This application claims the benefit of Korean Patent Application No. 10-2023-0008539, filed on Jan. 20, 2023 and No. 10-2023-0162257, filed on Nov. 21, 2023 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
The present inventive concept relates to a zeolite for direct air capture at room temperature, and more specifically, to a zeolite that can capture carbon dioxide whose surface is modified through sodium ion exchange.
Direct air capture, which has recently emerged as a key technology for carbon neutrality, is a technology that directly captures carbon dioxide from the atmosphere to produce concentrated carbon dioxide. The captured carbon dioxide can be permanently stored to remove carbon dioxide from the air or utilized as a raw material for various products. According to the IEA's 2050 Net Zero Emissions Report, the goal is to expand direct air capture to capture 60 Mt of CO2 annually by 2030. However, compared to other technologies for carbon reduction, direct air capture is superior in terms of additionally and durability, but it has the disadvantage of being difficult to commercialize and incurring significant costs, especially in the early stages of research.
Conventional direct air capture technologies include solid direct carbon capture and liquid direct carbon capture. Among others, solid direct carbon capture is based on solid adsorbents that operate at atmospheric pressure and medium temperature. It can also be used to extract moisture from the air and is a modular form, which facilitates the facility's expansion. Moreover, compared to liquid direct carbon capture that utilizes absorption techniques, adsorption technology has the advantage of lower energy consumption and cost savings. Moreover, there is little loss of capture and no wastewater, leading to reduced environmental pollution.
However, capturing CO2 from the air is inherently energy-intensive and more costly than extracting CO2 from gas sources such as power plants. Furthermore, it faces challenges in large-scale implementation and commercialization at present due to being in the early stages of research. Therefore, there is a need for the development of adsorbents that maximize the potential for carbon removal to complement and address these limitations.
The present inventive concept has been made in an effort to solve the above-described problems associated with prior art, and a first object of the present inventive concept is to provide a zeolite for carbon dioxide capture whose surface is modified through sodium ion exchange.
A second object of the present inventive concept is to provide a method for preparing a surface-modified zeolite for carbon dioxide capture to achieve the first object.
In order to achieve the first object as described above, the present inventive concept provides a zeolite for carbon dioxide capture whose surface is modified through sodium ion exchange.
In order to achieve the second object as described above, the present inventive concept provides a method for preparing a surface-modified zeolite for carbon dioxide capture. The zeolite may be obtained by mixing a zeolite and a supporting solution to form a mixed solution, followed by sodium ion exchange through heating, and the resulting zeolite may undergo additional processes such as washing, drying, and calcining.
According to the present inventive concept as described above, it is possible to reduce the atmospheric CO2 concentration by using a zeolite whose surface is modified through sodium ion exchange to achieve a high CO2 removal efficiency.
The interaction between the unique framework structure of zeolite and the ion-exchanged sodium ions results in high CO2 adsorption/desorption performance. Exchange of cations within the zeolite with sodium ions enhances the basicity of the zeolite and provides adsorption sites for CO2, allowing for efficient adsorption of acidic CO2. Furthermore, by adjusting the Si/Al ratio, the sodium ions exchanged in two different forms within the zeolite can provide distinct CO2 adsorption sites, enhancing the CO2 adsorption capacity and maintaining the activity of the zeolite consistently during repeated use.
The above and other features and advantages of the present inventive concept will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which:
As the present inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present inventive concept to particular modes of practice, and it is to be appreciated that all changes, equivalents, and substitutes that do not depart from the spirit and technical scope of the present inventive concept are encompassed in the present inventive concept.
Unless defined otherwise, all terms used herein including technical or scientific terms have the same meaning as those generally understood by those skilled in the art to which the present inventive concept pertains. It will be further understood that terms defined in dictionaries that are commonly used should be interpreted as having meanings that are consistent with their meanings in the context of the relevant art and should not be interpreted as having ideal or excessively formal meanings unless clearly defined in the present application.
