KR102089399B1 - A tubular reactor for mineralization of carbon dioxide, an apparatus comprising the same, and a method for mineralizing carbon dioxide using the same - Google Patents

Abstract

According to the present invention, a tubular reactor for a mineralization reaction of carbon dioxide, a device including the same, and a mineralization method of carbon dioxide using the same can capture carbon dioxide in exhaust gas without a separate capture process of carbon dioxide, convert carbon dioxide into a form of carbonate minerals with high efficiency and high purity, improve space efficiency by minimizing the volume of the reactor and a reaction device, and also convert carbon dioxide into the form of carbonate minerals with high conversion rate even under a room temperature and pressure. In addition, there is an economical and efficient effect that the present invention can reduce the cost due to the reduction of carbon dioxide and store the same stably and permanently.

Description

A tubular reactor for mineralization of carbon dioxide, an apparatus comprising the same, and a method for mineralizing carbon dioxide using the same}

The present invention relates to a tubular reactor for mineralization reaction of carbon dioxide, an apparatus comprising the same, and a method for mineralization of carbon dioxide using the same.

Recently, as various problems due to global warming have occurred, interest in a method of reducing greenhouse gas emission causing global warming has increased, and accordingly, related research has been actively conducted. Carbon dioxide, known as a representative greenhouse gas, is one of the substances that greatly affect global warming because it is contained in a large amount in the atmosphere. Therefore, various studies have been conducted to reduce the emission of carbon dioxide.

The carbon dioxide emission reduction technology that can be used in an actual industrial or internal combustion engine can be referred to as carbon capture and storage (CCS). The capture technology for reducing the emission of carbon dioxide is classified into a pre-combustion capture technology, a pure oxygen combustion technology, and a post-combustion capture technology, and the most easily applicable technology to existing facilities may be a post-combustion capture technology. Such a capture technique includes a method using a compound such as an amine-based absorbent or a method using a separator, and it is common to use an amine-based compound capable of capturing carbon dioxide at a high concentration. However, there is a problem in that high energy is required when carbon dioxide is collected in an amine compound and then the carbon dioxide collected is recovered.

The collected carbon dioxide can be disposed of by disposing it in the ocean, etc., and a more stable method of disposing carbon dioxide is a method of converting carbon dioxide into a carbonate mineral form such as calcium carbonate, and various studies have been conducted on this.

Specifically, as a source of calcium used to convert carbon dioxide into a calcium carbonate form, a method of extracting and using calcium contained in inorganic wastes such as slag discharged from the steel industry and cement industry has been proposed. However, when using this source to convert carbon dioxide into a carbonate mineral form such as calcium carbonate, there is a problem that the fixing efficiency of carbon dioxide is low.

KR10-2018-0106884A (2018.10.01)

An object of the present invention is a tubular reactor for the mineralization reaction of carbon dioxide capable of converting carbon dioxide in the form of carbonate minerals with high efficiency and high purity together with capturing carbon dioxide in exhaust gas without a separate capture process of carbon dioxide, and a device comprising the same It is to provide a method for mineralization of used carbon dioxide.

Another object of the present invention is to allow the reaction by introducing the exhaust gas containing carbon dioxide as it is, as well as having a high reaction efficiency while minimizing the volume of the reactor and the reaction device, a mineral of carbon dioxide that can improve the space efficiency It is to provide a tubular reactor for the chemical reaction, an apparatus comprising the same, and a method for mineralizing carbon dioxide using the same.

Another object of the present invention is to provide a tubular reactor for mineralization reaction of carbon dioxide capable of converting carbon dioxide into a carbonate mineral form at a high conversion rate even at normal temperature and pressure, an apparatus comprising the same, and a method for mineralizing carbon dioxide using the same.

Another object of the present invention is an economical and efficient tubular reactor for mineralization reaction of carbon dioxide that can stably and permanently store carbon dioxide in the form of a carbonate mineral with a high purity by lowering the cost associated with carbon dioxide reduction, and apparatus using the same It is to provide a method for mineralizing carbon dioxide.

The tubular reactor for mineralization reaction of carbon dioxide according to the present invention is a tubular reactor for mineralizing by reacting a carbon dioxide-containing gas and a calcium compound in a liquid medium, wherein a fluid containing a liquid medium, a calcium compound and a carbon dioxide-containing gas is from one end to the other end A tubular reaction unit having a flow path formed therein to flow in; Fixed agitation fixed to the inside of the reaction unit and formed on the central axis in the longitudinal direction of the reaction unit, a plate is formed to face the inner circumferential surface of the reaction unit, but a plurality of stirring units having a twisted shape based on the direction of the central axis are combined with each other part; And a gas filter unit positioned adjacent to one end of the reaction unit and including an external gas filter for dispersing carbon dioxide-containing gas in a liquid medium in a microbubble state.

In one example of the present invention, the plate of the stirring unit may be twisted to 150 to 210 degrees based on the central axis direction of the longitudinal direction of the reaction unit.

In one example of the present invention, one side end of the agitating units adjacent to each other is in contact with each other, but the junction may correspond to the central axis of the reaction unit.

In one example of the present invention, one side end of the stirring unit coupled to each other may be joined by crossing 60 to 120 degrees.

In one example of the present invention, the gas filter portion is fixed to the one side of the gas filter facing the central axis direction, so that the entire inlet gas is converted to a micro-bubble state, the entire rim of the gas filter is on the inner circumferential surface of the corresponding reactor. It may be formed to contact.

