KR20160096793A - Carbonic anhydrase mimetic enzyme comprising transition metal and tridentate ligands comprising nitrogens and use thereof - Google Patents
Carbonic anhydrase mimetic enzyme comprising transition metal and tridentate ligands comprising nitrogens and use thereof Download PDFInfo
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- KR20160096793A KR20160096793A KR1020150018191A KR20150018191A KR20160096793A KR 20160096793 A KR20160096793 A KR 20160096793A KR 1020150018191 A KR1020150018191 A KR 1020150018191A KR 20150018191 A KR20150018191 A KR 20150018191A KR 20160096793 A KR20160096793 A KR 20160096793A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention relates to a carbonic anhydrase mimetic catalyst comprising a tetra-coordinated transition metal and a tri-coordinating ligand bound to the transition metal through three nitrogen atoms; A composition for removing carbon dioxide, which comprises an amine compound as said carbonic anhydrase mimic catalyst and a carbon dioxide absorbent; A carbon dioxide removing method comprising the step of absorbing carbon dioxide into the composition for removing carbon dioxide; Novel trifunctional ligand compounds; And a complex in which the ligand compound is bonded to the tetra-coordinated transition metal through three nitrogen atoms.
The novel carbonic anhydrase mimic catalyst of the present invention is a catalyst chemically synthesized by simulating the structure of natural carbonic anhydrase which promotes the reaction of hydration of carbon dioxide molecules into bicarbonate and is a catalyst similar to natural carbonic anhydrase It can exhibit activity, but it can exhibit activity continuously without being denatured even at a relatively high temperature or pH condition change. In addition, when used in combination with carbon dioxide absorbent of conventional amines, carbon dioxide absorption can be promoted, as well as the regeneration rate due to desorption of carbon dioxide can be improved. Therefore, it can be reused and economically advantageously used for carbon dioxide removal.
Description
The present invention relates to a carbonic anhydrase mimetic catalyst comprising a tetra-coordinated transition metal and a tri-coordinating ligand bound to the transition metal through three nitrogen atoms; A composition for removing carbon dioxide, which comprises an amine compound as said carbonic anhydrase mimic catalyst and a carbon dioxide absorbent; A carbon dioxide removing method comprising the step of absorbing carbon dioxide into the composition for removing carbon dioxide; Novel trifunctional ligand compounds; And a complex in which the ligand compound is bonded to the tetra-coordinated transition metal through three nitrogen atoms.
According to the International Energy Agency (IEA), carbon dioxide capture and storage technology (CCS) is expected to account for about 19% of the global warming prevention alternatives, and diffusion of CO2 capture and storage technology What is most needed for diffusion is technical verification and economics. Based on the current state of the art, the cost of capturing and storing carbon dioxide is estimated to range from $ 68 to 121 per tonne of CO 2 ("Cost and Performance of Carbon Dioxide Capture from Power Generation", IEA, 2011; Report of the Interagency Task Force on Carbon Capture and Storage ", CSLF, 2010). Considering the current power supply system, the generation of carbon dioxide is inevitable because the fossil fuel-based thermal power generation is still dominant. Therefore, the cost for the carbon dioxide treatment is a cause of cost increase in the whole industry using electricity generation and further electricity. Therefore, various researches and developments are needed to reduce the installation cost and the operating cost for the carbon dioxide capture and storage process.
Most of the costs associated with the carbon dioxide capture and storage process is needed for CO 2 capture, CO 2 because it is used most of the collection cost to supply the required renewable energy to separate the carbon dioxide from the absorbing agent containing CO 2 and the present study The CO 2 capture process is focused on developing absorbent materials that can lower the renewable energy. Winning is the most important part of the CO 2 capture processes in terms of lowering the cost of renewable energy, but at the same time, more preferably lower renewable energy fast the CO 2 absorption rate should be parallel to it to reduce the size of the absorber.