As used herein, the terms “direct air capture” and “carbon dioxide capture” refer to the capture of CO2 from the atmosphere and can be interchangeably used throughout the specification.
Hereinafter, various s embodiments of the present inventive concept will be described in more detail with reference to the accompanying drawings.
Referring to
In the first step (S10), a mixed solution is formed by mixing a zeolite support and a supporting solution. The zeolite may be at least one selected from the group consisting of ZSM-5, mordenite, Y and beta zeolites, and preferably ZSM-5. The use of a surface-modified zeolite prepared using ZSM-5 enhances the formation of Lewis base sites through sodium ion exchange, resulting in a superior CO2 capture efficiency.
The supporting solution contains sodium cations and may comprise at least one selected from the group consisting of NaCl, NaNO3 and NaOH, with the use of NaCl being more desirable.
In the second step (S20), the mixed solution is heated to perform ion exchange. The ion exchange refers to the substitution of protons within the zeolite with sodium ions. Through the ion exchange, the zeolite contains 1.0 wt % to 2.5 wt % of sodium ions, preferably 1.5 wt % to 2.5 wt % of sodium ions, and more preferably 1.8 wt % to 2.4 wt % of sodium ions. If the amount of sodium ions within the zeolite is less than 1.5 wt %, the interaction between the framework structure of the zeolite and the sodium ions may be insufficient, leading to a decrease in CO2 adsorption/desorption performance, whereas if the amount of sodium ions within the zeolite exceeds 2.4 wt %, an excessive formation of Lewis base sites may occur, affecting the CO2 adsorption/desorption performance.
In the third step (S30), the ion-exchanged mixed solution from the second step (S20) is heated to evaporate the liquid, yielding a surface-modified zeolite.
In the fourth step (S40), the zeolite obtained in the third step (S30) is washed, followed by drying and calcining, yielding a zeolite whose surface is modified through sodium ion exchange.
The zeolite prepared through the above steps has a specific surface area of 350 m2/g to 420 m2/g, more preferably a specific surface area of 395 m2/g to 418 m2/g. If the specific surface area is less than 350 m2/g, the CO2 adsorption capacity may be compromised, and thus the desired effect of the present inventive concept cannot be achieved. Additionally, if the specific surface area exceeds 420 m2/g, the absorbency may be excessively high, making it difficult to selectively adsorb only CO2.
The zeolite whose surface is modified through sodium ion exchange during the above steps may be any one of ZSM-5, Y zeolite, beta zeolite, and mordenite, which may be represented by Na-ZSM-5, Na-Y, Na-beta, and Na-mordenite.
In the above steps, the ZSM-5 has an NH4-form and a Si/Al ratio of 11.5 to 16. If the Si/Al ratio is less than 11.5, it may affect the framework structure of ZSM-5, leading to insufficient structural space within the ZSM-5, whereas if the Si/Al ratio exceeds 16, the sodium ion exchange may not proceed smoothly, leading to a decrease in CO2 adsorption/desorption performance.
The sodium ion-exchanged zeolite prepared through the above steps can adsorb CO2 onto the surface at room temperature. The adsorption may involve sodium ions acting as Lewis acids and oxygen atoms of CO2 acting as Lewis bases to form a complex compound.
3 g of ZSM-5 with a Si/Al ratio of 16 used as a support and 25 ml of 0.8 M NaCl solution used as a supporting solution were mixed, and the resulting mixture was stirred at 80° C. at 300 RPM for 1 hour three times to form an ion-exchanged mixed solution. The resulting mixed solution was evaporated at 80° C. in a rotary evaporator to obtain a sodium ion exchanged zeolite Na-ZSM-5. The obtained zeolite was washed eight times for 5 minutes each at 3500 RPM, dried at a temperature of 80° C. for one day, and then calcined at 550° C. for 4 hours, preparing a surface-modified zeolite.
Except for replacing ZSM-5 with mordenite zeolite, a surface-modified zeolite was prepared under the same conditions as Preparation Example 1 using the same process.
