KR20160056420A - Apparatus and method for mineralizing carbon dioxide using 3-phase fluidized bed system - Google Patents

Abstract

Provided are an apparatus for mineralizing carbon dioxide and a method for mineralizing carbon dioxide using the same. The apparatus for mineralizing carbon dioxide comprises: a reaction chamber in which carbonic anhydrase fixing beads are accommodated inside; a gas supply pipe which is connected to a lower portion of the reaction chamber, and supplies carbon dioxide gas or flue gas containing carbon dioxide to the reaction chamber; a liquid supply pipe which is connected to a side portion of the reaction chamber, and supplies a solution containing divalent metal cations to the reaction chamber; and a reaction product discharge pipe which is connected to a side portion of the reaction chamber, and discharges metal carbonates and water. The apparatus and method for mineralizing carbon dioxide use a 3-phase fluidized bed system which includes the solution containing carbonic anhydrase fixing beads and divalent metal cations, and the carbon dioxide gas or flue gas containing carbon dioxide, thereby simultaneously performing a step of converting carbon dioxide into bicarbonate ions or carbonate ions to absorb the same and a mineralization step. In the apparatus for mineralizing carbon dioxide, the metal carbonates, formed by the mineralization reaction of carbon dioxide, exist in a fluidized bed region which does not include the carbonic anhydrase fixing beads, so that the reaction product can be easily separated.

Description

[0001] The present invention relates to a carbon dioxide mineralization apparatus and a carbon dioxide mineralization method using a three-phase fluidized bed system,

The present invention relates to an apparatus and a method for mineralizing carbon dioxide into a metal carbonate compound such as calcium carbonate, and more particularly, to a carbon dioxide mineralization apparatus using a three-phase fluidized bed system, It is about how to make.

Various technologies such as energy saving, high-efficiency power generation technology, renewable energy technology, artificial afforestation or biological treatment technology are being developed to reduce carbon dioxide emission, which is a representative greenhouse gas. However, in the reality that the industry base must be maintained and continuously developed, the technology that can reduce a large amount of carbon dioxide emissions in a short period of time is called carbon capture and storage (CCS). CCS technology can be divided into capture technology and storage technology. The capture technique consists of pre-combustion capture technology, oxy-fuel combustion technology, and post-combustion capture technology. The pre-combustion capture technology converts carbon-containing fuel into carbon dioxide and hydrogen fuel using appropriate reactions (such as reforming reaction and water gas conversion reaction), and then captures and removes carbon dioxide to produce carbon dioxide as a reaction product Is a technique for preventing the occurrence of a defect. Oxyfuel combustion technology is an oxidizer of fuel, which uses only oxygen that has been removed from nitrogen without using air, so that the absolute amount of exhaust gas is reduced, and the exhaust gas composition is easy to separate and remove carbon dioxide because there is only carbon dioxide and water. The post-combustion trapping technology is a technique for separating the carbon dioxide contained in the exhaust gas after combustion and has an advantage that it is most easily applied to existing sources. There is a method using a solvent (typical amine-based absorbent), a method using a separation membrane, and a method using absorption and desorption of carbon dioxide of solid particles according to the separation method.

Carbon dioxide captured using such techniques should be stored using appropriate methods. Current land or underground storage methods are mainly being studied. In this method, carbon dioxide is injected into a subterranean space such as a dielectric, a gas field, or a brine layer in a supercritical state, and is isolated and stored through thermal, hydraulic, mechanical and chemical behaviors. However, because of the limit of the space that can be stored in the ground, it stores carbon dioxide in the supercritical state, so there is a possibility of re-emission to the atmosphere or seawater by leaking due to high pressure. If carbon dioxide leaks into seawater, marine acidification can adversely affect marine ecosystems. Another large amount of CO2 sequestration and storage is ocean storage. The ocean storage method is a method of dissolving in the seawater by directly injecting carbon dioxide at a depth of 1,000 m or more, and a method of injecting high density liquid carbon dioxide obtained by liquefaction by a compression device in an isolated space of 3,000 m or more. However, when carbon dioxide is injected and stored directly in the ocean, the problem of marine ecosystem impacts due to ocean acidification and the fact that dissolved carbon dioxide ultimately equilibrates with the atmosphere, The liquid carbon dioxide sequestration method is disadvantageous in that it requires facilities and power for liquefaction as well as ocean acidification, equipment and power for transporting liquid carbon dioxide as it is in a liquid state.