The atmospheric carbon dioxide is rapidly dissolved in water to form hydrated carbon dioxide as shown in Scheme 1. The hydrated carbon dioxide then reacts with water to convert to carbonic acid (Scheme 2) or reacts with hydroxide ions at high pH to form bicarbonate (Scheme 4). Reaction Equation 4 is negligible at pH 8 or below, and Equation 4 is dominant at pH 8 <pH <10, and Reaction Equation 4 is dominant at pH 10 or higher. The bicarbonate ion is rapidly converted to carbonate ion as shown in Scheme 5. The converted carbonate ion easily precipitates in the form of metal carbonate (calcium carbonate; CaCO 3 , magnesium carbonate, MgCO 3, etc.) at normal temperature and atmospheric pressure in the presence of suitable cations. It is a form capable of storing the most stable carbon dioxide on the earth It can be used for paper, building materials, and industrial applications, which can partially offset the cost of CO2 storage and collection.
[Reaction Scheme 1]
[Reaction Scheme 2]
[Reaction Scheme 3]
[Reaction Scheme 4]
[Reaction Scheme 5]
[Reaction Scheme 6]
In the reaction, the rate constant of the reaction is only about 6.2 × 10 -2 / s (25 ° C.) (FR Keene et al . , Electrochemical and Electrocatalytic Reactions of Carbon Dioxide, Elsevier, 1993, 1-18). Therefore, it is necessary to identify a reaction medium capable of promoting the formation of carbonic acid or omitting the above process and producing carbonate ions. Carbonic anhydrase, which exists in nature, is known to be the best enzyme to perform this role. Carbonic anhydrase is a kind of metalloenzyme which contains zinc in the inside. It is involved in the ingestion and release of carbon dioxide from red blood cells during respiration, and is involved in the production and secretion of hydrogen ions and bicarbonate ions in various secretory organs. (TH Maren, Physiol. Res., 1967, 47: 595-781).
Among the carbonic anhydrase enzymes in the body, HCAII is known to be the enzyme that accelerates the fastest reaction on Earth and hydrates at least 1.4 × 10 6 carbon dioxide molecules per second. When the carbonic anhydrase is present in the carbon dioxide absorption reaction, bicarbonate is generated in the state of eliminating the rate determining step as shown in the reaction formula 2 to accelerate the overall reaction rate. Therefore, it can improve the absorption rate of carbon dioxide when it is applied to the carbon dioxide capture reaction and it shows the carbon dioxide absorption rate about 100 times faster than that of the monoethanolamine (MEA) which has a fast absorption rate of carbon dioxide in the amine absorbent (Carbozyme Inc. GHGT-9 , 2008).
However, when the carbonic anhydrase is applied to the carbon dioxide capture process for removing carbon dioxide emitted by the combustion of fossil fuel, the activity rapidly decreases due to the release of the enzyme protein at a temperature higher than 50 ° C., There are many difficulties in use in commercial processes. In addition, although carbonic anhydrase can be extracted from various sources such as human and bovine serum, its extraction and purification process is invasive, cumbersome, and expensive.
Therefore, the present inventors have made intensive studies to discover a catalyst capable of exhibiting an activity similar to that of the carbonic anhydrase without being influenced by temperature and pH conditions. As a result, it has been found that three histidines are bound to a transition metal The catalytic activity of these catalysts was similar to that of carbonic anhydrase and was also used with carbon dioxide absorbing agent of conventional amines. The present inventors have confirmed that the carbon dioxide adsorption is promoted and the regeneration rate by the carbon dioxide desorption is also improved.
One object of the present invention is to provide a quaternary transition metal; And a tertiary coordination ligand bound to the transition metal through three nitrogen atoms. The present invention also provides a carbonic anhydrase mimetic catalyst.
Another object of the present invention is to provide a process for producing the above-mentioned carbonic anhydrase mimic catalyst; And an amine compound as a carbon dioxide absorbent.