In one example of the present invention, the gas filter unit, but located inside the reaction unit, one or a plurality of internal gas filters located at the rear end of the stirring unit positioned at the forefront of the fluid flow direction; The carbon dioxide-containing gas may be redispersed in a liquid medium through the internal gas filter.

The apparatus for mineralization reaction of carbon dioxide according to the present invention includes a tubular reactor for the mineralization reaction of carbon dioxide. The mineralization reaction apparatus of carbon dioxide according to an embodiment of the present invention, the fluid flowing from one end of the reaction unit further includes an alkali metal hydroxide, the calcium compound is calcium chloride, and the mineralization reaction apparatus of carbon dioxide is Reactor; And a separation unit through which a fluid including calcium carbonate particles and alkali metal chloride as reactants flows from the reactor, and separates and discharges calcium carbonate particles from the fluid.

The apparatus for mineralization of carbon dioxide according to an embodiment of the present invention may further include an electrolysis unit for introducing a fluid containing alkali metal chloride from the separation unit and converting the alkali metal chloride to alkali metal hydroxide. In addition, the fluid containing the alkali metal hydroxide discharged from the electrolysis unit may be recycled to the fluid flowing into one end of the reaction unit.

The method for immobilizing carbon dioxide according to the present invention is performed using a tubular reactor for mineralization reaction of carbon dioxide. In the immobilization method of carbon dioxide according to an example of the present invention, s1) a fluid medium, a calcium compound, and a fluid containing a carbon dioxide-containing gas flow into and flow into the reaction unit through one end of the reaction unit to react through the other end of the reaction unit It may include the step of discharging the fluid containing and s2) is obtained by separating the calcium carbonate particles from the fluid containing the reactants.

In an example of the present invention, in the step s1), the volumetric flow rate ratio of the liquid medium and carbon dioxide may be 1: 4-20.

In an example of the present invention, in the step s1), the molar ratio of carbon dioxide and calcium compounds may be 1: 1 to 7.

In an example of the present invention, in the step s1), the fluid introduced may further include an alkali metal hydroxide, and the calcium compound may be calcium chloride.

In one example of the present invention, the concentration of the calcium compound for the liquid medium may be 0.2 to 2 M, and the concentration of the alkali metal hydroxide for the liquid medium may be 0.3 to 3 M.

In an example of the present invention, in the step s2), the purity of the calcium carbonate particles may be 95% or more.

The method for immobilizing carbon dioxide according to an embodiment of the present invention may be performed using the mineralization reaction apparatus for carbon dioxide. In the immobilization method of carbon dioxide according to an example of the present invention, s1) a fluid medium, calcium chloride, an alkali metal hydroxide and a gas containing carbon dioxide gas are introduced into the reaction unit through one end of the reaction unit and reacted, thereby reacting with the reaction unit. The step of discharging the fluid containing the reactant calcium carbonate particles and alkali metal chloride through the other end, s2) the fluid containing the reactant from the reaction unit flows into the separation unit, the separation of the calcium carbonate particles in the separation unit And s3) a fluid containing alkali metal chloride from the separation unit is introduced into the electrolysis unit, and the alkali metal chloride is converted into alkali metal hydroxide in the electrolysis unit. At this time, the fluid containing the alkali metal hydroxide converted in the electrolysis unit may be recycled to the fluid flowing into one end of the reaction unit.

The tubular reactor for mineralization reaction of carbon dioxide according to the present invention, an apparatus comprising the same, and a method for mineralization of carbon dioxide using the same, capture carbon dioxide in the exhaust gas and collect carbon dioxide in the form of carbonate minerals without a separate capture process of carbon dioxide. It has the effect of converting to purity.

The tubular reactor for mineralization reaction of carbon dioxide according to the present invention, an apparatus comprising the same, and a method for mineralization of carbon dioxide using the same can be reacted by introducing exhaust gas containing carbon dioxide as it is, as well as having a high reaction efficiency And it is possible to minimize the volume of the reaction device has the effect of improving the space efficiency.

The tubular reactor for mineralization reaction of carbon dioxide according to the present invention, an apparatus comprising the same, and a method for mineralization of carbon dioxide using the same have an effect of converting carbon dioxide into a carbonate mineral form at a high conversion rate even at normal temperature and pressure.

The tubular reactor for mineralization reaction of carbon dioxide according to the present invention, an apparatus comprising the same, and a method for mineralization of carbon dioxide using the same can reduce the cost of carbon dioxide reduction and convert carbon dioxide into a carbonate mineral form with high purity to stably and permanently store it. There are economical and efficient advantages.

Even if the effects are not explicitly mentioned in the present invention, the effects described in the specification expected by the technical features of the present invention and the inherent effects thereof are treated as described in the specification of the present invention.

1 is a view showing a fixed stirring unit according to the present invention.
2 is a view showing a tubular reactor for mineralization reaction of carbon dioxide according to the present invention, the upper view is a view showing a reactor including an external gas filter, the lower view is a reactor including an external gas filter and an internal gas filter It is the figure shown.
3 and 4 are conceptual views showing a method of immobilizing carbon dioxide according to the present invention.
5 and 6 is a process diagram showing a tubular reaction device for the mineralization reaction of carbon dioxide according to the present invention.

Hereinafter, a tubular reactor for mineralization reaction of carbon dioxide according to the present invention, an apparatus including the same, and a method for mineralizing carbon dioxide using the same will be described in detail with reference to the accompanying drawings.

The drawings described in this specification are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. Therefore, the present invention is not limited to the presented drawings and may be embodied in other forms, and the drawings may be exaggerated to clarify the spirit of the present invention.

