한국물환경학회지 (Journal of Korean Society on Water Environment)

  • 제34권6호
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  • Pages.621-631
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  • 2018
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  • 2289-0971(pISSN)
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  • 2289-098X(eISSN)
한국물환경학회 (Korean Society on Water Environment)
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팔라디움과 인디움을 담지한 Al 층간가교 몬모릴로나이트 촉매의 수중 질산성질소 환원 특성

The Reduction Properties of Nitrate in Water with Palladium and Indium on Aluminum Pillared Montmorillonite Catalyst

  • 정상조 (육군사관학교 토목.환경학과)
  • Jeong, Sangjo (Department of Civil Engineering and Environmental Science, Korea Military Academy)
  • 투고 : 2018.08.27
  • 심사 : 2018.11.12
  • 발행 : 2018.11.30
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초록

In this study, catalyst was made through incipient wetness method using palladium (Pd) as noble metal, indium (In) as secondary metal, and montmorillonite (MK10) and Al pillared montmorillonite (Al-MK10) as supporters. The nitrate reduction rate of the catalysts was measured by batch experiments where H2 gas was used as reducing agent and formic acid as pH controller. Transmission electron microscopy (TEM) equipped with energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were all used to determine the elemental distribution of Pd, In, Al, and Si on catalysts. It was observed that Al pillaring increased the Al/Si elemental composition ratio and point of zero charge of MK10, but decreased its BET specific surface area and pore volume. The nitrate reduction rate of Al-MK10 Pd/In was 2.0 ~ 2.5 times higher than that of MK10 Pd/In using artificial groundwater (GW) in ambient temperature and pressure. Nitrate reduction rates in GW were 1.2 ~ 1.7 times lower than those in distilled deionized water (DDW). Nitrate reduction rates in acidic conditions were higher than those in neutral condition in both GW and DDW. The amount of produced NH3-N over degraded NO3- at acid conditions was lower than that of neutral condition. Even though the leaching of Pd after reaction was measured in DDW it was not detected when both Al-MK10 Pd/In and MK10 Pd/In were used in GW. The modification of montmorillonite as a supporter significantly increased the reductive catalytic activities of nitrates. However, the ratio of producing ammonia by-products to degraded nitrates in ambient temperature and pressure was similar.

키워드

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Fig. 1. XRD patterns of (a) montmorillonite K-10, (b) 5%Pd-0.65%In on montmorillonite K-10, (c) aluminum pillared montmorillonite K-10, and (d) 5%Pd-0.65%In on aluminum pillared montmorillonite K-10.

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Fig. 2. Nitrogen sorption or desorption and average pore diameter of MK10, MK10 Pd/In, Al-MK10, and Al-MK10 Pd/In.

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Fig. 3. XPS signals of (a) Pd3d (b) In3d of MK10 Pd/In and (c) Pd3d (d) In3d of Al-MK10 Pd/In.

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Fig. 4. Point of zero charge (PZC) of MK10 Pd/In and Al-MK10 Pd/In.

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Fig. 5. Fourier transformation infrared spectroscopy of (a) montmorillonite K-10, (b) 5%Pd-0.65%In on montmorillonite K-10, (c) aluminum pillared montmorillonite K-10, and (d) 5%Pd-0.65%In on aluminum pillared montmorillonite K-10.

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Fig. 6. Reduction rates of nitrates with (a) MK10 Pd/In in distilled deionized water (DDW), (b) MK10 Pd/In in artificial groundwater (GW), (c) Al-MK10 Pd/In in DDW, and (d) Al-MK10 Pd/In in GW with different pH conditions.

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Fig. 7. Reduction rates of nitrates with (a) MK10 Pd/In and (b) Al-MK10 Pd/In in different pH conditions.

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Fig. 8. Ammonium produced during reduction of nitrates with (a) MK10 Pd/In and (b) Al-MK10 Pd/In in different pH conditions.

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Fig. 9. The ratios of ammonium produced to degraded nitrates with (a) MK10 Pd/In and (b) Al-MK10 Pd/In in different pH conditions.

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Fig. 10. The concentration of palladium in water after nitrate reduction using distilled deionized water.

Table 1. The experimental conditions for the reduction of nitrate in aqueous solution

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Table 2. BET specific surface area and average pore diameter of samples

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Table 3. The relative compositions of major elements (e.g., Si, Al, Pd, In) of MK10 Pd/In and Al-MK10 Pd/In measured by EDX and XPS

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