Yet another object of the present invention is to provide a method for removing carbon dioxide, comprising: a first step of contacting the composition for removing carbon dioxide with a gas containing carbon dioxide to absorb carbon dioxide; And a second step of converting the absorbed carbon dioxide to carbonate ion (HCO 3 - ).
Another object of the present invention is to provide a compound represented by the following formula 1:
[Chemical Formula 1]
Another object of the present invention is to provide a compound represented by the following formula 2:
(2)
Another object of the present invention is to provide a complex in which a compound represented by the above formula (1) or (2) is bonded to a quaternary coordination metal via three nitrogen atoms.
According to a first aspect of the present invention, And a tertiary coordination ligand bound to the transition metal through three nitrogen atoms. ≪ Desc / Clms Page number 2 >
The present invention is characterized by providing a novel carbonic anhydrase mimic catalyst. The above-described carbonic anhydrase-catalyzed catalyst is a compound of the present invention which chemically mimics a structure similar to the structure of three histidine-coordinated zinc known as catalytic sites of natural carbonic anhydrase, which rapidly converts carbon dioxide to bicarbonate. It is confirmed that it shows catalytic activity similar to anhydrous enzyme. Furthermore, the inventors of the present invention have confirmed for the first time that they exhibit the same catalytic activity even in the presence of transition metals such as copper or nickel instead of zinc, unlike natural carbonic anhydrase. In addition, when the carbonic anhydride-catalyzed catalyst according to the present invention is used together with the amine-based carbon dioxide absorbent, not only promotes the absorption of carbon dioxide but also facilitates the removal of the amine-based carbon dioxide absorbent, the amine-based carbon dioxide absorbent can be easily reused .
For example, the transition metal may be zinc (Zn), copper (Cu), or nickel (Ni).
For example, the tri-coordination ligand may be a carbonic anhydrase mimetic catalyst represented by the following formula 1 or 2:
[Chemical Formula 1]
(2)
In this formula,
R 1 and R 2 are each independently unsubstituted or is substituted aryl, they are connected form a C 2-6 alkylene or C 2 -6 hetero alkylene;
A is N or CR < 6 & gt ;;
R 3 to R 5 are each independently a C 5 -10 heteroaryl containing at least one unsubstituted or substituted nitrogen atom in the ring;
R 6 is hydrogen, hydroxy, C 1 -4 alkoxy, or C 1 -4 alkyl; And
l, m and n are each independently an integer of 0 to 2,
The substituted aryl and heteroaryl may be substituted by one or more substituents selected from the group consisting of C 1 -4 alkyl group, hydroxy, nitro and sulfonate.
Preferably, R 1 and R 2 are each independently unsubstituted or substituted phenyl or are connected to each other to form -C 2 H 4 - or -C 2 H 4 -NH-C 2 H 4 -;
A is N or CR < 6 & gt ;;
R 3 to R 5 are each independently an unsubstituted or substituted benzimidazolyl or pyridinyl;
R 6 is hydroxy or methoxy; And
l, m and n are each independently 0 or 1,
The substituted phenyl, benzimidazolyl, and pyridinyl may be substituted with one or more substituents selected from the group consisting of methyl, hydroxy, nitro, and sulfonic acid groups, but are not limited thereto.
More preferably, R 1 and R 2 are each independently phenyl, methylphenyl, or dimethylphenyl, or may be linked together to form -C 2 H 4 - or -C 2 H 4 -NH-C 2 H 4 -.
More preferably, when A is N, R 3 to R 5 are each independently hydroxybenzimidazolyl or nitrobenzimidazolyl, and l, m and n are all 1; When A is CR 6 , R 3 to R 5 are each independently pyridinyl or methoxypyridinyl, R 6 is hydroxy or methoxy, l, m and n can all be 0, but are not limited thereto Do not.