On the other hand, carbon dioxide conversion and reuse technology is a technology to use carbon dioxide as a resource, not to dispose of it in the earth or the ocean. Among them, carbon dioxide mineralization technology is related to a chemical reaction that converts carbon dioxide by producing calcium carbonate or magnesium carbonate using minerals such as calcium or magnesium silicate. In other words, the technology for converting carbon dioxide into minerals is a method of converting carbon dioxide captured or released by industry into natural minerals containing alkali metal and alkaline earth metal elements in the form of oxides and hydroxides, or inorganic circulation resources (steel making slag, fly ash, , Waste cement, etc.) to make carbonate minerals such as calcium carbonate (CaCO ₃ ) and magnesium carbonate (MgCO ₃ ) to stabilize or store carbon dioxide.

On the other hand, an enzyme can be utilized for the purpose of producing a useful substance through absorption and conversion of carbon dioxide. Enzymes are biological catalysts (biocatalysts) that accelerate chemical reactions in vivo. They are widely used in various fields such as cosmetics, pharmaceuticals, and biosensors, as well as industrial fields. Enzymes that can be used for carbon dioxide uptake and conversion include carbonic anhydrase. Carbonic anhydrase is a metalloenzyme which contains zinc in its inside. It is known to exist in mammalian tissues, plants, and green algae, and serves to catalyze the hydration reaction of carbon dioxide. The carbon dioxide in the atmosphere is dissolved in water to form carbonic acid and finally exist in the form of carbonic acid ion (CO 3 ^{2 -} ) as shown in the following reaction formula. When metal cations are present, it forms a precipitate.

_{CO 2 (g) → CO2 (} aq) ( Step 1)

CO ₂ (aq) + H ₂ O → H ₂ CO ₃ (step 2)

H ₂ CO ₃ → H + + HCO 3 ^- (step 3)

_{^{HCO3 - → H + + CO 3}} 2 - ( Step 4)

CO ₃ ^{2 -} + Ca ^{2 + -} > CaCO ₃ (step 5)

Here, steps 2 and 3, which are reactions in which carbon dioxide hydrates, act as a rate-determining step, which can be accelerated in the presence of carbonic anhydrase. Further, the thus-catalyze the absorption of carbon dioxide after the final form of carbonate ions obtained are calcium ions (Ca ^{2 +),} magnesium ions (Mg ^{2 +),} manganese ion (Mn ^{2 +),} iron ions (Fe ^{2 +),} etc. Can be converted into various carbonates such as calcium carbonate (CaCO ₃ ), magnesium carbonate (MgCO ₃ ), manganese carbonate (MnCO ₃ ), or iron carbonate (FeCO ₃ ) in the presence of metal cations of various metals, .

Regarding the mineralization conversion technology of carbon dioxide using carbonic anhydrase, Korean Patent Registration No. 10-1249734 (Prior Art 1) discloses a method of charging a carbonated raw material containing calcium into an elution reactor containing an eluent, A second step of filtering out the supernatant solution from which the calcium ions have been eluted and introducing the supernatant into a carbonation reactor; and a step of dissolving carbon dioxide in an aqueous solution of carbonic anhydrase in which the carbonic anhydrase is dissolved to remove the carbonic anhydrase And a third step of forming calcium carbonate by injecting the mixed solution into the carbonation reactor to promote the carbonation reaction after forming the mixed solution of the aqueous solution and the carbon dioxide. However, in the prior art 1, since the reaction for converting carbon dioxide into carbonate ion and the reaction for converting carbonate ion into carbonate compound are separately carried out, the apparatus is complicated and the solution in which calcium carbonate is formed is filtered and concentrated to extract calcium carbonate There is a problem that it is difficult to recycle the carbonic anhydrase, resulting in poor economical efficiency. Korean Patent Registration No. 10-1424605 (Prior Art 2) discloses a recombinant microorganism derived from Neisseria gonorrhoeae comprising the amino acid sequence of SEQ ID NO: 1, SEQ ID NO: 3 or SEQ ID NO: A transformant transformed with a vector containing a nucleic acid encoding a carbonic anhydrase and the recombinant carbonic anhydrase is expressed in a cytoplasm, a periplasmic space, or a cell surface Whole cell of; And a step of preparing a composition for capturing carbon dioxide, which comprises at least one selected from the group consisting of whole cell lysate of the whole cell or whole cell lysate, aqueous fraction, cytoplasm fraction, cell gap fraction or cell membrane fraction of the cell lysate And a step of supplying metal cations and carbon dioxide to the carbon dioxide capture composition. At this time, in the step of supplying the metal cations and the carbon dioxide to the carbon dioxide-capturing composition, the metal cations are supplied first and then the carbon dioxide is supplied sequentially, or the carbon cations are supplied first and then the metal cations are supplied sequentially, or the metal cations and the carbon dioxide At the same time. However, also in the prior art 2, there is a problem that it is difficult to recycle the carbonic anhydrase in the step of separating the reaction products, resulting in poor economical efficiency.