Unless otherwise defined in the technical terms and scientific terms used in the present specification, those skilled in the art to which the present invention pertains have the meanings commonly understood, and the subject matter of the present invention in the following description and the accompanying drawings. Descriptions of well-known functions and configurations that may unnecessarily obscure are omitted.

As used herein, the singular form of the term may be interpreted as including the plural form unless otherwise specified.

The terms s1, s2, s3 ..., etc. referred to in this specification are only used to refer to a certain step or means, and do not mean an order, meaning an order relationship of each object referred to by the terms It should not be interpreted as.

The units of% used in the present specification without specific mention mean the weight% unless otherwise specified.

The present invention is to reduce carbon dioxide gas by converting carbon dioxide gas into stable calcium carbonate on a particle, and in providing an apparatus and method therefor, its purpose is to significantly improve the conversion rate of carbon dioxide and the purity of the resulting calcium carbonate. There is this.

Therefore, for the above object, the present invention provides a carbon dioxide mineralization reaction apparatus, a tubular reactor for the mineralization reaction of carbon dioxide as a sub-module used in the apparatus, and a method of immobilizing carbon dioxide using the reactor or apparatus.

The tubular reactor for mineralization reaction of carbon dioxide according to the present invention is a tubular reactor 100 for mineralizing by reacting carbon dioxide-containing gas and calcium compounds in a liquid medium. The carbon dioxide-containing gas used as a reactant in the present invention may be carbon dioxide itself (100% concentration), or may be a mixed gas containing carbon dioxide. In the latter case, for example, exhaust gas containing carbon dioxide can be exemplified, and as the exhaust gas can be introduced and used as it is, facility space can be minimized and the amount of calcium carbonate produced per unit volume can be further increased. You can. Of course, the exhaust gas may include various gases such as nitrogen, nitrogen compounds, and sulfur compounds in addition to carbon dioxide.

In particular, according to the present invention, even when various gases are mixed, the conversion rate of carbon dioxide is high in the mineralization reaction of carbon dioxide, and the purity of the resulting calcium carbonate is also high.

The tubular reactor 100 for mineralization reaction of carbon dioxide according to the present invention includes a tubular reaction unit 110, a fixed stirring unit 120, and a gas filter unit 130, as shown in FIG.

The reaction unit 110 is a fluid medium, a calcium compound and a flow path formed therein so that a fluid containing a gas containing carbon dioxide flows from one end to the other. The structure of the reaction unit 110 is tubular, as illustrated in FIG. 2, as long as the flow path space is formed in the reaction unit 110 in the longitudinal direction.

The tubular reaction unit 110 is generally of a straight shape, which is a general pipe shape, but it is of course possible to include a portion having a curved shape or a curved shape in consideration of an installation space.

The total length and inner diameter of the reaction unit 110 may be appropriately adjusted according to the scale, and thus is not limited to a large extent, and may be, for example, 2 to 50 m and 5 to 200 mm, but is not limited thereto.

The material of the reaction unit 110 may be any material as long as it can maintain structural stability so that fluid such as polymer, glass, and ceramic can flow therein, but it is preferably a flexible material such as polymer in terms of efficiently utilizing the facility space. can do. In addition, the specification of the reaction unit 110, for example, inner diameter, outer diameter, length, etc., is not limited because it can be appropriately adjusted according to the scale of the equipment.

The fixed stirring unit 120 is fixed inside the reaction unit 110 and is formed in the central axis (C) in the longitudinal direction of the reaction unit 110, and a plate is formed to face the inner circumferential surface of the reaction unit 110. However, a plurality of stirring units in which the plate is twisted with respect to the central axis (C) direction are combined with each other. When this is satisfied, the fluid containing carbon dioxide and the calcium compound contacts and collides with the fixed agitation unit 120, so that the fluid adjacent to the fixed agitation unit 120 forms a vortex in various directions, so that the mineralization reaction is remarkable. Improves. Therefore, the conversion rate of carbon dioxide is improved, and the purity of the produced calcium carbonate is also increased.

As a specific example, as shown in FIG. 1, the first stirring unit 121 and the second stirring unit 122 are coupled to each other, and the first stirring unit 121 and the second stirring unit 122 are identical to each other or , Or it can be a mirror image. When the first stirring unit 121 and the second stirring unit 122 are combined as mirror images of each other, the formation of vortices can be further increased.

In addition, as a plurality of stirring units have a structure in which they are combined with each other, specifically, as the respective side ends of the joints coupled between the stirring units can be combined with each other at a predetermined angle, even if the reaction unit 110 takes a curved shape There is an effect that does not substantially affect the mineralization reaction. As a specific example, one side end of the stirring unit coupled to each other may be joined by crossing 60 to 120 degrees, but this is only described as an example, and the present invention is not necessarily limited to this.

In addition, since a plurality of stirring units have a structure in which they are combined with each other and can be combined in an appropriate number, there is an effect of easily adjusting the length of the reactor 100 including the reaction unit 110 and the fixed stirring unit 120.

As shown in FIG. 1, the fixed agitation unit 120 has one side end of the agitation units adjacent to each other in contact with each other, and a junction may correspond to a central axis (C) of the reaction unit 110. . When this is satisfied, the fluid is positioned away from the central axis (C) of the reaction unit 110, that is, it is formed by the fixed stirring unit 120 as the fluid is positioned closer to the inner surface direction of the reaction unit 110 It is possible to minimize the problem of decreasing the intensity of the vortex.

