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Received December 18, 2020
Accepted January 25, 2021
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Ni/SiO2-Al2O3 복합 산화물 촉매 상에서 에탄올의 직접 아민화 반응에 의한 선택적 아세토니트릴 합성
Selective Synthesis of Acetonitrile via Direct Amination of Ethanol Over Ni/SiO2-Al2O3 Mixed Oxide Catalysts
충북대학교 화학공학과, 28644 충청북도 청주시 서원구 충대로 1
Department of Chemical Engineering, Chungbuk National University, 1 Chungdaero, Seowongu, Cheongju, Chungbuk, 28644, Korea
chshin@chungbuk.ac.kr
Korean Chemical Engineering Research, May 2021, 59(2), 281-295(15), 10.9713/kcer.2021.59.2.281 Epub 3 May 2021
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Abstract
Si/(Si + Al) 몰비를 30 몰%까지 변화시켜 제조한 SiO2-Al2O3 복합 산화물(SA) 상에 니켈을 함침법으로 제조한 촉매 상에서 에탄올의 아민화반응에 미치는 영향을 연구하였다. 제조된 촉매의 물리·화학적 특성을 알아보기 위하여 X-선회절분석(XRD), N2 흡착분석, 이소프로판올 승온탈착(IPA-TPD), 에탄올 승온탈착(EtOH-TPD), 수소 승온환원(H2-TPR), H2 화학흡착, 투과전자현미경(TEM) 분석을 수행하였다. SA 복합 산화물 상에서 Si/(Si + Al) = 30 몰%가 될 때까지 지속적으로 산점이 증가하였다. 담지된 Ni 금속의 분산도, 비표면적 및 산 특성 등이 촉매 반응활성에 복합적으로 영향을 미쳤다. 산점 증가와 니켈 산화물의 낮은 환원 온도는 아세토니트릴 생성에 유리하게 작용하는 것으로 사료된다. 에탄올의 전환율 측면에서는 10 wt% Ni이 담지된 Si/(Si +Al) = 10 몰% 촉매가 가장 높은 전환율을 보였으며 이를 기준으로 화산형 형태를 나타냈고, Ni 금속 분산도와 경향이 일치했다.
In this study, the direct amination of ethanol was performed over impregnated Ni on SiO2-Al2O3 mixed oxide catalysts prepared by varying Si/(Si + Al) molar ratio to 30 mol%. To characterize the physico-chemical properties of the catalysts used, X-ray diffraction (XRD), N2-physisorption, temperature-programmed desorption of iso-propyl alcohol (IPA-TPD), temperature-programmed desorption of ethanol (EtOH-TPD), temperature-programmed reduction with H2 (H2-TPR), H2-chemisorption and transmission electron microscopy (TEM) were used. The acidic property was continuously increased until Si/(Si + Al) = 30 mol% in SiO2-Al2O3 mixed oxides used. The dispersion of Ni metal and surface area, acid characteristics of the supported Ni catalyst have a complex effect on the catalytic reaction activity. The low reduction temperature of nickel oxide and acidic properties were beneficial to the formation of acetonitrile. In terms of conversion of ethanol, Ni/SiO2-Al2O3 catalyst with a molar ratio of 10 mol% Si/(Si+Al) showed the highest activity and a volcanic curve based on it. The tendency of results were consistent in the metal dispersion and catalytic activity.
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Chen BS, Falconer JL, J. Catal., 147(1), 72 (1994)
Li CP, Chen YW, Thermochim. Acta, 256(2), 457 (1995)
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Card RJ, Schmitt JL, J. Org. Chem., 46(4), 754 (1981)
Jeong YS, An SH, Shin CH, Korean J. Chem. Eng., 36(7), 1051 (2019)
