KR101833233B1 - Series reactors for the carbon dioxide conversion and capture, and carbon dioxide conversion and capture process using series reactors - Google Patents

Abstract

The present invention relates to a series reactor for converting and collecting carbon dioxide, and a process for converting and collecting carbon dioxide using the same, and more particularly, to a process for converting a carbon dioxide contained in a flue gas discharged into the atmosphere to a significantly reduced carbon dioxide concentration, And a carbon dioxide conversion and collection process using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon dioxide conversion and collection process, and more particularly, to a carbon dioxide conversion and collection process.

Description

[0001] The present invention relates to a series reactor for converting and capturing carbon dioxide, and a process for converting and collecting carbon dioxide using the same,

The present invention relates to a series reactor for converting and collecting carbon dioxide, and a process for converting and collecting carbon dioxide using the same, and more particularly, to a process for converting a carbon dioxide contained in a flue gas discharged into the atmosphere to a significantly reduced carbon dioxide concentration, The present invention relates to a series reactor for converting and collecting carbon dioxide which can be separately collected and utilized and which can significantly reduce the load of the conversion and collection process of carbon dioxide and a process for converting and collecting carbon dioxide using the same.

Traditionally, as a method for reducing carbon dioxide, carbon dioxide capture and storage techniques have been proposed. Carbon dioxide capture and storage technology refers to the technology of capturing carbon dioxide from sources such as power plants before leaving to the atmosphere, and then transporting them and storing them in a stable form. The carbon dioxide capture step consists of adsorption and desorption processes. First, in the adsorption process, carbon dioxide is collected from the exhaust gas using an absorbent capable of physically or chemically strong bonding with carbon dioxide. In the desorption process, external energy is applied to the absorbent bonding with carbon dioxide to regenerate the absorbent and extract only pure carbon dioxide.

However, in order to stably reduce a large amount of carbon dioxide and to reduce the amount of carbon dioxide discharged without being captured, it is inevitably necessary to use an absorbent having a strong binding force with carbon dioxide. The process of desorbing the captured carbon dioxide requires a considerable amount of energy consumption Since the process of producing a large amount of energy involves the generation of carbon dioxide, a circulation structure for generating carbon dioxide again is formed to reduce the amount of carbon dioxide. Therefore, considering the effect of reducing the total carbon dioxide in the earth's atmosphere, It is very undesirable to use a strong absorbent.

On the contrary, when the absorbent having a weak bonding force with carbon dioxide is used, the energy consumed in the extraction of carbon dioxide and the regeneration of the absorbent is reduced, but it is difficult to collect carbon dioxide at a high speed from the exhaust gas supplied at a high flow rate Therefore, there is a problem that carbon dioxide is not collected properly and is released again.

Furthermore, if the problem is solved by increasing the carbon dioxide residence time in the collector, it is necessary to expand the size of the collector. In this case, space and cost problems arise due to the increase of the facility. Further, in order to increase the fluidity of the carbon dioxide supplied into the larger collector, the exhaust gas should be supplied to the collector at a higher pressure. However, as the back pressure applied to the collector increases, the collection process becomes unstable and the equipment is damaged and / There is a problem that can be.

On the other hand, recently, techniques for converting carbon dioxide in the atmosphere into useful by-products such as bicarbonate ions and cultivating algae have been introduced. However, the concentration of carbon dioxide in the atmosphere is about 400 ppm, so there is a problem that the amount of carbon dioxide is very small for converting carbon dioxide in the atmosphere into a useful by-product such as bicarbonate ion. Further, as described above, when the carbon dioxide collected through the flue gas is regenerated and then converted, the conversion efficiency is relatively low compared to the amount of carbon dioxide supplied, so that a considerable amount of carbon dioxide supplied is again released to the atmosphere.

Therefore, the carbon dioxide contained in the flue gas discharged at a high rate is captured with high efficiency, the back pressure is prevented from increasing sharply, so that carbon dioxide can be stably trapped and useful by-products can be obtained that can be applied to various fields System development is urgently needed.

Korean Patent Laid-Open Publication No. 2015-0006253

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a method and apparatus for reducing carbon dioxide concentration in exhaust gas discharged into the atmosphere, The present invention provides a series reactor for converting and collecting carbon dioxide which can significantly reduce the load of the collection process, and a process for converting and collecting carbon dioxide using the same.

In order to solve the above-described problems, the present invention provides a conversion reactor comprising an enzyme reaction unit comprising a liquid filled in a part of a conversion reactor and a carbonic anhydrase for a reaction for converting supplied carbon dioxide into bicarbonate ion; And a collection reactor which is in communication with the conversion reactor and collects the supplied carbon dioxide. The present invention also provides a series reactor for converting and collecting carbon dioxide.

According to a preferred embodiment of the present invention, the exhaust gas containing carbon dioxide is supplied to the conversion reactor or the collection reactor, and after the carbon dioxide is converted or captured, the exhaust gas containing unreacted carbon dioxide is supplied to the collection reactor or the conversion reactor, Unreacted carbon dioxide can be captured or converted.

According to another preferred embodiment of the present invention, the conversion reactor may further include a gas discharge unit for discharging the flue gas containing unreacted carbon dioxide in the gas supply unit to which the flue gas is supplied and the enzyme reaction unit.

According to another preferred embodiment of the present invention, the carbonic anhydrase may include at least one of wild type carbonic anhydrase and carbonic anhydrase variant. At this time, the wild-type carbonic anhydrase may include one or more selected from the group consisting of?,?,?,?,?, And recombinant carbonic anhydrase.

According to another preferred embodiment of the present invention, the carbonic anhydrase is selected from the group consisting of free enzymes dispersed in a liquid phase, a plurality of enzyme aggregates unbound and aggregated, and enzyme cross-linking complexes . ≪ / RTI > At this time, the carbonic anhydrase may further comprise a support and may be bonded to the support or supported within the support.