The 3-coordinate ligand forming the carbonic anhydrase mimic catalyst of the present invention is characterized in that it contains three nitrogen atoms appropriately spaced so as to be able to bind to the central transition metal in one molecule. Such a tri-coordinating ligand is relatively easy to bind as compared with the case where three single-site ligands are bonded, and when a ligand is bound, a predetermined steric hindrance is given to the coordination complex to form a dimer through an extra bonding site of the central transition metal It is also possible to exhibit an effect of preventing the
For example, a hydroxy group or a water molecule may be bonded to an extra coordination site which is not bonded to a ligand in the tetracoordination transition metal of the carbonic anhydrase mimic catalyst of the present invention.
A second aspect of the present invention is a carbonic anhydrase mimic catalyst according to the first aspect; And an amine compound as a carbon dioxide absorbent.
For example, the amine compound may be, but not limited to, MDEA (methyl diethanolamine), AMP (2-aminomethylpropanol), MEA (monoethanolamine), DEA (doethanolamine), PEI And an amine compound capable of absorbing the dissolved carbon dioxide.
For example, the composition of the present invention is characterized in that the regeneration efficiency of the carbon dioxide absorbent is improved as compared with the composition for removing carbon dioxide, which does not include the carbonic anhydrase catalytic catalyst, by including the carbonic anhydrase catalytic catalyst and the amine compound together.
In the specific examples of the present invention, the carbon dioxide absorbing agent was sufficiently absorbed by using MDEA as an amine compound absorbing carbon dioxide, and the amount of carbon dioxide released after conversion into the carbon dioxide desorption condition was measured to confirm the regeneration efficiency of the carbon dioxide absorbent . At this time, it was confirmed that the carbon dioxide anhydrase-catalyzed catalyst of the present invention was not included or included, and the carbon dioxide anhydrase release rate was increased by comparing the measured values, Indicating that the presence promotes the regeneration of the carbon dioxide absorbent.
In a third aspect of the present invention, there is provided a method for removing carbon dioxide according to the second aspect, comprising the steps of: (1) contacting carbon dioxide with a gas containing carbon dioxide to absorb carbon dioxide; And a second step of converting the absorbed carbon dioxide to carbonate ion (HCO 3 - ).
For example, the first step may be performed at a pressure in the range of 1 atm to 10 atmospheres and at a temperature in the range of 20 to 70 < 0 > C, but is not limited thereto.
For example, the third step may further include a third step of desorbing carbon dioxide after the second step to regenerate the composition for removing carbon dioxide, but the present invention is not limited thereto.
For example, the third step may be performed at a pressure in the range of 0.01 atm to 5 atm and at a temperature in the range of 80 to 150 < 0 > C, but is not limited thereto.
For example, the composition for removing carbon dioxide can be regenerated by desorbing excess carbon dioxide and then reused for the carbon dioxide removal process.
Since the natural carbonic anhydrase is a kind of protein, it is likely to be denatured by environmental conditions such as heat or acidity or to lose its catalytic activity. Therefore, when carbon dioxide is to be removed using the composition for removing carbon dioxide, Or pH, the removal efficiency may vary greatly. It may be impossible to use at high temperature or at too high or low pH. However, since the carbonic anhydrase-catalyzed catalyst of the present invention is a chemically synthesized compound, not a protein, it exhibits improved heat and / or pH stability, and thus can be used for removing carbon dioxide at a high temperature. In addition, the present invention provides a composition for removing carbon dioxide, which contains carbon dioxide absorbent, further includes a carbonic anhydride enzyme-catalyzed catalyst. Even if the composition is treated at a high temperature, it is not greatly affected by the absorption performance and promotes desorption of carbon dioxide, In general, since the desorption of gas is promoted at a high temperature, the composition of the present invention can promote absorption / desorption of carbon dioxide according to conditions, and thus can be usefully used for removing carbon dioxide .
A fourth aspect of the present invention provides a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
In this formula,
R 1 and R 2, each is independently an unsubstituted or substituted aryl, or, connected to each other to form a C 2-6 alkylene or C 2 -6 alkylene-heteroaryl,
The substituted aryl may be substituted by one or more C 1 -4 alkyl.