It is an object of the present invention to provide a device for mineralizing carbon dioxide into a metal carbonate compound such as calcium carbonate, which comprises the steps of converting carbon dioxide into bicarbonate ion or carbonate ion and absorbing it, In which the reaction product can be easily separated and carbonic anhydrase can be continuously used.

Another object of the present invention is to provide a method for mineralizing carbon dioxide using the carbon dioxide mineralization apparatus.

In order to accomplish the object of the present invention, the present invention provides a method of manufacturing a medical device, comprising: a reaction chamber in which a carbonic anhydrase immobilized bead is accommodated; A gas supply pipe communicating with the lower portion of the reaction chamber and supplying carbon dioxide gas or carbon dioxide-containing flue gas to the reaction chamber; A liquid supply pipe communicating with the side of the reaction chamber and supplying a solution containing a divalent metal cation to the reaction chamber; And a reaction product discharge pipe communicating with the side of the reaction chamber and discharging the metal carbonate compound and water. At this time, in the reaction chamber, the first fluidized bed region including the carbonic anhydrase immobilized bead in the upper direction with respect to the lower part of the reaction chamber and the first fluidized bed region including the carbonic anhydride enzyme immobilized bead And the second fluidized bed region including the second fluidized bed region are sequentially formed. In addition, the liquid supply pipe is located on the side of the reaction chamber corresponding to the first fluidized bed region, and the reaction product discharge pipe is located on the side of the reaction chamber corresponding to the second fluidized bed region. In addition, the particle size of the carbonic anhydrase-immobilized bead is 0.5 mm to 2 cm, and the particle size of the metal carbonate compound is 0.1 to 10 탆.

According to another aspect of the present invention, there is provided a method for preparing a carbon nanotube, comprising: supplying a solution containing a divalent metal cation to a reaction chamber containing a carbonic anhydrase immobilized bead through a liquid supply pipe; Supplying a carbon dioxide gas or a carbon dioxide-containing flue gas to the reaction chamber through a gas supply line to form a first fluidized bed region including a fluidized carbonic anhydrase immobilized bead, and mineralizing carbon dioxide into a metal carbonate compound; And a second fluidized bed region formed on the upper portion of the first fluidized bed region and containing no carbonic anhydrase immobilized bead and containing a metal carbonate compound on the basis of a lower portion of the reaction chamber, And a step of discharging water. At this time, the liquid supply pipe communicates with the side of the reaction chamber corresponding to the first fluidized bed region, the gas supply pipe communicates with the lower portion of the reaction chamber, and the reaction product discharge pipe is connected to the side of the reaction chamber corresponding to the second fluidized bed region . Also, the pH of the first fluidized bed region is maintained in the range of 7 to 10. In addition, the particle size of the carbonic anhydrase-immobilized bead is 0.5 mm to 2 cm, and the particle size of the metal carbonate compound is 0.1 to 10 탆.

The carbon dioxide mineralization apparatus and the carbon dioxide mineralization method according to the present invention utilize a three-phase fluidized bed system comprising a carbonic anhydrase immobilized bead, a solution containing a divalent metal cation, and a carbon dioxide gas or a carbon dioxide-containing flue gas, Bicarbonate ion or carbonate ion to be absorbed and mineralization step can be performed at the same time. In addition, since the metal carbonate compound formed by the mineralization reaction of carbon dioxide exists in the fluidized bed region that does not contain the carbonic anhydrase immobilized bead, the reaction product can be easily separated, and the carbonic anhydrase- Since it is still present in the chamber, the carbonic anhydrase can be used continuously.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a configuration of a carbon dioxide mineralization apparatus according to an embodiment of the present invention and a method of mineralizing carbon dioxide into a metal carbonate compound using the same.
FIG. 2 is a graph showing a region where carbon dioxide can be mineralized by changes in the content of carbon dioxide according to the pH of an aqueous solution and reaction with calcium ions. FIG.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention in which the object of the present invention can be specifically realized will be described with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a configuration of a carbon dioxide mineralization apparatus according to an embodiment of the present invention and a method of mineralizing carbon dioxide into a metal carbonate compound using the same.