According to another preferred embodiment of the present invention, the enzyme cross-linking complex further comprises a first support comprising a first functional group on its surface, and the first carbonic anhydrase, which binds directly to the first functional group, And a second carbonic anhydrase crosslinking complex that binds to the first carbonic anhydrase and cross-links the adjacent carbonic anhydrase. The enzyme cross-linking complex may further comprise a second functional group on its surface, and the second functional group may be bonded to at least one of the first carbonic anhydrase and the second carbonic anhydrase cross-linking complex through the second functional group, And may further comprise a support.

According to another preferred embodiment of the present invention, the conversion reactor may further include a bicarbonic acid aqueous solution discharge unit for discharging the bicarbonic acid aqueous solution converted and dissolved in the enzyme reaction unit.

According to another preferred embodiment of the present invention, the collection reactor may include at least one of a carbon dioxide absorbent and a carbon dioxide separation membrane.

According to another preferred embodiment of the present invention, it is possible to further include at least one of a bicarbonate aqueous solution reservoir and a bicarbonate aqueous solution reservoir to communicate with the bicarbonate aqueous solution discharge portion.

According to another preferred embodiment of the present invention, the collecting reactor may further include a carbon dioxide collector discharging unit for discharging a collecting object including at least one of a carbon dioxide absorbing agent, a carbon dioxide bonding agent and a reactive binder.

According to another preferred embodiment of the present invention, the carbon dioxide desorber may further include a carbon dioxide desorber for separating and collecting carbon dioxide from the discharged carbon dioxide discharged through the outlet.

The invention also relates to a conversion reactor comprising a liquid filled in a portion of a conversion reactor for a reaction to convert the supplied carbon dioxide to bicarbonate ions; And

And a collection reactor which is in communication with the conversion reactor and collects the supplied carbon dioxide. The present invention also provides a series reactor for converting and collecting carbon dioxide.

The present invention also provides a process for the production of carbon monoxide, comprising: (1) feeding an offgas containing carbon dioxide to a conversion reactor of a tandem reactor according to the present invention to convert the carbon dioxide to bicarbonate; And (2) supplying an exhaust gas containing unreacted carbon dioxide in the supplied carbon dioxide to a collection reactor to collect carbon dioxide, thereby providing a carbon dioxide conversion and collection process through a series reactor.

The present invention also provides a process for producing carbon dioxide, comprising the steps of: (a) supplying an exhaust gas containing carbon dioxide to a collection reactor of a tandem reactor according to any one of claims 1 to 12 to collect the carbon dioxide; And (b) supplying an exhaust gas containing uncoated carbon dioxide in the supplied carbon dioxide to a conversion reactor to convert the carbon dioxide to bicarbonate ions, thereby providing a carbon dioxide conversion and collection process through a series reactor.

According to a preferred embodiment of the present invention, the step of collecting and discharging the converted bicarbonate ions from the conversion reactor; And desorbing the collected carbon dioxide to collect carbon dioxide.

At this time, the step of separating the captured carbon dioxide can be performed at a temperature of 70 to 130 ° C.

Hereinafter, terms used in the present invention will be described.

The meaning of "on A phase" used in the present invention is meant to include both the surface of A directly or indirectly through B.

The present invention is suitable for maximizing the synergistic effect of the carbon dioxide reduction process through the conversion and capture of carbon dioxide.

The series reactor according to one embodiment of the present invention converts the high concentration of carbon dioxide generated from the emission source to the first rapidly, thereby performing the collection process on the carbon dioxide that has not been converted to the back pressure, and thus the thermodynamic limit The unreacted carbon dioxide can be reduced through the carbon dioxide capture process and only the unreacted carbon dioxide is supplied to the capture process, which is a significant effect in lowering the load of the capture process. Further, as the carbon dioxide is firstly reduced in the conversion step, a high level of carbon dioxide abatement efficiency can be maintained even if an absorbent having a relatively low carbon dioxide binding force is used in the subsequent absorption step. As a result, regeneration of the absorbent after absorption and extraction of carbon dioxide The required energy consumption can be reduced. In addition, byproducts generated during carbon dioxide abatement can be utilized in various fields, it is possible to prevent environmental pollution through reduction of carbon dioxide, and at the same time to obtain economic benefits of creating added value.

In addition, the series reactor according to one embodiment of the present invention collects carbon dioxide contained in exhaust gas at a very high efficiency, and at the same time, since uncoagulated carbon dioxide is supplied at a concentration higher than the concentration of carbon dioxide in the atmosphere, The production amount can be remarkably increased as compared with the conventional method in which by-products are obtained by converting carbon dioxide into the object.

1 and 2 are schematic diagrams of a series reactor according to a preferred embodiment of the present invention.
3 is a cross-sectional schematic diagram of a carbonic anhydrase complex included in a preferred embodiment of the present invention.
4 is a cross-sectional schematic diagram of a carbonic anhydrase complex included in a preferred embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same reference numerals are assigned to the same or similar components throughout the specification.

As shown in FIGS. 1 and 2, the series reactor for converting and collecting carbon dioxide according to an embodiment of the present invention includes a conversion reactor 100, 100 'communicating with one another so that carbon dioxide can flow from one side to the other, And a carbon dioxide desorber (300, 300 ') for collecting the bicarbonate ions converted through the conversion reactors (100, 100') and a carbon dioxide desorber (300, 300 ') for separating and collecting the carbon dioxide captured in the collecting reactors 400, 400 ').

1, the exhaust gas containing carbon dioxide is supplied to the conversion reactor 100 through the gas supply unit 110, and then supplied to the enzyme reaction unit 120 After the carbon dioxide is converted, the unreacted carbon dioxide is supplied to the collection reactor 200 through the gas outlet 140 of the conversion reactor 100 to capture the unreacted carbon dioxide, The exhaust gas containing may be discharged through the gas outlet 220 of the collection reactor 200.