In the fixed stirring unit 120, the plate of the stirring unit may be, for example, twisted 150 to 210 degrees based on the central axis (C) direction of the longitudinal direction of the reaction unit 110. An example of a structure including a plurality of stir plates of agitated units is one type of static mixer.

The gas filter unit 130 serves to disperse the carbon dioxide gas in the form of micro-bubbles on the liquid medium and increase the instantaneous solubility. When the gas filter unit 130 is not present, the amount of carbon dioxide present in the liquid medium is extremely reduced, thereby significantly reducing the production amount and process efficiency of the carbon compound. In addition, it can be very disadvantageous for mass production and commercialization.

Specifically, the gas filter unit 130 includes one or two or more gas filters, the gas filter unit 130 is located adjacent to one end of the reaction unit 110, the carbon dioxide-containing gas in a fine bubble state And an external gas filter 131 dispersed in a liquid medium. The external gas filter 131 is located outside the reaction unit 110, for example, adjacent to one end of the reaction unit 110, so that carbon dioxide gas can be present in a high content in the liquid medium.

In order for the carbon dioxide gas to be present in the liquid medium in a high content, the gas filter unit 130 is fixed with one surface of the gas filter facing the central axis (C) direction, and the entire inflowing gas is converted into a micro bubble state. The entire rim of the gas filter may be formed to contact the inner circumferential surface of the corresponding reactor 100.

On the liquid medium, the gas filter has fine pores to allow gas to permeate to form fine bubbles. When the average size (average diameter) of the micropores satisfies 100 to 1,000 μm, while maintaining a high level of the gas supply flow rate, the gas can form small micro-bubbles at a level that can exist in a high content on the liquid medium. It is preferred in terms of being possible.

As described above, the gas filter unit 130 may increase the conversion and reaction rate of carbon dioxide by allowing the carbon dioxide gas to be present in a high content in the liquid medium as it includes the external gas filter unit 130.

More preferably, the gas filter unit 130 has one or more internal gas filters so that the carbon dioxide gas can be maintained at a high content on the liquid medium even when the reaction proceeds to the end via the reaction unit 110 inside. (132) may be further included. As a preferred example, the internal gas filter 132 may be located inside the reaction unit 110, but may be located at a rear end of the stirring unit positioned at the foremost end based on the fluid flow direction. Accordingly, the carbon dioxide-containing gas is redispersed in the liquid medium through the internal gas filter 132, so that the carbon dioxide gas can be maintained at a high content on the liquid medium even when the reaction proceeds to the end via the inside of the reaction unit 110. have.

As a preferred example, the internal gas filter 132 may be located between the stirring units adjacent to each other, that is, at the junction. As described above, the fixed type stirring unit 120 may place the internal gas filter 132 on the bonding unit, as a plurality of stirring units are joined and connected to each other. In particular, as the fluid has a greater vortex intensity at the junction and the vortex direction becomes more random, the internal gas filter 132 is positioned at the junction, thereby further reducing resistance due to the gas filter itself.

Since the content of calcium carbonate particles generated by reaction increases as it approaches the rear end of the reaction unit 110, the number of gas filters per unit area decreases as it approaches the rear end of the reaction unit 110 where calcium carbonate particles are generated. It may be desirable. Specifically, when defining the front end of the reaction unit 110 as the first region and the rear end of the reaction unit 110 as the second region based on the fluid flow direction, the number of internal gas filters 132 in the first region It is preferable that it is larger than the number of internal gas filters 132 in the second region. A criterion for distinguishing the first region from the second region may be a location where calcium carbonate particles are generated. More specifically, the reference may refer to a point where calcium carbonate particles having a size equal to or greater than that of the internal gas filter 132 are initially generated.

The liquid medium may be any one as long as carbon dioxide reacts with the calcium compound to generate calcium carbonate particles, and water may be exemplified.

The calcium compound reacts with carbon dioxide to allow calcium carbonate particles to be generated, and preferably calcium chloride. In addition, a waste material containing calcium chloride as a source of the calcium chloride, specifically, cement kiln dust (Cement Kiln Dust) and the like. That is, as waste materials such as cement kiln dust can be used as a reaction raw material, there is a more environmentally friendly effect. In this case, of course, an intermediate process for processing a reaction raw material such as cement kiln dust, for example, a process of removing a specific material may be further performed.

The fluid flowing from one end of the reaction unit 110 may further include an alkali metal hydroxide. As described above, since a waste material such as cement kiln dust can be used as a raw material for the calcium compound, the fluid may contain impurities such as Al, Si, and Fe, and when the fluid further contains an alkali metal hydroxide, It may be desirable in terms of minimizing the problem of the reaction of impurities such as Al, Si, and Fe by changing the pH and increasing the purity and content of the calcium carbonate particles generated by the reaction.

The apparatus for mineralization reaction of carbon dioxide according to the present invention includes a tubular reactor 100 for the mineralization reaction of carbon dioxide.

In the mineralization reaction apparatus of carbon dioxide according to an exemplary embodiment of the present invention, the fluid flowing from one end of the reaction unit 110 may further include an alkali metal hydroxide, and the calcium compound may be calcium chloride, and the Carbon dioxide mineralization reaction apparatus, the reactor 100; And a separation unit 200 through which a fluid including calcium carbonate particles and alkali metal chloride as reactants flows in from the reactor 100, and separates and discharges calcium carbonate particles from the fluid.

The separation unit 200 separates the solid phase containing the generated calcium carbonate particles from the liquid medium, and various devices such as a filtration device and a device for separating sediment by centrifugation may be used. There are various known solid / liquid separation devices, so it may be referred to this.