1, a carbon dioxide mineralization apparatus according to the present invention includes a reaction chamber 10, a gas supply pipe 20, a liquid supply pipe 30, and a reaction product discharge pipe 30. The carbon dioxide mineralization apparatus includes a reaction chamber 10, (40).

A carbonic anhydrase immobilized bead is accommodated in the reaction chamber 10 and a carbonic anhydrase immobilized bead is supplied into the reaction chamber through a gas supply pipe And is fluidized by a predetermined gas to be present in the first fluidized bed region described later. The term "carbonic anhydrase (CA)" as used in the present invention refers to a metal enzyme containing zinc in its interior, which is a hydration reaction of carbon dioxide [CO ₂ (aq) + H ₂ O → H ⁺ + HCO 3 ^- ]. The carbonic anhydrase used in the present invention is not limited in its kind, and includes all commercially available enzymes, enzymes existing in nature, and enzymes expressed by gene recombination. In addition, the particle size of the carbonic anhydrase-immobilized bead is preferably 0.5 mm to 2 cm, more preferably 5 mm to 1 cm. When the particle size of the carbonic anhydrase-immobilized bead is less than 0.5 mm, in the process of mineralizing carbon dioxide using the carbon dioxide mineralization apparatus according to the present invention, a carbonic anhydrase immobilized bead bead is present in a second fluidized bed region to be described later, so that it is difficult to discharge only the reaction product and the economical efficiency of the whole process is deteriorated. In addition, when the particle size of the carbonic anhydrase-immobilized bead is more than 2 cm, it is difficult to fluidize the carbonic anhydrase-immobilized bead with only the gas supplied to the reaction chamber . In addition, the carbonic anhydrase-immobilized bead is immobilized or supported on a predetermined porous substrate by adsorption, covalent bonding or the like. The porous substrate that can be used is not limited in its kind as long as it can be used as a carrier in the catalytic field. For example, silica gel particles, alginate particles, alginate / chitosan composite particles, alginate / carboxymethyl cellulose particles, zeolite Particles and the like. Among them, it is preferable to be composed of at least one selected from silica gel particles, alginate particles and zeolite particles. In addition, the carbonic anhydrase immobilized bead may be prepared by modifying the end of SBA-15, which is a porous silica, with an amine group, and then covalently bonding a carbonic anhydrase thereto.

The gas supply pipe 20 communicates with the lower portion of the reaction chamber, and serves to supply a carbon dioxide gas or a carbon dioxide-containing flue gas to the reaction chamber. Flue gas refers to the exhaust gas that is released into the atmosphere through the flue after combustion, and occurs in thermal power plants, steel mills, and chemical manufacturing plants. The flue gas generally comprises nitrogen, carbon dioxide, water vapor and oxygen. The carbonic anhydrase immobilized bead is fluidized by the gas supplied to the reaction chamber through the gas supply pipe. At this time, a sparger 21 is preferably provided between the lower part of the reaction chamber and the gas supply pipe. The sparger gas is uniformly dispersed in the reaction chamber to facilitate the fluidization of the carbonic anhydrase immobilized bead and to make contact between the carbon dioxide and the bivalent metal cations described later in the first fluidized bed region The production rate of the metal carbonate compound can be accelerated. A spar is a tube or plate for blowing gas into an aeration-stirring type culture vessel or a bubble column type culture vessel. The shape of the sparger used in the present invention is not particularly limited and may be a tubular shape such as a single hole nozzle type blown from an open end pipe, a horizontal pipe or a cruciform, a method of blowing a hole into an annular pipe, It may be in the form of a plate such as a porous plate or a porous plate in which a plurality of holes are formed in one plate.