2, the exhaust gas containing carbon dioxide is supplied through the gas supplying unit 220 'of the collecting reactor 200', and then the carbon dioxide is collected, and the uncoated carbon dioxide is supplied to the gas supplying unit 110 ' The carbon dioxide is converted through the enzyme reaction unit 120 'and the unreacted carbon dioxide is supplied to the conversion reactor 100' through the gas outlet 140 'of the conversion reactor 100' .

Compared to conventional CO 2 reduction or conversion devices, the series reactors as shown in FIGS. 1 and 2 can be used to control the rapid flow rate of the supplied flue gas and thus the back pressure on the reactor, the CO 2 conversion / It is possible to considerably reduce the backpressure in the reactor and considerably increase the efficiency of the reduction and conversion efficiency of the carbon dioxide when considering both the exhaust gas concentration and the residence time of the flue gas in the reactor necessary for the conversion and capture of the desired level of carbon dioxide Can be obtained.

In particular, the conventional carbon dioxide abatement apparatus reduces carbon dioxide by using an absorber or a separator. The absorber or separator requires a certain time for collecting carbon dioxide in the flue gas due to its efficiency. In addition, There is a problem in that satisfactory efficiency can not be exhibited in separating the gases such as carbon dioxide and other gases from each other on the development level. Accordingly, in order to collect the entire amount of carbon dioxide contained in the flue gas, it is required not only to use an absorbent or separation membrane having a high collection efficiency but also to keep the flue gas in the reactor for a predetermined time or more. However, considering the amount of exhaust gas discharged from a thermal power plant or the like and the high flow rate, the exhaust gas flowing into the reactor having a limited volume and a limited collection efficiency is difficult to secure the residence time in the reactor to the extent necessary for capturing the entire amount of carbon dioxide, The flue gas discharged through the reactor without being allowed to stay in the reactor may contain a large amount of unoccupied carbon dioxide, so that the efficiency of reducing carbon dioxide may not be good.

In order to solve this problem, when a sorbent having a high collection efficiency is used, a great amount of energy is consumed in the separation process of collected carbon dioxide, and there may be a problem that carbon dioxide is generated / discharged for the production of such energy. Also, if the residence time of the carbon dioxide in the reactor is sufficiently secured by another method, the carbon dioxide capture efficiency can be increased. However, considering the amount and flow rate of the exhaust gas discharged very rapidly, the increase of the back pressure in the reactor, Destabilization of the reactor and damage / breakage of the reactor.

Further, in the case of the method of converting carbon dioxide into another substance and reducing the amount of carbon dioxide, the concentration of carbon dioxide in the atmosphere may be relatively low when the carbon dioxide is converted to atmospheric carbon dioxide, resulting in a very small amount of the conversion product through the conversion reactor there is a problem. In addition, the conversion of carbon dioxide into other materials requires a certain period of time for the conversion reaction. If the carbon dioxide in the flue gas is to be converted, the conversion efficiency of the supplied carbon dioxide is low and a large amount of carbon dioxide is contained in the exhaust gas discharged through the reactor So that the reduction efficiency may not be good. If the residence time is increased to improve the conversion efficiency, there is a problem that the back pressure increases. In addition, if a biocatalyst is used to reduce carbon dioxide, it is difficult to maintain the enzyme activity stably for a long period of time. Therefore, it is not possible to continuously operate the carbon dioxide reduction process for a long period of time with the addition of one enzyme, .

Accordingly, the present invention is characterized in that the conversion reactors 100 and 100 'and the collecting reactors 200 and 200' are connected in series and the supplied exhaust gas passes through the conversion reactor 100 or 100 'or the collecting reactor 200 or 200' It is possible to remarkably improve the reduction efficiency of carbon dioxide and to obtain a reflex effect that can prolong the residence time of the flue gas staying in the entire series reactor, The target conversion / reduction efficiency and the prevention of the increase in the back pressure of the reactor can be achieved at the same time, and it is possible to prevent the process load caused by having any one of them.

Furthermore, the reduction of the process load may be free from the restriction that the carbon dioxide conversion power of the carbonic anhydrase used in the carbon dioxide conversion and / or the capture process and / or the trapping power of the carbon dioxide sorbent should meet a certain level or more, It is very advantageous in terms of cost reduction.

In addition, the conversion process of the carbon dioxide through the conversion reactors 100 and 100 'can produce not only the reduction of carbon dioxide in the flue gas but also the byproducts that can be utilized in various sales, thereby achieving the economic benefits of preventing environmental pollution and creating added value.

1, when carbon dioxide is reduced through the conversion reactor 100 and the unreacted carbon dioxide is collected, the carbon dioxide in the flue gas is primarily reduced through the conversion reactor 100, 200) can maintain a high level of carbon dioxide abatement efficiency because only a very low concentration of carbon dioxide is contained in the exhaust gas discharged through the series reactor even though an absorbent having a relatively weak bonding force with carbon dioxide is used and separation of carbon dioxide , There is less concern about the additional emission of carbon dioxide due to energy generation for separating carbon dioxide. In contrast, the series reactor shown in FIG. 1 can achieve the desired level of conversion and reduction of carbon dioxide even when the collection efficiency in the collection reactor is relatively low as compared with the series reactor shown in FIG. 2, As energy can be consumed, it can be advantageous in terms of economy and environment.

When a plurality of collecting reactors are connected in series, it is possible to prevent the back pressure from occurring, but the energy required for separating the collected carbon dioxide is increased by that much And there is a problem that the generation and emission of carbon dioxide are further increased due to the increased energy production. In addition, as described later, there is a problem in that it is not possible to simultaneously produce useful by-products during the reduction process through the capture of carbon dioxide, which is disadvantageous to economic benefits through creation of added value. In addition, if several conversion reactors are connected in series, the number of conversion reactors to be provided can be remarkably increased considering the reduction efficiency of carbon dioxide through the conversion reactor, . In addition, when the conversion reaction of carbon dioxide is a reversible reaction, the limitation on the carbon dioxide reduction efficiency is clear.

