공업화학 (Applied Chemistry for Engineering)

  • 제28권6호
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  • Pages.720-725
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  • 2017
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  • 1225-0112(pISSN)
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  • 2288-4505(eISSN)
한국공업화학회 (The Korean Society of Industrial and Engineering Chemistry)
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M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm) 촉매상에서 합성가스 제조를 위한 메탄의 부분산화반응

Partial Oxidation of Methane to Syngas over M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm) Catalysts

  • 투고 : 2017.09.18
  • 심사 : 2017.11.06
  • 발행 : 2017.12.10
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초록

메탄의 부분 산화반응으로부터 합성가스를 제조하기 위해 M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm)를 제조하였다. 촉매는 BET, TEM, XPS의 기기를 사용하여 특성화하였다. M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm)의 BET 비표면적, 평균 기공 크기는 각각 538.8, 504.3, $447.3m^2/g$과 6.4, 6.8, 7.1 nm이었다. SBA-15 담체의 TEM 이미지는 중기공성 육방정계 구조를 보여주었고, Ce(10)-Ni(5)/SBA-15 촉매는 Ni와 Ce의 금속 입자가 SBA-15 담체의 구속효과에 의해서 담체 표면상에 균일하게 분포하고 있었다. XPS 분석으로 촉매 표면상에 격자산소($O^{2-}$, $O^-$)와 $Ce^{4+}$과 $Ce^{3+}$의 두개의 산화상태가 존재함을 알 수 있었다. 촉매상에서 메탄의 부분 산화 반응으로부터 합성가스의 수율은 1 atm, 973 K, $CH_4/O_2=2$, $GHSV=1.08{\times}10^5mL/g_{cat.}{\cdot}h$에서 52.9% $H_2$와 21.7% CO이었으며, 75 h의 반응에서도 이 값을 일정하게 유지하였다. M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm)촉매는 합성가스 수율이 같은 경향을 보여주었다. 이러한 결과는 조촉매인 Ce, Nd, Sm의 Redox 반응이 촉매의 수율과 안정성을 향상시킨다는 것을 보여주었다.

M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm) catalysts were prepared for the partial oxidation of methane (POM) to syngas. The catalysts were characterized by BET, TEM, and XPS. The BET-specific surface area and average pore size for M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm) were 538.8, 504.3, and $447.3m^2/g$ and 6.4, 6.8, and 7.1 nm, respectively. TEM results showed that the mesoporous hexagonol structure was formed for SBA-15, while the homogeneous dispersion of Ni and Ce particles on the surface was formed for Ce(10)-Ni(5)/SBA-15 caused by the confinment effect of SBA-15. XPS data confirmed that $Ce^{4+}$ and $Ce^{3+}$ on the surface catalyst have two oxidation states due to the lattice oxygen species ($O^{2-}$, $O^-$). The yields of POM to syngas over Ce(10)-Ni(5)/SBA-15 were 52.9% $H_2$ and 21.7% CO at 1 atm, 973 K, $CH_4/O_2=2$, $GHSV=1.08{\times}10^5mL/g_{cat.}{\cdot}h$, and these values were kept constant even after 75 h on streams. The same tendency of syngas yields was observed for M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm). These results confirm that the redox reaction of promoters including Ce, Nd, and Sm enhanced the stability and yield of catalysts.

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