The liquid supply pipe 30 communicates with the side of the reaction chamber, and serves to supply a solution containing a divalent metal cation to the reaction chamber. When the solution containing the divalent metal cation and the carbon dioxide gas or the carbon dioxide-containing flue gas are sequentially or simultaneously supplied into the reaction chamber, fluidization of the carbonic anhydrase-immobilized bead starts in the reaction chamber After stabilizing after a predetermined period of time, it is stabilized to form a three-fluidized first fluidized bed (first fluidized bed) comprising a liquid phase (a solution containing a divalent metal cation), a gaseous phase (carbon dioxide gas or carbon dioxide- Regions are formed. Further, in the first fluidized bed region, the carbon dioxide is converted into carbonic acid and reacts with the divalent metal cations to form the metal carbonate compound (12). At this time, the metal carbonate compound has a particle size of 0.1 to 10 탆, preferably 0.5 to 10 탆, more preferably 2 to 8 탆. The kind of the metal carbonate compound is determined by the divalent metal cations supplied to the reaction chamber, and examples thereof include calcium carbonate, magnesium carbonate, iron carbonate, manganese carbonate, strontium carbonate, barium carbonate, zinc carbonate, . Meanwhile, the metal carbonate compound formed in the reaction chamber is relatively smaller in particle size than a carbonic anhydrase-immobilized bead, and floats over the first fluidized bed region to form a second fluidized bed region . That is, in the reaction chamber, the first fluidized bed region including the carbonic anhydrase-immobilized bead in the upper direction with respect to the lower part of the reaction chamber and the first fluidized bed region including the carbonic anhydride-immobilized bead immobilized bead, And the second fluidized bed region including the second fluidized bed region are sequentially formed. The second fluidized bed zone further includes a liquid phase such as water in addition to the metal carbonate compound, and is discharged out of the reaction chamber through a reaction product discharge pipe described later. Therefore, it is preferable that the liquid supply pipe is located on the side of the reaction chamber corresponding to the first fluidized bed region, not the side of the reaction chamber corresponding to the second fluidized bed region. On the other hand, a solution containing a bivalent metal cation supplied through the liquid supply pipe into the reaction chamber reacts with carbonate ions (CO 3 ^{2 -} ) to form a metal carbonate compound in the form of a precipitate, wherein the bivalent metal cation is calcium It may be at least one selected from the group consisting of an ion, a magnesium ion, an iron ion, a manganese ion, a strontium ion, a barium ion, a zinc ion and a lead ion and is preferably a calcium ion or a magnesium ion in consideration of an extraction raw material of a divalent metal cation . Specifically, the solution containing the divalent metal cations may be a solution extracted by a predetermined extraction solvent from one or more industrial wastes selected from steelmaking slag, fly ash, bottom ash, waste cement waste concrete and waste rock. The extraction solvent for extracting the divalent metal cations from the industrial wastes may be selected from a variety of known solvents such as an acid solution or a base solution. In view of extraction efficiency and the like, hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, , Phosphoric acid, citric acid, and oxalic acid. When the solution containing the divalent metal cation is a solution obtained by treating an industrial waste with an aqueous acid solution, it is preferable to add a basic aqueous solution after extraction to adjust the pH to a basic range and supply the solution to the inside of the reaction chamber.

The reaction product discharge pipe (40) communicates with the side of the reaction chamber, and discharges the metal carbonate compound and water out of the reaction chamber. At this time, the reaction product discharge pipe is filled with the solution corresponding to the second fluidized bed region to minimize the discharge of the solution containing the divalent metal cations, the carbon dioxide and the carbonic anhydrase immobilized bead together with the metal carbonate compound, It is preferably located on the side of the chamber.

FIG. 2 is a graph showing a region where carbon dioxide can be mineralized by changes in the content of carbon dioxide according to the pH of an aqueous solution and reaction with calcium ions. FIG. As shown in FIG. 2, in order for carbon dioxide to exist in the form of bicarbonate ions (HCO 3 ^- ) in the aqueous solution, the pH should be at least 4 or more. In order to exist in carbonate ion (CO 3 ^{2 -} ) form, the pH must be at least 7. In addition, the pH must be at least 7 in order for carbon dioxide to react with calcium ions in an aqueous solution to form crystalline calcium carbonate. Therefore, in order to effectively form the metal carbonate compound using the carbon dioxide mineralization apparatus according to the present invention, the pH of the first fluidized bed zone in which the conversion of carbon dioxide to carbonate ion and the carbonation reaction thereof takes place should be 7 or more. On the other hand, in the first fluidized bed zone, a carbonic anhydrase-immobilized bead exists to promote the conversion of carbon dioxide to carbonate ion, and the activity of the carbonic anhydrase is maintained at an appropriate level The pH of the first fluidized bed region must be limited to a certain level. Carbonic anhydrase is generally known to lose enzyme activity when the pH exceeds 10. In the present invention, the pH of the first fluidized bed region is preferably maintained at a level of 7 to 10, To < RTI ID = 0.0 > 9.5. ≪ / RTI > The carbon dioxide mineralization apparatus according to the present invention may further include a basic aqueous solution supply pipe (50, 50 ') for maintaining or adjusting the pH of the first fluidized bed zone to an appropriate level. For example, when the basic aqueous solution feed pipe 50 is in communication with the side of the reaction chamber, a basic aqueous solution may be supplied into the reaction chamber to directly control the pH of the first fluidized bed zone to be in the range of 7 to 10. In addition, when the basic aqueous solution supply pipe 51 'is in communication with the side of the liquid supply pipe, the basic aqueous solution may be supplied to the solution containing the metal cations to adjust the pH of the solution containing the metal cations before entering the reaction chamber, Whereby the pH of the first fluidized bed zone can be indirectly controlled to be in the range of 7 to 10. At this time, the amount of the basic aqueous solution supplied through the basic aqueous solution supply pipe can be calculated by measuring the pH value of the first fluidized bed region formed in the reaction chamber in real time. In the present invention, the kind of the basic aqueous solution used to adjust the pH of the first fluidized bed region to a predetermined range is not limited, and may be, for example, one or more selected from an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide and an aqueous solution of ammonium hydroxide And is preferably sodium hydroxide.