On the other hand, it can be considered to cause the carbon dioxide capture reaction and the conversion reaction to occur in one reactor simultaneously to achieve reduction of equipment and conversion / collection. For example, in one reactor, carbon dioxide absorbent and carbonic anhydrase However, since most of the absorbent solution has a temperature of 40 to 60 ° C and a pH of about 9 to 12 at a high temperature and a strong alkaline environment, the carbonic anhydrase is a very harsh environment for maintaining long-term activity, The enzyme activity can not be stably maintained for a long period of time and frequent enzyme replacement is required, which may lead to an increase in conversion cost. Even if carbonic anhydrase is provided at the same time, since the carbon dioxide in the flue gas is very concentrated, the amount of carbon dioxide discharged as the flue gas increases and the amount of carbon dioxide in the flue gas is reduced It can be difficult.

Hereinafter, the respective constituent elements constituting the series reactor will be described with reference to Fig. 1 in order from the initial supply of the exhaust gas to the final discharge.

First, the conversion reactor 100 in which the exhaust gas containing carbon dioxide is initially supplied will be described.

The conversion reactor 100 serves to convert the high concentration of carbon dioxide contained in the exhaust gas into bicarbonate ions, and the conversion of the carbon dioxide has a primary reduction effect of the supplied carbon dioxide. Such a carbon dioxide conversion process is more environmentally friendly than other methods of reducing and / or converting carbon dioxide, and can convert carbon dioxide into industrially available bicarbonate ions to create added value, which is very advantageous in terms of economy and productivity. In addition, since carbonic anhydrase can theoretically convert one million carbon dioxide molecules per second into bicarbonate ion, it is very suitable for the conversion of carbon dioxide which flows at a high rate, thereby preventing further increase of the back pressure in the reactor And there is an advantage that no additional process such as desorption of carbon dioxide is required.

And an enzyme reaction unit (120) including a liquid filled in a part of the conversion reactor and a carbonic anhydrase for promoting the conversion reaction for a reaction for converting the supplied carbon dioxide into bicarbonate ions, wherein the enzyme reaction unit (120) A gas supply unit 110 for supplying an exhaust gas containing carbon dioxide to the reaction chamber 150 in which the interior of the reaction chamber 100 is empty, An unreacted carbon dioxide, a gas outlet 140 through which the exhaust gas is discharged, and a bicarbonate aqueous solution discharging unit 130 through which the aqueous solution in which the bicarbonate ions converted in the enzyme reaction unit 120 are discharged is discharged.

The generated exhaust gas is supplied into the conversion reactor 100 through the gas supply unit 110, and the supplied exhaust gas passes through the enzyme reaction unit 120.

The enzyme reaction unit 120 performs a function of firstly reducing carbon dioxide contained in the exhaust gas by converting carbon dioxide contained in the exhaust gas into bicarbonate ions. The enzyme reaction unit 120 is a catalyst capable of promoting a reaction for converting carbon dioxide into bicarbonate ions and includes a carbonic anhydrase 120a and a liquid 120b serving as a mediator and / ). The liquid 120b can be used without limitation in the case of a solvent (or a solution) which functions as a reaction medium and / or reaction material for converting carbon dioxide to bicarbonate ions and has no problem in dissolving bicarbonate ions to be converted. By way of non-limiting example, the solvent (or solution) may be water and / or a conventional buffer solution, and as a non-limiting example of the buffer solution, 2-amino-2-hydroxymethyl- Propanediol can be used.

The carbonic anhydrase 120a can be used without limitation as long as it is a known enzyme having a function of promoting the conversion of carbon dioxide to bicarbonate. For example, wild type carbonic anhydrase and carbonic anhydride And enzyme variants. At this time, the wild-type carbonic anhydrase may be an enzyme naturally existing in vivo in an animal, a plant, or the like, and therefore it may be one or more selected from the group consisting of?,?,?,? And / or in vivo, or by artificially recombining the enzyme, or in combination with the in vivo carbonic anhydrase. The artificially recombined carbonic anhydrase may be a known one, and the amino acid sequence thereof is not particularly limited in the present invention. The carbonic anhydrase mutant is a modification of a part or all of the amino acid sequence of a carbonic anhydrase which exists naturally, and has a basic function of carbonic anhydrase and naturally occurring carbonic anhydrase And can be naturally or artificially modified. In the present invention, the amino acid sequence therefor is not particularly limited.

The carbonic anhydrase 120a may be in the form of any one or more of a free enzyme dispersed in a liquid phase, an enzyme aggregate in which a plurality of uncoated and coagulated enzyme aggregates, and an enzyme crosslinking complex in which a plurality of uncrosslinked enzyme coagulated complexes are combined.

In addition, the carbonic anhydrase 120a may further include a support, and the enzyme reaction unit 120 may be provided on the support or supported on the support.

The support serves to bind or support a carbonic anhydrase, to serve as a base for integrating carbonic anhydrase, and to protect the carbonic anhydrase from external force. In addition, when the carbonic anhydrase is in the form of an aggregate or a cross-linked complex, it can be distributed and distributed throughout the enzyme reaction unit while stably maintaining the form. There is no particular limitation on the shape of the support, as long as it does not inhibit or inhibit the activity of the enzyme, and is not limited to beads, fibers, or plates. For example, the support may be any one or more selected from the group consisting of polymer fibers, electrically conductive polymers, porous particles, spherical particles, nanoparticles, beads, carbon nanotubes, wires, pillars, graphene, have. Furthermore, the size of the reactor can be designed differently according to the specific structure and shape of the conversion reactor, so that the present invention does not particularly limit it.

When the above-mentioned carbonic anhydrase is bound on a support, the bond is formed by physical bonding (e.g., adsorption) of carbonic anhydrase and / or chemical bonding of carbonic anhydrase through a specific functional group provided on the support Ionic bonding, covalent bonding, etc.). It may also be adhered to the support by an adhesive material. In the case where the support has a porous structure, the support may be provided with a carbonic anhydrase in the pores or cavities contained therein, and may be formed by forming an aggregate or a cross-linked complex. The supported carbonic anhydrase may be bound to the inner surface of the pores or the cavity of the cavity or may be accommodated in a non-bonded state, but the present invention is not limited thereto.