Except for replacing ZSM-5 with beta zeolite, a surface-modified zeolite was prepared under the same conditions as Preparation Example 1 using the same process.
Except for replacing ZSM-5 with Y zeolite, a surface-modified zeolite was prepared under the same conditions as Preparation Example 1 using the same process.
Except for using ZSM-5 as a support with a Si/Al ratio of 11.5, a surface-modified zeolite was prepared under the same conditions as Preparation Example 1 using the same process.
Except for using ZSM-5 as a support with a Si/Al ratio of 25, a surface-modified zeolite was prepared under the same conditions as Preparation Example 1 using the same process.
Except for using ZSM-5 as a support with a Si/Al ratio of 40, a surface-modified zeolite was prepared under the same conditions as Preparation Example 1 using the same process.
Except for using ZSM-5 as a support with a Si/Al ratio of 140, a surface-modified zeolite was prepared under the same conditions as Preparation Example 1 using the same process.
ZSM-5 without sodium ion exchange was used.
Mordenite zeolite without sodium ion exchange was used.
Beta zeolite without sodium ion exchange was used.
Y zeolite without sodium ion exchange was used.
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In
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It can be seen from
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Therefore, it can be inferred that the Lewis base sites created through sodium ion exchange affect the CO2 adsorption performance.
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It was observed from (a) that as the Si/Al ratio decreases, the CO2 adsorption amount increases. This can be attributed to the fact that as the Si/Al ratio in (b) increases, a single peak for CO2 desorption at high temperatures is observed at the chemical adsorption site on the right side of the dotted line, indicating that the chemical adsorption is less efficient than in zeolite with low Si/Al ratios. The reason for observing a single desorption peak is that as the Si/Al ratio increases, the relatively low-energy sodium ions are pushed out. Preparation Examples 1 and 5 with low Si/Al ratios increase the adsorption strength of sodium ions and CO2, causing the CO2 desorption peak to shift to higher temperatures.
Preparation Example 1 and 5 with low Si/Al ratios also exhibited excellent physical adsorption performance. Therefore, it can be inferred that Na-ZSM-5 with low Si/Al ratios exhibits high CO2 adsorption capacity and strong interaction between zeolite and CO2.
Referring to
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Table 4 above compares the CO2 adsorption/desorption performance when O2 is included in N2 and when O2 is not included in He. When the experiment was conducted with O2 under conditions similar to atmospheric concentrations, the performance is lower than when O2 was absent. However, under the condition where O2 is not included in He, the total flow rate is 100 sccm, which is twice as different from this experiment, and thus it is expected that the performance degradation would not be significant even when conducting CO2 absorption/desorption under atmospheric conditions.
Therefore, it is preferable to use Na-ZSM-5 catalyst with a Si/Al ratio of 11.5 for CO2 capture.
According to the present inventive concept as described above, it is possible to reduce the atmospheric CO2 concentration by using a zeolite whose surface is modified through sodium ion exchange to achieve a high CO2 removal efficiency. Moreover, the interaction between the unique framework structure of zeolite and the ion-exchanged sodium ions results in high CO2 adsorption/desorption performance. Exchange of cations within the zeolite with sodium ions enhances the basicity of the zeolite and provides adsorption sites for CO2, allowing for efficient adsorption of acidic CO2. Furthermore, by adjusting the Si/Al ratio, the sodium ions exchanged in two different forms within the zeolite can provide distinct CO2 adsorption sites, enhancing the CO2 adsorption capacity and maintaining the activity of the zeolite consistently during repeated use.
While the inventive concept has been shown and described with reference to certain preferred embodiments thereof, 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 inventive concept as defined by the appended claims. Therefore, the scope of the inventive concept is defined not by the detailed description of the inventive concept but by the appended claims, and all differences within the scope will be construed as being included in the present inventive concept.
Number | Date | Country | Kind |
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10-2023-0008539 | Jan 2023 | KR | national |
10-2023-0162257 | Nov 2023 | KR | national |