A fifth aspect of the present invention provides a compound represented by Formula 2:
(2)
In this formula,
A is N or CR < 6 & gt ;;
R 3 to R 5 are each independently a C 5 -10 heteroaryl containing at least one unsubstituted or substituted nitrogen atom in the ring;
R 6 is hydrogen, hydroxy, C 1 -4 alkoxy, or C 1 -4 alkyl; And
l, m and n are each independently an integer of 0 to 2,
The substituted heteroaryl may be substituted with one or more substituents selected from the group consisting of hydroxy, nitro, and sulfonic acid groups.
A sixth aspect of the present invention provides a complex in which a compound according to the fourth or fifth aspect is bonded to a tetracoordinated transition metal through three nitrogen atoms.
For example, the transition metal may be zinc (Zn), copper (Cu), or nickel (Ni), but is not limited thereto.
The novel carbonic anhydrase mimic catalyst of the present invention is a catalyst chemically synthesized by simulating the structure of natural carbonic anhydrase which promotes the reaction of hydration of carbon dioxide molecules into bicarbonate and is a catalyst similar to natural carbonic anhydrase It can exhibit activity, but it can exhibit activity continuously without being denatured even at a relatively high temperature or pH condition change. In addition, when used in combination with carbon dioxide absorbent of conventional amines, carbon dioxide absorption can be promoted, as well as the regeneration rate due to desorption of carbon dioxide can be improved. Therefore, it can be reused and economically advantageously used for carbon dioxide removal.
Brief Description of the Drawings Fig. 1 shows a carbonic anhydrase-catalyzed catalyst containing a tetra-coordinated transition metal (Cu and Ni) and a pyridine derivative containing two aromatic amine substituents as a three-coordinate ligand, and a carbon dioxide- Fig. In the comparative example, the carbon dioxide absorbent MDEA was used alone.
FIG. 2 is a graph showing the results of a carbonic anhydrase-catalyzed catalyst containing a quadrature transition metal (Zn) as a trifunctional ligand and a closed ring-form pyridine derivative connected with diethylenetriamine as an aliphatic amine compound, and carbon dioxide Fig. 5 is a graph showing the absorption rate of carbon dioxide in the composition for removal. In the comparative example, the carbon dioxide absorbent MDEA was used alone.
FIG. 3 shows a carbonic anhydrase-catalyzed catalyst containing a quadrature transition metal (Zn) and a closed ring-type pyridine derivative linked with diethylenamine, which is an aliphatic amine compound, as a trifunctional ligand, and a carbon dioxide- Fig. 2 is a graph showing the absorption rate of carbon dioxide in a composition for use in the present invention. In the comparative example, the carbon dioxide absorbent MDEA was used alone.
4 is a graph showing a change in carbon dioxide desorption rate depending on whether or not a simulated catalyst is added.
FIG. 5 is a graph showing the carbon dioxide absorption rate of the carbonic anhydrase-catalyzed catalyst according to the present invention with respect to temperature and treatment time. FIG.
Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited by these examples.
Example
1 to 9: aromatic
Amine
Included
Ligand
And < RTI ID = 0.0 >
Carbonic acid
Preparation of anhydrous enzyme-catalyzed catalyst
Pyridine-2,6-dicarbonyl chloride (1.45 mmol) was dissolved in 100 ml of tetrahydrofuran. To this solution, 2,6-dimethylaniline (3.9 mmol) and triethylamine The reaction was allowed to proceed at 0 ° C for 1 hour and then at 25 ° C for 2 hours. The precipitated salt was removed by filtration, dried thoroughly with anhydrous sodium sulfate, and washed several times with a solvent such as diethyl ether to obtain the ligand shown in Table 1.
The ligands shown in Tables 2 and 3 were obtained in the same manner as above except that aniline or p-toluidine was used in place of the 2,6-dimethylaniline.