On the other hand, there may be a difference between an optimum condition in which the reaction for converting carbon dioxide into bicarbonate ion occurs optimally and an optimum condition for maintaining the enzyme activity of carbonic anhydrase, and in some cases, the environment in the conversion reactor is a carbonic anhydrase Enzyme activity may be difficult to maintain. As shown in FIG. 3, the enzyme cross-linking complex 1000 may include a first support (1001) having a first functional group (1001) on the surface thereof, 1010) to bind to the first carbonic anhydrase 1100 and the first carbonic anhydrase 1100 fixed to the first functional group 1001 and to bind a plurality of carbonic anhydrase cross-linked 1212, 1212, and 1213 of the second carbonic anhydrase cross-linking complexes 1210, 1211, 1212, and 1213.

The functional group (1001) provided on the surface of the support (1010) may be used without limitation in the case of a functional group capable of fixing the first carbonic anhydride enzyme (1100). For example, a functional group such as carboxyl group, amine group, imine group, An ether group, an acetal group, a sulfide group, a phosphate group, and an iodo group, preferably a carboxyl group and / or an alkyl group, Or an amine group.

When the carbonic anhydrase forms a carbonic anhydrase crosslinking complex (1000) having the structure shown in FIG. 3, the enzyme activity is excellent even at a temperature and a pH condition which may not be suitable for maintenance / expression of carbonic anhydrase activity There is an advantage that the period can be stably expressed.

The carbonic anhydrase crosslinking complex (1000) as shown in FIG. 3 can be prepared by the same method as in Example 1 described later. In this case, only the crosslinking agent is added without introducing the precipitating agent, An enzyme crosslinking complex can be prepared. However, when a precipitating agent is added, a carbonic anhydrase crosslinking complex in which a carbonic anhydrase is accumulated more densely can be prepared. However, the method for producing the carbonic anhydrase crosslinking complex as shown in FIG. 3 is not limited to the example 1, and the method disclosed in Korean Patent Laid-Open Nos. 10-2011-0128182, 10-2011-0128134 No. 10-2013-0127916, and the like can be incorporated by reference.

On the other hand, in order to express more excellent enzyme activity and to express the activity stably for a long period of time, a large amount of enzyme bound to the complex is required, and at the same time, an excellent binding force capable of preventing the enzyme from falling off by the external force is required.

4, the carbonic anhydrase crosslinking complex 2000 may include a first support 2010 having a first functional group 2001 on its surface, a second functional group 2301 on the surface thereof, , 2302), wherein the second support (2300)

The first carbonic anhydrase 2100 and the second carbonic anhydrase crosslinking complexes 2211, 2212 and 2213 can be bonded to the second support body 2300 through the second functional group.

The second carbonic anhydrase cross-linking complex is not crosslinked only between the enzymes but can be bound between the enzymes with a stronger binding force as they are covalently bound through the second support, and the second support bodies 2300 Since this enzyme can be a binding point to be covalently bonded in a cluster, a larger amount of the enzyme can be included in the complex and can be advantageously used for expressing the enzyme activity remarkably improved and the enzyme activity stably for a long time have. The second support body 2300 is the same as the above description of the support body (first support body). The first support body may be the same as or different from the second support body, and may have the same shape or size as the second support body This is not particularly limited in the present invention. The second functional group is also the same as the functional group described above, and the first functional group may be the same as or different from the second functional group. 4 may be a magnetic support. In this case, the liquid 120b, in which the bicarbonate ions converted in the conversion reactor 100 are dissolved, is discharged through the bicarbonate ion outlet 130 It is advantageous to use magnetism to prevent the release of the carbonic anhydrase crosslinking complex or to enable the separation and recycling of the carbonic anhydrase crosslinking complex contained in the discharged liquid.

The carbonic anhydrase crosslinking complex 2000 according to FIG. 4 can be prepared by the manufacturing method according to Example 2 described later. However, as in the case of the carbonic anhydrase complex according to FIG. 3, only the introduction of the crosslinking agent 4 can also be realized. However, it is possible to realize a complex in which a higher concentration of enzyme is accumulated by introducing a precipitating agent, and thus, it is possible to exhibit improved physical properties through this. The method for producing the carbonic anhydrase cross-linking complex as shown in FIG. 4 is not limited to that of Example 2, and Korean Patent Laid-Open Nos. 10-2011-0128182, 10-2011-0128134, 10-2013-0127916 and the like can be inserted by reference.

The carbonic anhydrase 120a may be provided in the enzyme reaction unit 120 to promote the conversion of carbon dioxide to bicarbonate ions. The converted bicarbonate ions are discharged through the bicarbonate aqueous solution discharging unit 130 , The discharged bicarbonate ion solution is collected in a separate bicarbonate aqueous solution reservoir 300 communicating with the bicarbonate aqueous solution discharge portion 130 of the conversion reactor and / or at the utilization site of bicarbonate ion communicated with the bicarbonate aqueous solution discharge portion 130 Can be used. The utilization site of the bicarbonate ion may include, but is not limited to, synthesis of bicarbonate ions converted and / or collected as carbonates, cultivation of microorganisms as a raw material, removal of metal cations, purification of radioactive materials, and the like.

In addition, the present invention can also be formed with a liquid filled in a part of the conversion reactor for the reaction to convert the carbon dioxide supplied to the bicarbonate ion, unlike in Fig.

On the other hand, when the concentration of carbon dioxide contained in the supplied exhaust gas is high because the concentration of the carbon dioxide in the liquid filled in the conversion reactor 100 or the enzyme reaction unit 120 including the liquid is limited, the enzyme reaction unit The unreacted carbon dioxide may be supplied to the collection reactor 200 through a gas discharge unit 140 provided in the conversion reactor 100.

Next, a collection reactor 200 connected in series with the above-described conversion reactor 100 will be described.