A mineralization reaction apparatus for carbon dioxide according to a more preferred example includes: an electrolysis unit 300 for introducing a fluid containing alkali metal chloride from the separation unit 200 and converting the alkali metal chloride into alkali metal hydroxide; It may further include. In addition, the fluid containing alkali metal hydroxide discharged from the electrolysis unit 300 may be recycled to the fluid flowing into one end of the reaction unit 110. In the electrolysis unit 300, potassium chloride, an alkali metal chloride that has not participated in the mineralization reaction, is electrolyzed in the reaction unit 110 of the reactor 100 to generate potassium hydroxide, which is an alkali metal hydroxide. The potassium hydroxide, that is, the alkali metal hydroxide is an alkali metal hydroxide that is initially introduced from the reaction unit 110 and can be recycled to significantly reduce the use content of the alkali metal hydroxide.

The electrolytic unit 300 may refer to various well-known documents as long as it can generate an alkali metal hydroxide by electrolyzing a fluid containing an alkali metal chloride.

As a specific first aspect of the electrolytic unit 300, the electrolysis unit 300 may include an anode chamber, a cathode chamber, an anode, a cathode, and an ion exchange membrane. Specifically, the electrolysis unit 300, a fluid containing potassium chloride and a liquid medium is supplied, an anode chamber in which chlorine gas is generated; An anode provided in the anode chamber; A cathode chamber located adjacent to the anode chamber, where water is supplied and hydrogen gas is generated; A cathode provided in the cathode chamber; And an ion exchange membrane positioned between the anode chamber and the cathode chamber to partition them and to transmit potassium ions in the anode chamber to the cathode chamber. More specifically, a fluid containing potassium chloride and a liquid medium discharged from the separator 200 flows into the anode chamber. The ion exchange membrane is interposed between the anode and the cathode to allow potassium ions generated from the anode reaction to selectively permeate and participate in the cathode reaction. The cathode electrode electrolyzes the supplied water to generate hydroxide ions and hydrogen. At this time, the hydroxide ions react with potassium ions supplied through the ion exchange membrane to generate potassium hydroxide. The potassium hydroxide can be efficiently supplied to the reaction unit 100 as it can be used.

In a specific second aspect of the electrolytic unit 300, the electrolysis unit 300 includes a cation exchange membrane; Anion exchange membrane; And a cell including a cathode chamber, an anode chamber, and a supply liquid chamber. Fluid including potassium chloride and a liquid medium discharged from the separation unit 200 flows into the supply liquid chamber. The cation exchange membrane is interposed between the anode chamber and the feed liquid chamber to allow potassium ions to selectively permeate from the feed liquid chamber to the oxide chamber. The anion exchange membrane is placed between the cathode chamber and the feed chamber to allow chlorine ions to selectively permeate from the feed chamber to the cathode chamber. The anode chamber electrolyzes water as a liquid medium to be supplied to generate hydroxide ions and hydrogen. The hydroxide ions react with potassium cations permeated through the cation exchange membrane to produce potassium hydroxide, that is, alkali metal hydroxide. The cathode chamber may be a gas diffusion type cathode, and may include a gas diffusion catalyst film. The gas diffusion catalyst film oxidizes hydrogen supplied from the anode chamber to hydrogen ions and supplies it to the cathode chamber.

The cathode chamber is supported by one or more metals selected from platinum, iridium, ruthenium, nickel, rhodium, and palladium, etc., or dispersed on titanium or the like, and then sprayed with an ion exchange membrane, brush method, etc., to 1 to 200 atm, 20 It may be prepared by pressing with a hot press under conditions such as 300 ° C. However, this is only described as a preferred example, and the present invention is not necessarily interpreted as being limited thereto.

The anode chamber is a metal containing one or more selected from platinum, iridium, ruthenium, palladium, rhodium, gold and silver, etc., supported or dispersed on titanium or the like, and then sprayed with an ion exchange membrane, brush method, etc. 1 It may be prepared by pressing with a hot press under conditions such as 200 atm, 20 to 300 ° C. However, this is only described as a preferred example, and the present invention is not necessarily interpreted as being limited thereto.

The anode chamber may be a gas diffusion type anode, and may include an anode gas diffusion catalyst film. When oxygen is supplied to the anode gas diffusion catalyst membrane, hydroxide ions are generated, and the hydroxide ions react with potassium ions in the anode chamber to generate potassium hydroxide.

The gas diffusion catalyst film uses a titanium metal mesh, a titanium pore film, carbon paper, or the like as a current collector, and a metal containing any one or two or more selected from platinum, iridium, ruthenium, nickel, rhodium, and palladium, etc., as the current collector. It can be prepared by being supported or dispersed to pressurize with a hot press under conditions of 1 to 200 atm, 20 to 300 ° C, and the like. However, this is only described as a preferred example, and the present invention is not necessarily interpreted as being limited thereto.

The ion exchange membrane may be prepared by dissolving a polymer resin having a cation exchange group or an anion exchange group in an organic solvent, that is, applying an ion exchange resin solution containing the polymer resin and an organic solvent to form a membrane. Specific examples of the polymer resin having a cation exchange group, sulfonic acid group (-SO ₃ H), carboxyl group (-COOH), phosphonic group (-PO ₃ H ₂ ), phosphinic group (-HPO ₂ H), asonic group ( And polymer resins having a functional group containing any one or two or more selected from -AsO ₃ H ₂ ), a selinonic group (-SeO ₃ H), and the like. Specific examples of the polymer resin having an anion exchange group, quaternary ammonium salt (-NH ₃ ), primary to tertiary amine (-NH ₂ , -NHR, -NR ₂ ), quaternary phosphonium group (-PR ₄ ), tertiary And a polymer resin having a functional group containing any one or two or more selected from sulfonium groups (-SR ₃ ) and the like. However, this is only a specific example, and of course, the present invention is not limited thereto.