The carbon dioxide mineralization apparatus according to the present invention may further include a gas discharge pipe (60). The gas discharge pipe communicates with the upper part of the reaction chamber, and discharges the flue gas from which at least a part of carbon dioxide is removed. In the present invention, when pure carbon dioxide is supplied into the reaction chamber through the gas supply pipe 20, most of the carbon dioxide is converted into the metal carbonate compound by reacting with the divalent metal cation. Meanwhile, in the present invention, when the carbon dioxide-containing flue gas is supplied into the reaction chamber through the gas supply pipe 20, most of the carbon dioxide contained in the flue gas reacts with the divalent metal cations to convert to the metal carbonate compound, The cleaned gas can be discharged to the atmosphere through the gas discharge pipe.

The carbon dioxide mineralization apparatus according to the present invention may further include a solid / liquid separator (70). The solid / liquid separator is connected to a reaction product discharge pipe, and separates the reaction product discharged through the reaction product discharge pipe into a solid phase containing a metal carbonate compound and a liquid phase containing water. The solid / liquid separator used in the present invention may be, for example, a centrifugal separator, a press filter, or the like, unless the kind thereof is greatly limited.

The carbon dioxide mineralization apparatus according to the present invention may further comprise a recirculation line (80). The recycle line serves to recycle the liquid phase separated in the solid / liquid separator, in particular water, to the reaction chamber. The recycled water can be used to convert carbon dioxide to carbonate ions by reacting with carbon dioxide. Therefore, in the present invention, it is preferable that the recycle line is communicated with the side of the reaction chamber corresponding to the first fluidized bed region.

Another aspect of the present invention relates to a carbon dioxide mineralization method, wherein a carbon dioxide mineralization method according to the present invention comprises the steps of introducing a bivalent metal cation into a reaction chamber containing a carbonic anhydrase immobilized bead through a liquid supply pipe Supplying a solution containing Supplying a carbon dioxide gas or a carbon dioxide-containing flue gas to the reaction chamber through a gas supply line to form a first fluidized bed region including a fluidized carbonic anhydrase immobilized bead, and mineralizing carbon dioxide into a metal carbonate compound; And a second fluidized bed region formed on the upper portion of the first fluidized bed region and containing no carbonic anhydrase immobilized bead and containing a metal carbonate compound on the basis of a lower portion of the reaction chamber, And discharging the water.

At this time, the liquid supply pipe communicates with the side of the reaction chamber corresponding to the first fluidized bed region, the gas supply pipe communicates with the lower portion of the reaction chamber, and the reaction product discharge pipe is connected to the side of the reaction chamber corresponding to the second fluidized bed region . It is preferable that the pH of the first fluidized bed region is maintained in the range of 7 to 10. In addition, the particle size of the carbonic anhydrase-immobilized bead is preferably 0.5 mm to 2 cm. The particle size of the metal carbonate compound is preferably 0.1 to 10 mu m.

In addition, the carbonic anhydrase immobilized bead is obtained by immobilizing a carbonic anhydrase on a porous substrate, wherein the porous substrate is at least one selected from silica gel particles, alginate particles and zeolite particles.

In addition, it is preferable that a sparger is provided between the lower part of the reaction chamber and the gas supply pipe to uniformly distribute the gas inside the reaction chamber.

The divalent metal cation may be at least one selected from calcium ion, magnesium ion, iron ion, manganese ion, strontium ion, barium ion, zinc ion and lead ion.

Also, the solution containing the divalent metal cations may be a solution extracted from one or more industrial wastes selected from steelmaking slag, fly ash, bottom ash, waste cement waste concrete and waste rock. The extraction solvent used for extracting the divalent metal cations from industrial wastes is preferably at least one selected from hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, propionic acid, phosphoric acid, citric acid and oxalic acid.