The collection reactor 200 plays a role of collecting unreacted carbon dioxide in the conversion reactor 100. When the exhaust gas containing carbon dioxide is supplied into the reaction chamber 230 of the collection reactor 200 through the gas discharge part 140 of the conversion reactor 100, the supplied carbon dioxide is collected in the reactor, and uncoated carbon dioxide May be discharged to the outside through the gas outlet 220 of the collection reactor 200. [ The collection reactor 200 can separate and collect carbon dioxide through a carbon dioxide separation membrane and / or carbon dioxide through an absorbent.

Since the carbon dioxide separation membrane may be a conventional carbon dioxide separation membrane, the carbon dioxide separation membrane known in the art may be used without limitation in specific materials and structures. As a non-limiting example, the material of the carbon dioxide separation membrane may be 6FDA polyimide, Cardo-type polyimide, polysulfone, cellulose acetate or the like, which is excellent in separation characteristics of CO ₂ / N ₂ as an organic polymer. In addition, the specific structure may be a structure including a porous inorganic film coated on porous steel or a ceramic support, or a polymer membrane structure having a glass-like polymer or a rubber-like polymer having a permeability selectivity. In the mechanism, if the separation membrane is the porous inorganic membrane, it may be classified into Knudsen diffusion according to molecular weight, surface diffusion due to surface attraction, capillary condensation, molecular sieve mechanism depending on the size of molecules, but not limited thereto. Accordingly, it is possible to select and use an appropriate separation membrane.

The carbon dioxide absorbent may be a conventional carbon dioxide absorbent, and may specifically include at least one of a dry absorbent and a wet absorbent. The dry absorbent may, for example, include solid amines, alkali metal salts, alkaline earth metal salts, zeolites, metal organic structures and the like. The wetting agent may be a conventional wetting agent, preferably an amine-based aqueous solution, and may be a monoethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine, dimethylglycine, N-methyldiethanolamine Amino-2-hydroxymethyl-1, 3-propanediol, piperidine, pyperazine, potassium carbonate, sodium carbonate, ammonia and ammonium carbonate And may include any one selected.

According to a preferred embodiment of the present invention, the collection reactor may further include a carbonic anhydrase cross-linking complex when it comprises a carbon dioxide absorbent, preferably a wet absorbent. When the carbonic anhydrase crosslinking complex is further included in the collection reactor, the collection efficiency of carbon dioxide can be further improved and the collection rate can be further increased. However, the carbon dioxide capture environment of the capture reactor may be an alkaline pH of 9 to 12 and a temperature of 40 to 60 ° C. Under such conditions, denaturation of the carbonic anhydrase may occur and the activity of the enzyme may be significantly lowered . Therefore, in order to stably and excellently express the enzymatic activity for a long period of time, the carbonic anhydrase may be different from the carbonic anhydrase contained in the conversion reactor, and preferably, the carbonic anhydrase is cross- And an integrated carbonic anhydrase crosslinking complex may be advantageous.

The absorbent-carbon dioxide reactant collected by the absorbent while the carbon dioxide supplied from the conversion reactor 100 passes through the collection reactor 200 is then supplied to the carbon dioxide desorber 400 for separating and collecting the carbon dioxide, The remaining amount of the exhaust gas excluding the carbon dioxide captured in the exhaust gas containing carbon dioxide supplied from the exhaust gas purification unit 100 is discharged to the final atmosphere through the exhaust gas discharge unit 220 or supplied again to the gas supply unit 110 of the conversion reactor 100, The abatement process may be repeatedly performed.

The desorber 400 may include a chamber 420 for storing the supplied absorbent-carbon dioxide reactant and separated carbon dioxide, and an energy supply unit 410 for generating energy, for example, heat in the carbon dioxide separation process And a carbon dioxide discharging unit 430 for discharging the separated carbon dioxide. The heat applied at this time may be 70-130 ° C, but is not limited thereto, and may be changed depending on the kind of the absorbent of carbon dioxide used.

1 and 2, a series reactor according to another preferred embodiment of the present invention is different from the one shown in FIG. 1 and FIG. 2 in that the conversion reactor and the collection reactor are not directly connected to each other through any one of the conversion reactor and the collection reactor, Each of the gas supply units may be configured to be opened and closed, and when either one of the gas supply units is opened, the other of the gas supply units may be closed and the carbon dioxide conversion and collection process may be performed have. That is, the reactor in which the flue gas flows first may be selected in consideration of the amount of the supplied flue gas, the concentration of carbon dioxide, and the required degree of bicarbonate ion. At this time, the flue gas directly flows into the selected reactor, The gas supply may be closed to prevent direct entry of the flue gas. The opening or closing of the gas supply unit may be changed in consideration of the amount of the exhaust gas remaining in the reactor even during the process of converting and collecting the exhaust gas after the exhaust gas is supplied to the series reactor.

The carbon dioxide contained in the flue gas through the series reactor according to the present invention can be used in the following manner: (1) when the flue gas is directly supplied to the conversion reactor as shown in FIG. 1, the flue gas containing carbon dioxide Converting the carbon dioxide into bicarbonate ions by supplying the converted carbon dioxide to a conversion reactor of a series reactor; And (2) supplying exhaust gas containing unreacted carbon dioxide in the supplied carbon dioxide to a collection reactor to collect carbon dioxide, so that carbon dioxide can be converted and collected.

 In addition, when the exhaust gas is directly supplied to the collection reactor as shown in FIG. 2, (a) the exhaust gas containing carbon dioxide is supplied to a collection reactor of a tandem reactor according to an embodiment of the present invention to collect the carbon dioxide; And (b) supplying a flue gas containing uncoated carbon dioxide in the supplied carbon dioxide to a conversion reactor to convert the carbon dioxide to bicarbonate ions, whereby carbon dioxide can be converted and collected.

