청정기술 (Clean Technology)

  • 제24권1호
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  • Pages.41-49
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  • 2018
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  • 1598-9712(pISSN)
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  • 2288-0690(eISSN)
한국청정기술학회 (The Korean Society of Clean Technology)
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이산화탄소 압력순환흡착을 위한 칼슘 이온교환 Y 제올라이트의 작업용량과 선택계수 향상

Enhancement of the Working Capacity and Selectivity Factor of Calcium-Exchanged Y Zeolites for Carbon Dioxide Pressure Swing Adsorption

  • 김문현 (대구대학교 공과대학 환경공학과)
  • Kim, Moon Hyeon (Department of Environmental Engineering, Daegu University)
  • 투고 : 2017.10.16
  • 심사 : 2017.10.29
  • 발행 : 2018.03.30
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초록

$25^{\circ}C$에서 $CO_2$ 흡착을 위한 작업용량과 $CO_2/CO$ 선택계수를 현저하게 향상시키기 위하여 서로 다른 전하와 이온반경을 갖는 $Na^+$, $N^+$, $Ca^{2+}$와 $Cu^{2+}$로 이온교환된 Y 제올라이트들이 연구되었다. 매우 소량인 0.012% $Ca^{2+}$로 이온교환된 NaY는 7회의 반복적인 $CO_2$ 흡착/탈착 싸이클 동안에도 완전히 가역적이었으므로 기존에 보고된 것들과는 달리 표면에 카보네이트는 생성되지 않는 것으로 생각된다. 4 bar 이상에서 2.00% CaY, 1.60% CuY와 1.87% LiY 모두 NaY와 매우 유사한 $CO_2$ 흡착성능을 보였다할지라도 그보다 낮은 압력에서는 이들의 흡착능은 감소하였고 그 정도는 금속이온들의 종류에 의존하였다. 0.5 ~ 2.5 bar에서 $CO_2$ 흡착성능은 NaY > 1.60% CuY > 2.00% CaY > 1.87% LiY의 순으로 나타났는데, 이들 모두 동일한 faujasite 골격과 약 2.6의 Si/Al 비율을 가지므로 골격, 골격조성, 유효세공크기와 채널구조에 있어서 차이는 없기 때문에 약한 루이스산의 특성을 갖는 $CO_2$의 구별되는 흡착거동은 이온교환에 따른 국부염기도와 흡착 포텐셜 에너지의 변화 때문일 것이다. $CO_2$ 흡착과는 다른 경향성이 CO 흡착에서 나타났고 이는 보다 약한 사극자 상호작용 때문이다. 0.012 ~ 5.23% Ca 함량을 갖는 Y 제올라이트에 $CO_2$와 CO 흡착 시 Ca 함량에 따른 현저한 의존성이 존재하였는데 0.05% 이하에서 $CO_2$ 흡착능은 증가한 반면에 그 이상에서는 감소하였다. 이러한 경향에도 불구하고 Ca 함량의 증가와 함께 작업용량과 $CO_2/CO$ 선택계수는 현저히 증가하였고, 5.23% CaY의 경우 작업용량은 $2.37mmol\;g^{-1}$, 선택계수는 4.37이었는데 본 연구에서 얻어진 작업용량은 문헌에 보고된 벤치마크와 유사한 수준이었다.

Y zeolites with different extra-framework cations, such as $Na^+$, $N^+$, $Ca^{2+}$, and $Cu^{2+}$, with different charge and ionic radius have been investigated to greatly enhance a working capacity (W) of $CO_2$ adsorption at $25^{\circ}C$ and a $CO_2/CO$ selectivity factor (S). A sample of NaY with a very small amount of 0.012% $Ca^{2+}$ was fully reversible for seven times repeated $CO_2$ adsorption/desorption cycles, thereby forming no surface carbonates unlikely earlier reports. Although at pressures above 4 bar, 2.00% CaY, 1.60% CuY and 1.87% LiY all showed a $CO_2$ adsorption very similar to that measured for NaY, they gave a significant decrease in the adsorption at lower pressures, depending on the metal ion. At 0.5 ~ 2.5 bar, the extent of $CO_2$ adsorption was in the order NaY > 1.60% CuY > 2.00% CaY > 1.87% LiY. All the $Na^+-based$ metals-exchanged zeolites have a FAU (faujasite) framework and a Si/Al value near 2.6; thus, there is no discernible difference in the framework topology, framework chemical compositions, effective aperture size, and channel structure between the zeolite samples. Therefore, the distinctive behavior in the adsorption of $CO_2$ with a character as a weak Lewis acid is associated with the site basicity of the zeolites, and the interaction potentials of the cations. Different trend was shown for a CO adsorption due to weaker quadrupole interactions. Adsorption of $CO_2$ and CO on samples of CaY with 0.012 to 5.23% Ca disclosed a significant dependence on the Ca loading. The $CO_2$ adsorption increased when the cation exists up to ca. 0.05%, while it decreased at higher Ca amounts. However, values for both W and S could greatly increase as the bare zeolite is enriched by $Ca^{2+}$ ions. The 5.23% CaY had $W=2.37mmol\;g^{-1}$ and S = 4.37, and the former value was comparable to a benchmark reported in the literature.

키워드

참고문헌

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