Conditions for electrolysis, specifically, the temperature may be 10 to 200 ° C, and the pressure may be 1 to 50 atm, but this is only described as a preferred example, and the present invention is not necessarily limited to this.

The method for immobilizing carbon dioxide according to the present invention is performed using the tubular reactor 100 for mineralization reaction of carbon dioxide.

In a method of immobilizing carbon dioxide according to a preferred embodiment, s1) a liquid medium, a fluid containing a calcium compound and a carbon dioxide-containing gas, flows into the interior of the reaction unit 110 through one end of the reaction unit 110 and reacts to the above. It may include the step of discharging the fluid containing the reactant through the other end of the reaction unit 110 and s2) is obtained by separating the calcium carbonate particles from the fluid containing the reactant.

In a preferred embodiment, in the step s1), the volumetric flow rate ratio of the liquid medium and carbon dioxide may be 1: 4-20, more preferably 1: 6-16. When this is satisfied, the carbon dioxide conversion rate and the purity of the resulting calcium carbonate particles are significantly improved. Specifically, when the volume flow rate ratio satisfies 1: 6 ~ 16, the CO2 conversion rate and the purity of the resulting calcium carbonate particles can be maintained at a very high level of 99.8% or more.

In the present invention, the volumetric flow rate of the liquid medium and the volumetric flow rate of the carbon dioxide-containing gas are not particularly limited, and may be, for example, 10 to 200 ml / min and 500 to 5,000 ml / min, respectively. However, this is only described as a specific example, and the present invention is not necessarily limited to this.

In this specification, values used for volume and volume mean values at 25 ° C. and 1 atm. For example, the values for volume flow rate and volume flow rate may mean values measured at 25 ° C and 1 atm.

In the present invention, in the mineralization reaction of carbon dioxide, the temperature and pressure are not significantly limited, and may be exemplified by 5 to 50 ° C. and 0.5 to 2 atm, but are not limited thereto. good. However, the temperature and pressure may be adjusted in some cases, so it is of course not limited within a range not detrimental to the object of the present invention.

In a preferred example, in the step s1), the molar ratio of carbon dioxide and calcium compounds may be 1: 1 to 7, more preferably 1: 1 to 3. When this is satisfied, the carbon dioxide conversion rate and the purity of the resulting calcium carbonate particles are significantly improved. Specifically, when the molar ratio satisfies 1: 1 to 7, the conversion rate of carbon dioxide and the purity of the resulting calcium carbonate particles can be maintained at a high level of 95% or more. More preferably, when the molar ratio satisfies 1: 1 to 3, the carbon dioxide conversion rate and the purity of the resulting calcium carbonate particles may be maintained at a higher level of 97% or more.

In the step s1), the flowing fluid may further include an alkali metal hydroxide. If it satisfies this, as described above, it is possible to minimize the problem of impurities such as Al, Si, Fe reacting by appropriate pH change, and increase the purity and content of the calcium carbonate particles generated by the reaction.

In one example of the invention, the concentration of the calcium compound in the liquid medium may be 0.1 to 5 M, 0.2 to 2 M, 0.2 to 1 M. In addition, the concentration of the alkali metal hydroxide in the liquid medium may be 0.1 to 5 M, 0.3 to 3 M, 0.5 to 2 M. If this is satisfied, it may be preferable in terms that the effects on the above-described liquid medium and the volume flow rate range of carbon dioxide and the molar ratio range of carbon dioxide and calcium compounds can be exerted, but the present invention should not be interpreted as being limited thereto. .

In step s1), the calcium compound in the flowing fluid may be calcium chloride. When this is satisfied, as described above, that is, as illustrated in FIG. 4, potassium chloride is converted into potassium hydroxide through the electrolysis unit 300, and when using the electrolysis unit 300, the generated hydrochloric acid is separately Separately discharged. Therefore, when the calcium compound introduced from the reaction unit 110 is calcium chloride, chlorine ions of calcium chloride are separated and discharged through the electrolysis unit 300, thereby improving the mineralization reaction efficiency.

The method for immobilizing carbon dioxide according to an embodiment of the present invention may be performed using the mineralization reaction apparatus for carbon dioxide. Immobilization method of carbon dioxide according to an embodiment of the present invention, s1) a liquid medium, a calcium chloride, an alkali metal hydroxide and a fluid containing carbon dioxide-containing gas through the one end of the reaction unit 110 inside the reaction unit 110 And reacting to discharge a fluid containing calcium carbonate particles and alkali metal chloride as reactants through the other end of the reaction unit 110, s2) the fluid containing the reactant from the reaction unit 110 is separated A step of separating calcium carbonate particles from the separation part 200, and s3) a fluid containing alkali metal chloride from the separation part 200 flows into the electrolysis part 300. , In the electrolysis unit 300 may include the step of converting the alkali metal chloride to alkali metal hydroxide. At this time, the fluid containing the alkali metal hydroxide converted by the electrolysis unit 300 may be recycled to the fluid flowing into one end of the reaction unit 110.

Through the recycling of the electrolysis unit 300 and the alkali metal hydroxide, the content of the alkali metal hydroxide can be reduced, the conversion rate of carbon dioxide and the purity of the resulting calcium carbonate can be significantly improved, and overall process efficiency and maintenance are maintained. , Advantageous effects can be realized in reducing costs for equipment, maintenance, mass production, and commercialization.