The method of carbon dioxide mineralization according to the present invention preferably further comprises the step of supplying a basic aqueous solution to a liquid supply pipe through a basic aqueous solution supply line communicated with the side of the liquid supply pipe to adjust the pH of the solution containing the divalent metal cations . The method of carbon dioxide mineralization according to the present invention preferably further comprises the step of supplying a basic aqueous solution into the reaction chamber through a basic aqueous solution supply line communicated with the side of the reaction chamber to adjust the pH of the first fluidized bed zone to 7 to 10 . At this time, it is preferable that the basic aqueous solution used for adjusting the pH of the solution containing the divalent metal cations or the pH of the first fluidized bed region is at least one selected from an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide and an aqueous solution of ammonium hydroxide.

In addition, the carbon dioxide mineralization method according to the present invention may further include the step of discharging the flue gas from which at least part of the carbon dioxide has been removed through the gas discharge pipe communicated with the upper part of the reaction chamber.

Further, the carbon dioxide mineralization method according to the present invention preferably further comprises the step of supplying the reaction product discharged from the reaction chamber to a solid / liquid separator to separate into a solid phase containing a metal carbonate compound and a liquid phase containing water .

The carbon dioxide mineralization method according to the present invention may further include recycling the liquid phase separated in the solid / liquid separator through the recycle line communicating with the side of the reaction chamber corresponding to the first fluidized bed region .

It will be apparent to those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit or scope of the invention as defined in the appended claims. It is obvious to them. Therefore, the above-described embodiments are to be considered as illustrative rather than restrictive, and the invention is not limited to the above description, but may be modified within the scope of the appended claims and equivalents thereof.

10: reaction chamber
11: Carbonic anhydrase immobilized bead
12: Metal carbonate compound
20: gas supply pipe
21: The Spar
30: liquid supply pipe
40: Reaction product discharge pipe
50, 50 ': Basic aqueous solution supply pipe
60: gas discharge pipe
70: high / liquid separator
80: recirculation line

Claims (26)