The three ligands thus prepared were respectively reacted as a metal precursor with copper trifluoromethanesulfonate (Cu (OTf) 2 ), trifluoromethanesulfonated nickel (Ni (OTf) 2 ), zinc perchlorate hexaphosphate ClO 4 ) 2 · 6H 2 O) or trifluoromethanesulfonate (Zn (OTf) 2 ) and tetrohydrofuran in a mixed solution of 0.3 mL tetraethylammonium hydroxide (Et 4 NOH ) Was added and reacted at 25 占 폚 for 12 hours to obtain transition metal coordination complexes (Examples 1 to 9) in which the ligand was three-coordinateed.
The reactants used in the examples and the resulting ligands and the transition metal coordination compounds prepared therefrom, that is, the carbonic anhydrase mimic catalyst, are shown in Tables 1 to 3 below.
Example
10 to 17: aliphatic
Amine
Included
Ligand
And < RTI ID = 0.0 >
Carbonic anhydrase
Manufacture of simulated catalysts
Pyridine-2,6-dicarbonyl chloride (1.45 mmol) was dissolved in 100 ml of tetrahydrofuran. Diethyltriamine (4.2 mmol) and triethylamine (3 mmol) RTI ID = 0.0 > 25 C < / RTI > for 2 hours. The precipitated salts were removed by filtration, dried thoroughly with anhydrous sodium sulfate, washed several times with diethyl ether and methylene chloride as solvents, and the ligands shown in Table 4 were obtained.
Further, the ligands shown in Table 5 were obtained in the same manner as above except that ethylenediamine was used instead of diethyltriamine.
A ligand of two or above prepared respectively as precursors of zinc perchlorate hexahydrate (Zn (ClO 4) 2 · 6H 2 O), zinc acetate (Zn (CH 3 CO) 2 ), zinc nitrate hexahydrate (Zn (NO 3 ) 2 .6H 2 O) or trifluoromethanesulfonated zinc (Zn (OTf) 2 ) and tetrohydrofuran, followed by reaction at 25 ° C for 12 hours to obtain a ligand Transition metal coordination complexes (Examples 10 to 17) were obtained.
The reactants used in the examples and the resulting ligands and the transition metal coordination compounds prepared therefrom, that is, the carbonic anhydrase mimic catalysts, are shown in Tables 4 and 5 below.
Experimental Example
One:
Carbonic anhydrase
Enhancement of Carbon Dioxide Absorption of Carbon Dioxide Absorbent by Addition of Simulated Catalyst
In order to investigate the effect of addition of a carbonic anhydrase (CA) catalyst on the absorption of carbon dioxide, MDEA (methyl diethanolamine), which is a tertiary amine with a relatively low carbon dioxide absorption rate, The rate of reaction for carbon dioxide uptake at the time of addition and at the time of no addition was measured and shown in FIGS. 1 to 3 together. An aqueous MDEA solution containing no CA simulated catalyst was used as a comparative example (Comparative Example 1). Since the absorption rate of carbon dioxide in CA is very fast, it is impossible to measure with a general reaction rate analysis system. Therefore, the rate of carbon dioxide uptake of CA-based catalyst was measured using a stopped-flow spectrometer (SX20, Applied Photophysics) . Specifically, 30% MDEA exemplary solution according to the invention in 100 ml of Examples 1 to A 17 an indicator for CA simulate catalyst 0.01 mmol and the absorbance measured at 25 ℃ After addition bomo mol blue (bromothymolblue) of 1 mmol concentration The absorbance changes were measured by instantaneous mixing with an aqueous solution saturated with carbon dioxide, and the reaction rate and rate constants were calculated from these values. Comparative Example 1 was carried out in the same manner as above using a 30% MDEA aqueous solution to which no CA catalyst catalyst was added.