Specifically, the conversion rate of carbon dioxide may be 90% or more, specifically 95% or more, more specifically 99% or more, and the purity of the resulting calcium carbonate may be 95% or more, specifically 97% or more, and more specifically 99% or more. have.

Hereinafter, the present invention will be described in detail through examples, but these are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples.

[Examples 1 to 4]

The apparatus as shown in the process diagrams of FIGS. 3 and 5 was designed, and an experiment was conducted to convert carbon dioxide into calcium carbonate particles by reacting a carbon dioxide-containing mixed gas and a mixed solution (calcium chloride, calcium hydroxide and water). At this time, the flow rate ratio of water and carbon dioxide was adjusted to 1: 1, 1: 2, 1: 6, and 1:12 to measure the carbon dioxide conversion rate (removal rate) and purity of the calcium carbonate particles according to the flow rate ratio. The results are shown in Table 1 below.

Specifically, as shown in the upper view of FIG. 2, a tubular reaction unit (urethane material) having an inner diameter of 12 mm, a static mixer (NORITAKE CO., LIMITED) located inside the reaction unit, and one end of the reaction unit A tubular reactor comprising an external gas filter located at was used. A first mixed solution containing calcium chloride and water, through one end of the reactor; A second mixed solution containing potassium hydroxide and water; And a mixed gas containing 20% by volume of carbon dioxide and 80% by volume of nitrogen. At this time, the flow rate ratio of water and carbon dioxide is adjusted to 1:12 (Example 1), 1: 6 (Example 2), 1: 2 (Example 3), and 1: 1 (Example 4) to adjust the flow rate of carbon dioxide according to the flow rate ratio. Conversion rate (removal rate) and purity of the calcium carbonate particles were measured. In addition, the volume flow rate of the second mixed solution was 60 ml / min, and the volume flow rate of the mixed gas was adjusted to 1,800 ml / min. The carbon dioxide conversion was measured by gas chromatography, and the purity of the calcium carbonate particles was measured by X-ray analysis (XRD).

Example 1 Example 2 Example 3 Example 4 CO ₂ concentration (% by volume) 20 20 20 20 KOH concentration (M) One One One One CaCl ₂ concentration (M) 0.5 0.5 0.5 0.5 Mixed gas / liquid ratio 60 30 10 5 CO ₂ / H ₂ O ratio 12 6 2 One CO ₂ conversion (%) 99.8 100.0 100.0 100.0 CaCO ₃ purity (%) 100.0 99.9 72.3 50.5

As shown in Table 1, when using the reactor according to the present invention, it can be seen that although the content of carbon dioxide, which is a gaseous reactant, is high, the conversion rate (removal rate) of carbon dioxide is 99.8% or more, and almost all of the introduced carbon dioxide reacts. When using a conventional reactor, considering that the ratio of carbon dioxide to liquid medium (water) must be significantly lower than 1: 2 to maintain a high conversion rate of carbon dioxide, when using the reactor according to the present invention, the ratio It can be seen that even in a very high 1:12 ratio, the conversion rate of carbon dioxide can be maintained at a very high level of 99.8% or more.

However, in the present invention, considering the purity of the resulting calcium carbonate particles, that is, considering both the conversion rate of the carbon dioxide and the purity of the calcium carbonate particles, the ratio of carbon dioxide to liquid medium (water) is 1: 4-20, preferably It can be seen that the range of 1: 6 to 16 is more preferable.

From Table 1, when the ratio of carbon dioxide to liquid medium (water) decreases to 1: 2 or less, it can be confirmed that the purity of calcium carbonate is significantly reduced, which is a liquid medium while the concentration of carbon dioxide flowing into the reactor decreases. It is judged that the hydroxide ions of water react with calcium ions to form calcium hydroxide (Ca (OH) ₂ ).

[Examples 5 to 10]

The same experiment as in Example 1 was performed, but the molar ratio of carbon dioxide and calcium chloride was 1: 0.5 (Example 5), 1: 1 (Example 6), 1: 3 (Example 7), and 1: 7 (Example 8). ), 1:12 (Example 9), 1:42 (Example 10), except that the experiment was carried out in the same manner as in Example 1, to convert carbon dioxide into calcium carbonate particles. The results are shown in Table 2 below.

Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 CO ₂ concentration (% by volume) 20 20 20 20 20 20 Ca / CO ₂ molar ratio 0.5 One 3 7 12 42 KOH / CaCl ₂ molar ratio 2 2 2 2 2 2 CO ₂ conversion (%) 47 97 100 100 100 100 CaCO ₃ purity (%) 100 100 100 95 47 13

As shown in Table 2, when using a reactor according to the present invention, Ca / CO ₂ and molar ratio is maintained at a 1-7 range of carbon dioxide conversion rate, and is more than 95% in both the purity of the calcium carbonate particles in, Ca / CO ₂ molar ratio is It can be seen that both the carbon dioxide conversion rate and the purity of the calcium carbonate particles are maintained at a higher level of 97% or more in the range of 1-3.