The conversion and trapping process of carbon dioxide will be described with reference to a series reactor as shown in FIG. 1, and the detailed description of the step (1) is the same as that of the above-described conversion reactor. It may be more advantageous to carry out the carbon dioxide conversion process in the conversion reactor, preferably at a pH of 7.5 to 8.5 and a temperature of 25 to 45 < 0 > C.

Further, the detailed description of the step (2) is the same as the description in the above-described collecting reactor and is omitted. The carbon dioxide capture step in the collection reactor is preferably carried out at a pH of 9 to 12 and a temperature of 40 to 60 ° C, preferably 45 to 55 ° C. If the temperature is lower than 40 ° C., the carbon dioxide can not be reduced to the desired level. If the temperature is higher than 60 ° C., the solubility of carbon dioxide is lowered and the amount of carbon dioxide discharged into the gaseous state is significantly increased. There is a problem that the amount of the carbon dioxide which is generated by the combustion is remarkably increased.

According to a preferred embodiment of the present invention, the method further comprises collecting carbon dioxide with the carbon dioxide absorbent in the collection reactor, discharging uncoated carbon dioxide, and separating the carbon dioxide absorbent and carbon dioxide from the collected carbon dioxide to collect carbon dioxide And the carbon dioxide separation and collection process may be performed through the desorber 400 which may be further included in the above-described series reactor, but the present invention is not limited thereto. Since the carbon dioxide desorber may be a carbon dioxide desorber applied to a conventional carbon dioxide abatement apparatus, the present invention is not particularly limited thereto, and the energy level of heat input for separating carbon dioxide may be a specific kind of absorbent And the separation time may be different depending on the specific type of the absorbent. Therefore, the present invention is not particularly limited thereto.

The present invention will now be described more specifically with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

≪ Preparation Example 1 > - Preparation of carbonic anhydrase complex 1

A fibrous support having a carboxyl group-containing polyaniline (polymerized with 1: 3 parts by weight of each of aniline and 3-aminobenzoic acid as monomers) having a diameter of about 50 nm was prepared. Then, a carbonic anhydridease The EDC-NHS reaction in which the carboxyl group is substituted is proceeded so as to be easily bonded. Specifically, 2 mg was dispersed in 10 ml of distilled water, and 2 ml of EDC (10 mg / ml), 4 ml of NHS (50 mg / ml) and 4 ml of 100 mM MES (2- (N-morpholino) ethanesulfonic acid) buffer pH 6.0) to prepare a total of 20 ml of mixed solution. Then, the mixture was stirred at room temperature for 1 hour, washed with water by centrifugation, and then 10 mg / ml of a carbonic anhydrase (CA) solution dissolved in 100 mM PB buffer (pH 7.6) Followed by stirring to induce a covalent bond between the enzyme and the polyaniline support.

The concentration of the ammonium sulfate solution in the solution was then adjusted to 55% v / v as a precipitating agent. The mixture was stirred at room temperature for 30 minutes at 150 rpm to facilitate the precipitation of the enzyme. Then 12.5% v / v glutaraldehyde is added as a cross-linking agent so that the concentration of glutaraldehyde in the solution is 0.5%. Then, the reaction was carried out in a refrigerator of 4 for 17 hours for sufficient reaction of the crosslinking agent. Then, the solution containing the matrix complex was stirred at 200 rpm for 30 minutes with 100 mM Tris buffer pH 7.6, and then washed again with 100 mM PB. All treated enzyme immobilization materials were stored at 4 to produce a carbonic anhydrase complex as shown in Fig.

≪ Preparation Example 2 > - Preparation of carbonic anhydrase complex 2

A fibrous support having a carboxyl group-containing polyaniline (polymerized with 1: 3 parts by weight of each of aniline and 3-aminobenzoic acid as monomers) having a diameter of about 50 nm was prepared. Then, a carbonic anhydridease The EDC-NHS reaction in which the carboxyl group is substituted is proceeded so as to be easily bonded. Specifically, 2 mg was dispersed in 10 ml of distilled water and mixed with 2 ml of EDC (10 mg / ml), 4 ml of NHS (50 mg / ml), 4 ml of 100 mM MES (2- (N-morpholino) ethanesulfonic acid) .0) to make a total of 20 ml of mixed solution. Thereafter, the mixture is stirred at room temperature for 1 hour and is washed by centrifugation. Then, 10 mg / ml 1 ml of a carbonic anhydrase (CA) solution dissolved in 100 mM PB buffer (pH 7.6) was added and stirred at 150 rpm for 2 hours to induce the covalent bond between the enzyme and the polyaniline support. Thereafter, as the precipitating agent, the ammonium sulfate solution concentration was adjusted to 55% v / v in the solution, and 2.5 mg of the silica beads modified with amine groups were hydrodynamically measured to have a hydrodynamic diameter of 50 nm. Lt; / RTI > solution. Respectively. The mixture was stirred at room temperature for 30 minutes at 150 rpm to facilitate the precipitation of the enzyme. Then 12.5% v / v glutaraldehyde is added as a cross-linking agent so that the concentration of glutaraldehyde in the solution is 0.5%. Then, the reaction was carried out in a refrigerator of 4 for 17 hours for sufficient reaction of the crosslinking agent. Then, the solution containing the matrix complex was stirred at 200 rpm for 30 minutes with 100 mM Tris buffer pH 7.6, and then washed again with 100 mM PB. All the treated enzyme immobilization materials were stored at 4 to prepare a carbonic anhydrase complex as shown in Fig.

≪ Preparation Example 3 > - Preparation of carbonic anhydrase complex 3

A fibrous support having a carboxyl group-containing polyaniline (polymerized with 1: 3 parts by weight of each of aniline and 3-aminobenzoic acid as monomers) having a diameter of about 50 nm was prepared. Then, a carbonic anhydridease The EDC-NHS reaction in which the carboxyl group is substituted is proceeded so as to be easily bonded. Specifically, 2 mg was dispersed in 10 ml of distilled water, and 2 ml of EDC (10 mg / ml), 4 ml of NHS (50 mg / ml) and 4 ml of 100 mM MES (2- (N-morpholino) ethanesulfonic acid) buffer pH 6.0) to prepare a total of 20 ml of mixed solution. Then, the mixture was stirred at room temperature for 1 hour, washed with water by centrifugation, and then 10 mg / ml of a carbonic anhydrase (CA) solution dissolved in 100 mM PB buffer (pH 7.6) Followed by stirring to induce covalent bonding between the enzyme and the polyaniline support. Thus, a carbonic anhydrase conjugate having an enzyme bound to a polyaniline support was prepared.