As shown in FIGS. 1 to 3, it was confirmed that the carbon dioxide absorption reaction occurred remarkably rapidly in the MDEA solution containing the CA-modified catalyst according to the present invention. This indicates that the CA catalyst according to the present invention promotes the absorption of carbon dioxide by the MDEA and is attributed to the promotion of the carbon dioxide hydration reaction in the transition metal which is the active point of the catalyst. In addition, it has been confirmed that the effect of promoting the absorption of carbon dioxide and promoting the catalytic activity also occurs in a simulated catalyst containing a metal other than Zn such as Cu and Ni as a central metal, and metals other than Zn can be used as a center metal in CA- Indicating that it can act as an active site for catalysis.
Experimental Example
2:
Carbonic anhydrase
Catalytic activity regeneration promotion effect of composition for removal of carbon dioxide by addition of simulated catalyst
Using the compound of Example 14, which is the CA simulated catalyst showing the best carbon dioxide absorption promoting effect, the effect on the regeneration of the catalyst by carbon dioxide desorption was confirmed through the above Experimental Example 1.
Specifically, the solution containing Comparative Examples 1 and 14 was sufficiently absorbed at 25 占 폚. After confirming that each of the solutions was saturated with carbon dioxide, the amount of carbon dioxide released by removing carbon dioxide at 90 ° C was measured by gas chromatography to confirm the rate of desorption and desorption of dioxide in the solution over time. The results are shown in FIG. 4 . As shown in FIG. 4, the solution containing Example 14 produced a faster rate of desorption of oxygen dioxide than that of Comparative Example 1, indicating that the catalyst activity was regenerated more rapidly at the same temperature.
Experimental Example
3:
Carbonic anhydrase
Evaluation of Thermal Stability of Composition for Removing Carbon Dioxide by Addition of Simulated Catalyst
The composition for removing carbon dioxide containing the compound of Example 10 and the compound of Example 14, which were found to have the best carbon dioxide absorption promoting effect among the carbonic anhydrase mimic catalysts of Examples 1 to 17 of the present invention, The carbon dioxide absorption rate after heat treatment at high temperature was compared.
Specifically, the solutions containing the compounds of Comparative Examples 1, 10 and 14 were heat-treated at 120 ° C for 1 hour or 24 hours, cooled to 25 ° C to measure the carbon dioxide absorption rate, and maintained at 25 ° C And compared with the results for one composition. The carbon dioxide absorption rate was measured in the same manner as in Experimental Example 1. The measured carbon dioxide absorption rates were normalized based on the measured values for the composition including Example 14, and the results are shown in FIG. As shown in FIG. 5, the composition of Example 10 or 14 maintained at room temperature exhibited remarkably improved carbon dioxide absorption rate as compared with Comparative Example 1. Further, even after the heat treatment at 120 ° C for 1 hour or 24 hours, the carbon dioxide absorption rate reduction rate remained at a significantly low level as compared with the comparative example. This indicates that the carbonic anhydrase-catalyzed catalyst of the present invention has excellent thermal stability, so that the catalytic activity for promoting the absorption of carbon dioxide can be maintained even for a long period of heat treatment.
Claims (19)
Wherein the transition metal is zinc (Zn), copper (Cu), or nickel (Ni).
Wherein the tri-coordinating ligand is represented by the following formula (1) or (2): < EMI ID =
[Chemical Formula 1]
(2)
In this formula,
R 1 and R 2 are each independently unsubstituted or is substituted aryl, they are connected form a C 2-6 alkylene or C 2 -6 hetero alkylene;
A is N or CR < 6 & gt ;;
R 3 to R 5 are each independently a C 5 -10 heteroaryl containing at least one unsubstituted or substituted nitrogen atom in the ring;
R 6 is hydrogen, hydroxy, C 1 -4 alkoxy, or C 1 -4 alkyl; And
l, m and n are each independently an integer of 0 to 2,
The substituted aryl and heteroaryl may be substituted by one or more substituents selected from the group consisting of C 1 -4 alkyl group, hydroxy, nitro and sulfonate.