100: reactor, 101: first reactor,
102: second reactor, 103: third reactor,
110: tubular reaction unit, 120: fixed stirring unit,
121: first stirring unit, 122: second stirring unit,
130: gas filter unit, 131: external gas filter,
132: internal gas filter, 200: separation unit,
300: electrolysis unit, 410: carbon dioxide-containing gas inlet,
420: calcium compound inlet, 430: alkali metal hydroxide inlet,
C: Central axis in the longitudinal direction of the reaction part

Claims (15)

A tubular reactor that mineralizes by reacting carbon dioxide-containing gas and calcium compounds in a liquid medium,
A tubular reaction unit having a flow path formed therein so that a fluid containing a liquid medium, a calcium compound and a carbon dioxide-containing gas flows from one end to the other;
Fixed agitation fixed to the inside of the reaction unit and formed on the central axis in the longitudinal direction of the reaction unit, a plate is formed to face the inner circumferential surface of the reaction unit, but a plurality of stirring units in a shape in which the plate is twisted based on the central axis direction part; And
A gas filter unit positioned adjacent to one end of the reaction unit and including an external gas filter for dispersing carbon dioxide-containing gas in a liquid medium in a micro-bubble state;
A tubular reactor for mineralization reaction of carbon dioxide comprising a. According to claim 1,
The plate of the stirring unit is a tubular reactor for mineralization reaction of carbon dioxide in a form twisted from 150 to 210 degrees based on the direction of the central axis of the longitudinal direction of the reaction unit. According to claim 1,
A tubular reactor for mineralization reaction of carbon dioxide, wherein one end of the stirring units adjacent to each other is in contact with each other and is joined, and the junction portion corresponds to the central axis of the reaction unit. According to claim 3,
One side end of the stirring unit coupled to each other is a tubular reactor for mineralization reaction of carbon dioxide that is joined by crossing 60 to 120 degrees. According to claim 1,
The gas filter part is fixed to the one side of the gas filter facing the central axis direction, so that the entire inlet gas is converted into a micro-bubble state, the entire rim of the gas filter is formed to contact the inner circumferential surface of the corresponding reactor mineralization Reactor tubular reactor. According to claim 1,
The gas filter unit,
One or a plurality of internal gas filters located inside the reaction unit, but located at the rear end of the stirring unit positioned at the foremost end based on the fluid flow direction;
Further comprising,
A tubular reactor for mineralization reaction of carbon dioxide in which carbon dioxide-containing gas is redispersed in a liquid medium through the internal gas filter. Claim 1 to claim 6, wherein any one of the carbon dioxide mineralization reaction apparatus comprising a tubular reactor for the mineralization reaction of carbon dioxide,
The fluid flowing from one end of the reaction part further includes an alkali metal hydroxide, and the calcium compound is calcium chloride,
The carbon dioxide mineralization reaction device,
The reactor; And
A separation unit for introducing a fluid containing calcium carbonate particles and alkali metal chloride as reactants from the reactor, and separating and discharging calcium carbonate particles from the fluid;
Mineralization reaction device of carbon dioxide comprising a. The method of claim 7,
The carbon dioxide mineralization reaction device,
An electrolysis unit for introducing a fluid containing alkali metal chloride from the separation unit, and converting the alkali metal chloride into alkali metal hydroxide;
Further comprising,
A mineralization reaction apparatus for carbon dioxide in which a fluid containing alkali metal hydroxide discharged from the electrolysis unit is recycled to a fluid flowing into one end of the reaction unit. A method for immobilizing carbon dioxide using a tubular reactor for mineralization reaction of carbon dioxide of any one of claims 1 to 6,
s1) a fluid containing a liquid medium, a calcium compound and a carbon dioxide-containing gas is introduced into the reaction unit through one end of the reaction unit and reacted to discharge a fluid containing a reactant through the other end of the reaction unit;
s2) the step of obtaining the calcium carbonate particles are separated from the fluid containing the reactant
Immobilization method of carbon dioxide comprising a. ◈ Claim 10 was abandoned when payment of the set registration fee was made.◈ The method of claim 9,
In the step s1), the volumetric flow rate ratio of the liquid medium and carbon dioxide is 1: 4 to 20, the method of immobilizing carbon dioxide. ◈ Claim 11 was abandoned when payment of the set registration fee was made.◈ The method of claim 9,
In the step s1), the molar ratio of carbon dioxide and calcium compounds is 1: 1 to 7 immobilization method of carbon dioxide. The method of claim 9,
In the step s1), the flowing fluid further includes an alkali metal hydroxide, and the calcium compound is a method for immobilizing carbon dioxide, which is calcium chloride. ◈ Claim 13 was abandoned when payment of the set registration fee was made.◈ The method of claim 12,
The concentration of the calcium compound in the liquid medium is 0.2 to 2 M,
The method of immobilizing carbon dioxide having a concentration of alkali metal hydroxide in the liquid medium of 0.3 to 3 M. ◈ Claim 14 was abandoned when payment of the set registration fee was made.◈ The method of claim 9,
In the step s2), the method of immobilizing carbon dioxide having a purity of calcium carbonate particles of 95% or more. A method for immobilizing carbon dioxide using the mineralization reaction device of claim 8,
s1) A fluid containing a liquid medium, calcium chloride, alkali metal hydroxide, and carbon dioxide-containing gas flows into and reacts with one end of the reaction unit to react with calcium carbonate particles and alkali metal chloride as reactants through the other end of the reaction unit. The step of discharging the containing fluid
s2) a fluid containing a reactant is introduced into the separation unit from the reaction unit, and calcium carbonate particles are separated from the separation unit,
s3) the step of the fluid containing the alkali metal chloride from the separation unit is introduced into the electrolysis unit, and the alkali metal chloride is converted into alkali metal hydroxide in the electrolysis unit.
It includes,
A method of immobilizing carbon dioxide in which a fluid containing alkali metal hydroxide converted in the electrolysis unit is recycled to a fluid flowing into one end of the reaction unit.

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