 72 L

[0090] 2) CO2 capture amount per kg of the example calculation

[0091] Total amount of exhaust gas: 951.62 Nm 3 / h = 15.86 Nm 3 / min

[0092] CO2 in the exhaust gas: 10.98%, capture efficiency: 20%, CO2 density: 1.977 (g / L)

[0093] Amount of CO2 captured by the scrubber: 951.62 Nm 3 / h x 1000 L / Nm 3 x 0.1098 x 0.2 x 1.977 g / L

[0094] = 41,314.52 g / h = 41.31 kg / h

[0095] CO2 capture amount per 1 kg of the example: 0.392 kg / h (41.31 kg / 105.48 kg = 0.392 kg / h)

[0096] 3) pH after CO2 capture: 12.2, specific gravity: 1.545

[0097] Figure 2 is a graph illustrating the carbon dioxide capture test results of Comparative Example 1 and Comparative Example 2.

[0098] Referring to Figure 2The CO2 capture amount per 1 kg of the comparative example 1 was 0.135 (13.5%), and the CO2 capture amount per 1 kg of the comparative example 2 was 0.155 (15.5%). When calculated on the basis of 28 kg, the total capture amount of the comparative example 1 was 3.78 kg (13.5%), and the total capture amount of the comparative example 2 was 4.34 kg (15.5%).

[0099] The CO2 capture amount per 1 kg of the comparative example 1 was 0.135 (13.5%), and the CO2 capture amount per 1 kg of the comparative example 2 was 0.155 (15.5%). When calculated on the basis of 28 kg, the total capture amount of the comparative example 1 was 3.78 kg (13.5%), and the total capture amount of the comparative example 2 was 4.34 kg (15.5%).

[0100]

Table 1

[0101] Boiler scrubber CO2 capture rate CO2 capture amount (kg / klc kg.h) Comparative Example 1 13.5% (area under curve) 0.11 kg / h Comparative Example 2 15.5% (area under curve) 0.156 kg / h Example 20% (area under curve) 0.392 kg / h

[0102] As can be confirmed from the above Table 1, the example including KOH showed about 2.5 to 4 times of the CO2 capture amount compared to the comparative example 1 and the comparative example 2 not including KOH.

[0103] In other words, the CO2 capture amount per 1 kg of the CO2 capture conversion catalyst according to the example was 0.392 kg / h, which was about 60% higher than that of the CO2 capture conversion catalyst according to the comparative examples (0.11 kg / h and 0.156 kg / h, respectively).

[0104] Industrial applicability

[0105] The present application can be widely used in the field of the manufacturing method of the CO2 capture conversion catalyst and the catalyst.

Claims

1. A method of manufacturing a carbon dioxide capture conversion catalyst, comprising: (a) a step of manufacturing oxide fine powder and metal fine powder each having an average size of 0.5 to 5 μm by micronizing each of the oxide powder and the metal powder; (b) a step of manufacturing a crystallized synthetic zeolite by charging an alumina-based raw material, a silica-based raw material, and sodium hydroxide into a reaction furnace and stirring for 1 to 10 hours at 30 to 70°C; (c) a step of mixing a first alkaline solution after charging the oxide fine powder into the crystallized synthetic zeolite at a certain time interval and stirring; (d) a step of charging the metal fine powder into the mixture of the step (c) at a certain time interval and stirring after mixing a second alkaline solution into the mixture of the step (c); and, (e) a step of obtaining a carbon dioxide capture conversion catalyst by stabilizing for 40 to 50 hours after mixing an H2O2 solution into the mixture of the step (d) and extracting only a liquid portion; the oxide contains SiO215 to 90 parts by weight, Al20315 to 100 parts by weight, Fe20310 to 50 parts by weight, TiO25 to 15 parts by weight, MgO 20 to 150 parts by weight, MnO 10 to 20 parts by weight, CaO 20 to 200 parts by weight, Na20 15 to 45 parts by weight, K20 20 to 50 parts by weight, and P2035 to 20 parts by weight, the metal contains Li 0.0035 to 0.009 parts by weight, Cr 0.005 to 0.01 parts by weight, Co 0.001 to 0.005 parts by weight, Ni 0.006 to 0.015 parts by weight, Cu 0.018 to 0.03 parts by weight, Zn 0.035 to 0.05 parts by weight, Ga 0.04 to 0.08 parts by weight, Sr 0.02 to 0.05 parts by weight, Cd 0.002 to 0.01 parts by weight, and Pb 0.003 to 0.005 parts by weight, the zeolite contains 75 to 420 parts by weight, the first alkaline solution contains KOH 15 to 120 parts by weight, Na2B4O7•10H2O 20 to 130 parts by weight, NaOH 15 to 120 parts by weight, the second alkaline solution contains Na2SiO350 to 250 parts by weight, the H2O2 solution contains H2O210 to 50 parts by weight, and the carbon dioxide capture efficiency is improved by containing the KOH in the first alkaline solution.

2. The method of manufacturing a carbon dioxide capture conversion catalyst according to claim 1, wherein: the average size of the oxide fine powder and the metal fine powder is 0.5 to 5 μm.

3. The method of manufacturing a carbon dioxide capture conversion catalyst according to claim 1, wherein: In the step (b), the crystallized synthetic zeolite is produced by stirring for 1 hour to 10 hours at 30°C to 70°C after the alumina-based raw material, the silica-based raw material, and the sodium hydroxide are charged into the reaction furnace.

4. The method of claim 1, wherein: When the charging is performed at a certain time interval in the step (c) and the step (d), the prescribed charging amount is distributed and charged at intervals of 1 minute to 10 minutes.

5. The method of claim 1, wherein: In the step (e), the liquid composition and the precipitated powder composition are separated by natural cooling after mixing the H2O2 solution and performing stabilization for 40 hours to 50 hours.

6. The method of claim 1, wherein: The obtained carbon dioxide capture conversion catalyst converts into sodium carbonate or sodium bicarbonate while capturing carbon dioxide, thereby removing the carbon dioxide.

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