R 1 and R 2 are each independently unsubstituted or substituted phenyl or are connected to each other to form -C 2 H 4 - or -C 2 H 4 -NH-C 2 H 4 -;
A is N or CR < 6 & gt ;;
R 3 to R 5 are each independently an unsubstituted or substituted benzimidazolyl or pyridinyl;
R 6 is hydroxy or methoxy; And
l, m and n are each independently 0 or 1,
Wherein said substituted phenyl, benzimidazolyl, and pyridinyl are substituted with one or more substituents selected from the group consisting of methyl, hydroxy, nitro, and sulfonic acid groups.
R 1 and R 2 are each independently a phenyl, methylphenyl, or dimethylphenyl, or, they are connected -C 2 H 4 - or -C 2 H 4 -NH-C 2 H 4 - in that the carbonic acid anhydrase simulated catalyst .
When A is N,
R 3 to R 5 are each independently hydroxybenzimidazolyl or nitrobenzimidazolyl,
l, m and n are all 1;
When A is CR 6 ,
R 3 to R 5 are each independently pyridinyl or methoxypyridinyl,
R < 6 > is hydroxy or methoxy,
l, m, and n are all 0.
Wherein the extra coordination site of the tetracoordinated transition metal is a hydroxy acid group or a water molecule.
Wherein the amine compound is one selected from the group consisting of MDEA (methyl diethanolamine), AMP (2-aminomethylpropanol), MEA (monoethanolamine), DEA (doethanolamine), PEI (polyethyleneimine) and mixtures thereof.
Wherein the composition comprises a carbonic anhydrase catalyzed catalyst and an amine compound so that the regeneration efficiency of the carbon dioxide absorbent is improved as compared with a composition for removing carbon dioxide which does not contain a carbonic anhydrase catalytic catalyst.
And a second step of converting the absorbed carbon dioxide to carbonate ion (HCO 3 - ).
Wherein the first step is carried out at a pressure in the range from 1 atmosphere to 10 atmospheres and at a temperature in the range from 20 to 70 < 0 > C.
And a third step of desorbing carbon dioxide after the second step to regenerate the composition for removing carbon dioxide.
Wherein the third step is carried out at a pressure in the range of 0.01 to 5 atm and at a temperature in the range of 80 to 150 < 0 > C.
The carbon dioxide removing composition according to claim 13, wherein the regenerated carbon dioxide removing composition is reused.
[Chemical Formula 1]
In this formula,
R 1 and R 2, each is independently an unsubstituted or substituted aryl, or, connected to each other to form a C 2-6 alkylene or C 2 -6 alkylene-heteroaryl,
The substituted aryl may be substituted by one or more C 1 -4 alkyl.
(2)
In this formula,
A is N or CR < 6 & gt ;;
R 3 to R 5 are each independently a C 5 -10 heteroaryl containing at least one unsubstituted or substituted nitrogen atom in the ring;
R 6 is hydrogen, hydroxy, C 1 -4 alkoxy, or C 1 -4 alkyl; And
l, m and n are each independently an integer of 0 to 2,
The substituted heteroaryl may be substituted with one or more substituents selected from the group consisting of hydroxy, nitro, and sulfonic acid groups.
Wherein the transition metal is zinc (Zn), copper (Cu), or nickel (Ni).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114231518A (en) * | 2021-12-17 | 2022-03-25 | 浙江工业大学 | Immobilized carbonic anhydrase and application thereof in preparation of carbon dioxide absorbent |
| CN115611813A (en) * | 2022-11-09 | 2023-01-17 | 天津大学 | Preparation method and application of artificial enzyme with carboxylesterase and carbonic anhydrase double-enzyme activities |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114231518A (en) * | 2021-12-17 | 2022-03-25 | 浙江工业大学 | Immobilized carbonic anhydrase and application thereof in preparation of carbon dioxide absorbent |
| CN115611813A (en) * | 2022-11-09 | 2023-01-17 | 天津大学 | Preparation method and application of artificial enzyme with carboxylesterase and carbonic anhydrase double-enzyme activities |
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