Catalytic Oxidation of Aromatic Compounds over Spent Ni-Mo and Spent Co-Mo based Catalysts: Effect of Physico-chemical Pretreatments

Transition metal based spent catalysts (Ni-Mo and Co-Mo), which were scrapped from the petrochemical industry, were reused for the removal processes of volatile organic compounds (VOCs). Especially the optimum regeneration procedures were determined using the removal efficiency of VOCs. In this work, the spent Ni-Mo and spent Co-Mo catalysts were pretreated with different physic-chemical treatment procedure: 1) acid aqueous solution, 2) alkali solution, 3) chemical agent and 4) steam. The various characterization methods of spent and its regenerated catalysts were performed using nitrogen adsorption, X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive spectrometry (EDS). It was found that all spent catalysts were found to be potentially applicable catalysts for catalytic oxidation of benzene. The experimental results also indicated that among the employed physico-chemical pretreatment methods, the oxalic acid aqueous (0.1 N, $C_2H_2O_4$) pretreatment appeared to be the most efficient in increasing the catalytic activity, although the catalytic activity of spent Ni-Mo and spent Co-Mo catalysts in the oxidation of benzene were greatly dependent on the pretreatment conditions. The pretreated spent catalysts at optimum condition could be also applied for removing other aromatic compounds (Toluene/Xylene).

폐 Ni-Mo 및 폐 Co-Mo계 촉매상에서 방향족 화합물의 촉매산화: 물리화학적 전처리 효과

석유화학공업에서 발생한 2종류의 금속산화물계열 폐 촉매(Ni-Mo, Co-Mo)를 휘발성유기화합물(VOCs) 제거를 위한 촉매 연소 공정에 재이용하였다. 특히 폐 촉매의 재생방법에 따른 VOCs 제거효과를 검토하여 최적의 재생 조건을 살펴보았다. 폐 촉매는 1) 산 수용액, 2) 알칼리 수용액, 3) 세정액 및 4) 스팀(steam) 등을 이용하여 재생 처리하였고, 재생 처리 전-후의 이들 촉매의 물리화학적 특성 변화는 질소흡착등온선, X-선 회절분석기(XRD) 및 에너지분산 X-선 분광기(EDS)를 갖춘 주사현미경(SEM)으로 조사하였다. Benzene 산화반응 실험 결과 폐 촉매는 VOCs 연소 촉매로 재이용 가능성이 높았다. 그리고 이들 폐 촉매의 활성은 전처리 조건에 따라 다르게 나타났으나, 두 폐 촉매 모두 0.1 N $C_2H_2O_4$ 용액으로 처리할 때 활성이 가장 좋았다. 또한 최적 조건(0.1 N $C_2H_2O_4$)에서 처리한 촉매는 다른 방향족 화합물(Toluene/Xylene) 처리에도 충분히 적용할 수 있었다.