Hydrogenation of Methyl Dodecanoate Using Copper Chromite

분산액에서의 Copper Chromite 합성 및 Methyl Dodecanoate의 수소화반응

The hydrogenation reaction of methyl dodecanoate for the synthesis of 1-dodecanol has been carried out in the presence of a copper chromite catalyst. The catalysts were synthesized by ceramic method, co-precipitation, and improved co-precipitation method and the particles were characterized by SEM and XRD. Also, the products of the reaction were assigned by GC, GC/MSD and NMR. The particles synthesized by each method showed (1) a spherical shape with the size of 3.2 to $7.0{\mu}m$, (2) an agglomerated spherical shape with the size of 50 to 500 nm and (3) a spherical shape with smaller particle size, respectively. Especially, in order to control the size of particles, the particles were synthesized in various dispersant solutions as Span 80, polyacrylate, and polyethyleneglycols (PEGs). The particles synthesized in PEG (Mw = 4000) solution showed the smallest particle size of 30 to 50 nm and the regularity of the particle size distribution. Our experimental results elucidated that the activity of catalyst for hydrogenation increases with decreasing the size of catalyst particle. The highest yield of dodecanol in the hydrogenation reaction was 95.5% when copper chromite synthesized in the PEG solution was used as a catalyst in the optimized reaction condition.

Dodecanol 합성을 위한 methyl dodecanoate의 수소화반응을 위하여 copper chromite를 세라믹법, 공침법 및 개량된 공침법으로 합성하였다. 입자의 형상은 SEM 및 XRD로 확인하였으며 수소화 반응후 얻어진 생성물은 GC, GC/MSD 및 NMR로 분석하였다. 합성된 입자는 (1) 3.2에서 $7.0{\mu}m$ 크기의 구형형태(세라믹법), (2) 50에서 500 nm 크기의 구형이 혼재한 판형태(공침법) 및 (3) 작고 균일한 구형형태(개량된 공침법)를 보였다. 입자의 크기를 제어하기 위하여 PEG, Span 80 및 polyacrylate등 다양한 분산제 용액에서 copper chromite를 합성하였다. PEG (Mw = 4000) 수용액에서 합성한 입자가 30~50 nm 크기로 가장 작고 균일하였으며, $280^{\circ}C$ 및 100 atm에서 촉매의 반응성을 테스트한 결과, dodecanol의 수율은 79.9%로 얻어졌다. 수소화반응에서 촉매의 반응성은 촉매의 크기가 작고 균일할수록 높아지는 경향을 보였다. 최적화된 반응조건인 $280^{\circ}C$ 및 240 atm에서 dodecanol의 수율은 95.5%였다.