≪ Example 1 >

In the conversion reactor, the carbonic anhydrase complex and water as shown in Fig. 3 prepared in Preparation Example 1 were placed in an enzyme reaction unit, and a 50% by weight aqueous solution of N-methyldiethanolamine as a wetting agent was added as a carbon dioxide absorbent And a carbonic anhydrase complex as shown in FIG. 3 prepared in Preparation Example 1 was provided to implement a serial reactor in which a conversion reactor and a collection reactor were connected in series as shown in FIG.

≪ Example 2 >

The same procedure as in Example 1 was carried out, except that the carbonic anhydrase crosslinking complex provided in the enzyme reactor was replaced with the carbonic anhydrase cross-linking complex prepared in Preparation Example 2 to prepare a serial reactor.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

100, 100 ': conversion reactor 110, 110': gas supply unit
120, 120 ': enzyme reaction unit 120a, 121': carbonic anhydrase complex
120b, 122 ': Liquid 130, 130': Bicarbonate aqueous solution discharge portion
140, 140 ': gas discharge part 150, 150': reaction chamber
200, 200 ': collection reactor
210, 210 ': Carbon dioxide capture discharge unit
220, 220 ': gas supply part 230, 230': reaction chamber
300,300 ': Bicarbonate ion storage 400,400': Desorber

Claims (18)

A conversion reactor comprising an enzyme reaction part comprising a liquid filled in a part of the conversion reactor and a carbonic anhydrase for a reaction for converting the supplied carbon dioxide to bicarbonate ion; And
And a collection reactor communicating with the conversion reactor and collecting the supplied carbon dioxide,
The carbonic anhydrase may be one or more of a free enzyme enzyme dispersed in a liquid phase, an enzyme aggregate in which a plurality of uncoated and aggregated enzymes are aggregated, and an enzyme cross- . The method according to claim 1,
The exhaust gas containing carbon dioxide is supplied to the conversion reactor or the collection reactor to convert or capture carbon dioxide, and then the exhaust gas containing unreacted carbon dioxide is supplied to a collection reactor or a conversion reactor to collect or convert the unreacted carbon dioxide A series reactor for carbon dioxide conversion and collection. The method according to claim 1,
Wherein the conversion reactor further comprises a gas supply part for supplying the exhaust gas and a gas exhaust part for exhausting the exhaust gas containing unreacted carbon dioxide in the enzyme reaction part. The method according to claim 1,
Wherein said carbonic anhydrase comprises at least one of a wild type carbonic anhydrase and a carbonic anhydrase variant. delete The method according to claim 1,
Wherein the carbonic anhydrase has a support and is bonded on the support or supported inside the support. The method according to claim 1,
Wherein the conversion reactor further comprises a bicarbonate aqueous solution discharge unit for discharging the bicarbonate aqueous solution converted and dissolved in the enzyme reaction unit. The method according to claim 1,
Wherein the collection reactor comprises at least one of a carbon dioxide absorbent and a carbon dioxide separation membrane. 8. The method of claim 7,
Further comprising at least one of a bicarbonate aqueous solution reservoir and a bicarbonate aqueous solution reservoir to communicate with the bicarbonate aqueous solution discharge portion. The method according to claim 1,
Wherein the enzyme cross-linking complex further comprises a first support comprising a first functional group on its surface,
A second carbonic anhydrase binding to the first functional group directly and a second carbonic anhydrase crosslinking complex that binds to the first carbonic anhydrase and crosses the adjacent carbonic anhydrase, Collecting series reactors. 11. The composition of claim 10, wherein the enzyme cross-linking complex comprises
Further comprising a second support which comprises a second functional group on its surface and which binds to the enzyme through at least one of the first carbonic anhydrase and the second carbonic anhydrase crosslinking complex through the second functional group, Collecting series reactors. The method according to claim 1,
Wherein the trapping reactor further comprises a carbon dioxide capture and discharge unit for discharging a capture including at least one of carbon dioxide absorbent, carbon dioxide bond, and reaction bond. 13. The method of claim 12,
And a carbon dioxide desorber for separating and collecting carbon dioxide from the discharged carbon dioxide collected in the discharged carbon dioxide collection unit. delete (1) supplying an exhaust gas containing carbon dioxide to a conversion reactor of a series reactor according to any one of claims 1 to 4 and 6 to 13 to convert the carbon dioxide to bicarbonate ion; And
(2) supplying the exhaust gas containing unreacted carbon dioxide in the supplied carbon dioxide to a collection reactor to collect carbon dioxide, and a step of converting and collecting carbon dioxide through a series reactor. (a) supplying an exhaust gas containing carbon dioxide to a collection reactor of a tandem reactor according to any one of claims 1 to 4 and 6 to 13 to collect the carbon dioxide; And
(b) feeding a flue gas containing uncoated carbon dioxide out of the supplied carbon dioxide to a conversion reactor to convert the carbon dioxide to bicarbonate ions, and a process for converting and collecting carbon dioxide through a series reactor. 16. The method of claim 15,
Withdrawing the converted bicarbonate ions from the conversion reactor to collect; And
Desorbing the collected carbon dioxide to collect carbon dioxide; and converting and collecting the carbon dioxide through the series reactor. 17. The method of claim 16,
Withdrawing the converted bicarbonate ions from the conversion reactor to collect; And
Desorbing the collected carbon dioxide to collect carbon dioxide; and converting and collecting the carbon dioxide through the series reactor.

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