A reaction chamber in which a carbonic anhydrase immobilized bead is accommodated;
A gas supply pipe communicating with the lower portion of the reaction chamber and supplying carbon dioxide gas or carbon dioxide-containing flue gas to the reaction chamber;
A liquid supply pipe communicating with the side of the reaction chamber and supplying a solution containing a divalent metal cation to the reaction chamber;
And a reaction product discharge pipe communicating with the side of the reaction chamber and discharging the metal carbonate compound and water,
In the reaction chamber, a first fluidized bed region including a carbonic anhydrase-immobilized bead in an upward direction with respect to the lower part of the reaction chamber and a metal carbonate compound are not contained in the first fluidized bed region and the carbonic anhydrase immobilization bead, The second fluidized bed region is formed sequentially,
Wherein the liquid supply pipe is located at a side of the reaction chamber corresponding to the first fluidized bed region and the reaction product discharge pipe is located at a side of the reaction chamber corresponding to the second fluidized bed region,
Wherein the particle size of the carbonic anhydrase-immobilized bead is 0.5 mm to 2 cm, and the particle size of the metal carbonate compound is 0.1 to 10 μm.
The carbon dioxide mineralization apparatus according to claim 1, wherein the carbonic anhydrase immobilized bead is a carbonic anhydrase enzyme immobilized on a porous substrate.
The carbon dioxide mineralization apparatus according to claim 2, wherein the porous substrate is at least one selected from silica gel particles, alginate particles and zeolite particles.
The apparatus of claim 1, wherein a sparger is provided between the lower portion of the reaction chamber and the gas supply pipe to evenly distribute the gas inside the reaction chamber.
The carbon dioxide mineralization apparatus according to claim 1, wherein the divalent metal cation is at least one selected from calcium ion, magnesium ion, iron ion, manganese ion, strontium ion, barium ion, zinc ion and lead ion.
The method according to claim 1, wherein the solution containing the divalent metal cations is a solution extracted from at least one industrial waste selected from steelmaking slag, fly ash, bottom ash, waste cement waste concrete and waste rock .
The carbon dioxide mineralization apparatus according to claim 6, wherein the extraction solvent is at least one aqueous acid solution selected from hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, propionic acid, phosphoric acid, citric acid and oxalic acid.
The method according to claim 1, further comprising a basic aqueous solution supply pipe communicating with the side of the reaction chamber and supplying a basic aqueous solution to the reaction chamber to adjust the pH of the first fluidized bed region to 7 to 10, .
2. The apparatus according to claim 1, further comprising a basic aqueous solution supply pipe communicating with the side of the liquid supply pipe and supplying a basic aqueous solution to the liquid supply pipe for adjusting the pH of the solution containing the metal cation, .
The carbon dioxide mineralization apparatus according to claim 8 or 9, wherein the basic aqueous solution is at least one selected from an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide and an aqueous solution of ammonium hydroxide.
10. A carbon dioxide mineralization apparatus according to any one of claims 1 to 9, further comprising a gas discharge pipe communicating with the upper part of the reaction chamber and discharging flue gas from which at least part of the carbon dioxide has been removed.
10. The process according to any one of claims 1 to 9, further comprising a solid / liquid separator connected to the reaction product discharge pipe and separating the discharged reaction product into a solid phase containing a metal carbonate compound and a liquid phase containing water Wherein the carbon dioxide mineralization apparatus comprises:
13. The method according to claim 12, further comprising a recycle line communicating with the side of the reaction chamber corresponding to the first fluidized bed region and recirculating the liquid phase separated in the solid / liquid separator to the reaction chamber, Device.
Supplying a solution containing a divalent metal cation to a reaction chamber containing a carbonic anhydrase immobilized bead through a liquid supply pipe;
Supplying a carbon dioxide gas or a carbon dioxide-containing flue gas to the reaction chamber through a gas supply line to form a first fluidized bed region including a fluidized carbonic anhydrase immobilized bead, and mineralizing carbon dioxide into a metal carbonate compound; And
And a second fluidized bed region formed above the first fluidized bed region and containing no carbonic anhydrase immobilized bead and containing a metal carbonate compound on the basis of a lower portion of the reaction chamber, And discharging water,
The liquid supply pipe communicates with the side of the reaction chamber corresponding to the first fluidized bed region, the gas supply pipe communicates with the lower portion of the reaction chamber, and the reaction product discharge pipe communicates with the side of the reaction chamber corresponding to the second fluidized bed region ,
The pH of the first fluidized bed zone is maintained in the range of 7 to 10,
Wherein the particle size of the carbonic anhydrase-immobilized bead is 0.5 mm to 2 cm, and the particle size of the metal carbonate compound is 0.1 to 10 μm.
15. The method according to claim 14, wherein the carbonic anhydrase immobilized bead is a carbonic anhydrase immobilized on a porous substrate.
16. The method of claim 15, wherein the porous substrate is at least one selected from silica gel particles, alginate particles and zeolite particles.
16. The method of claim 15, wherein a sparger is provided between the lower portion of the reaction chamber and the gas supply pipe to evenly distribute the gas inside the reaction chamber.
16. The method according to claim 15, wherein the divalent metal cation is at least one selected from calcium ion, magnesium ion, iron ion, manganese ion, strontium ion, barium ion, zinc ion and lead ion.
The method according to claim 15, wherein the solution containing the divalent metal cations is a solution extracted from at least one industrial waste selected from steel making slag, fly ash, bottom ash, waste cement waste concrete and waste rock. How to do it.
20. The method of claim 19, wherein the extraction solvent is at least one aqueous acid solution selected from hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, propionic acid, phosphoric acid, citric acid and oxalic acid.
16. The method of claim 15, further comprising the step of supplying a basic aqueous solution to a liquid supply line through a basic aqueous solution supply line communicated with the side of the liquid supply line to adjust the pH of the solution containing the divalent metal cation.
16. The method of claim 15, further comprising the step of supplying a basic aqueous solution to the reaction chamber through a basic aqueous solution supply line communicated with the side of the reaction chamber to adjust the pH of the first fluidized bed zone to 7 to 10.
The method according to claim 21 or 22, wherein the basic aqueous solution is at least one selected from an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide and an aqueous solution of ammonium hydroxide.
23. The method of any one of claims 14 to 22, further comprising discharging flue gas from which at least some of the carbon dioxide has been removed through a gas discharge line communicating with the top of the reaction chamber.
23. The method as claimed in any one of claims 14 to 22, further comprising the step of supplying the reaction product discharged from the reaction chamber to a solid / liquid separator to separate into a solid phase containing a metal carbonate compound and a liquid phase containing water Carbon dioxide mineralization method.
26. The method of claim 25, further comprising recirculating the liquid phase separated in the high-liquid separator through a recycle line in communication with a side of the reaction chamber corresponding to the first fluidized bed region.

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