지구 온난화, 석유고갈, 환경오염에 대한 해결 방안으로 수송부분에서 국제적으로 바이오연 료에 관한 연구가 활발하게 이루어지고 있다. 그 중 바이오디젤은 석유계 디젤과 비교해 이산화탄소 및 대기오염 물질 배출이 적고 세탄가가 높은 장점을 가지고 있다. 현재 국내 바이오디젤 수요는 지속적으로 증가하고 있으나 원료부족으로 인해 수입의존도가 커지고 있는 상황이다. 이러한 문제를 해결하기 위해 본 연구는 현재 사용되지 않는 음폐유(약 33 % 유리지방 산 함유)를 Amberlyst-15 촉매가 이용한 에스테르화 반응을 통해 바이오디젤 원료로서 활용가능성을 확인 하였다. 다양한 반응 조건의 영향을 조사하기 위한 실험을 수행한 결과 반응온도 383 K에서 97.62 %의 전환 율을 얻었으며, 반응속도는 353 K에서 373 K로 증가 할 때 최대 1.99 배까지 상승하였다. 또한 동역학 적 결과를 이용하여 29.75 kJ/mol의 활성화 에너지를 확인하여 선행연구에서 연구된 타 고체촉매에 비 해 에스테르화반응에 Amberlyst-15 더 적합함을 확인하였다. 그리고 메탄올 몰 비가 증가함에 따라 최 대 91.43 %의 반응 전환율을 확인하였고, 촉매량 영향의 경우 0 wt%에서 20 wt%까지 증가시킨 결과 반응 전환율이 43.78 %에서 94.62 %까지, 초기 반응 속도는 1.1∼1.4 배로 상승하는 것을 확인하였 다. 교반속도의 경우 100∼900 rpm의 조건에 따라 실험을 수행하였으나 반응 전환율에는 큰 영향을 주 지 않음을 확인하였고 반응 시간에 따른 영향의 경우 240 분 까지 산가 감소를 보이다가 300 분이 지 나면서부터 산가가 상승하는 결과를 가져왔다. 그리고 위 실험들을 통해 도출된 최적 조건을 적용하여 음폐유 에스테르화 반응에 적용하였고 그 결과 반응시간 60 분에서 음폐유와 모사 폐유지간의 13 %의 반응 전환율 차이를 보였으나 최종 240 분 반응 전환율은 모사 폐유지 98.12 %, 음폐유는 97.62 %로 거의 유사한 결과를 얻었다.

The esterification of the reactants of Jatropha oil and methanol added by propyleneglycol was done using p-TSA catalyst. And then the emulsification of triglyceride and methanol was conduced by 1.0vol% GMS. The emulsified reactants were transesterified at 65℃ using TMAH and mixed catalyst (50wt%-TMAH+50wt%-NaOH) respectively. The esterification conversion at the 1:8 molar ratio of free fatty acid to methanol using 8.0wt% p-TSA was 94.7% within 80min. The overall conversion at the 1:8 molar ratio of mixed fat(50wt% Beef Tallow) to methanol and 65℃ using mixed catalyst was 95.4% The cloud point of Biodiesel decreased with the addition of petroleum diesel.

The esterification of free fatty acid in Jatropha oil added by propylene glycol using p-TSA catalyst was done, and then the transesterification of Jatropha oil added by 1.0vol% GMS as an emulsifier using TMAH, and mixed catalyst(60wt%-TMAH+ 40wt%-KOH) respectively was followed at 60℃. The esterification conversion at the 1:8 molar ratio of free fatty acid to methanol using 8.0wt% p-TSA was 94.7% within 60min. The overall conversion at the 1:8 molar ratio of Jatropha oil to methanol and 60℃ using mixed catalyst was 95.4%. The kinematic viscosity of Biodiesel using TMAH and mixed catalyst in 24h met the ASTM D-6751 above 30℃, and showed a little more than its criterion.

The esterification of palmitic acid in rapeseed oil and methanol emulsified by propylene glycol with PTSA(p-toluene sulfonic acid) was followed by the transesterification of rapeseed oil into biodiesel with 1(w/v)% GMS(glycerol monostearate) as an emulsifier using TMAH(tetramethyl ammonium hydroxide) catalysts at 60℃. The former reaction was optimized at the 1:20 of molar ratio of oil to methanol and 5wt% PTSA, and the latter was optimized at the 1:8 of molar ratio of oil to methanol and 0.8wt% TMAH. The overall conversion into biodiesel was 98% after 60min of reaction time at the 1:8 of molar ratio, 0.8wt% TMAH and 60℃. TMAH was a good catalyst to control the viscosity of biodiesel mixture.

고분자전해질형 연료전지에서 촉매의 활성을 증가시키기 위하여 기존에 사용되고 있는 백금과 전이금속인 chromium, nickel과의 합금을 제조하였다. XRD를 이용하여 합금의 구조가 33˚에서 superlattice line을 가지고 있는 것으로 보아 face centered cubic 구조를 가진 ordered alloy로 이루어졌다는 것을 알 수 있었다. 열처리 온도가 증가할수록 합금의 입자 크기는 증가하였으며, 결정 격자 상수는 감소하였다. 전지성능테스트, cyclic voltammogram 등을 통하여 mass activity, specific activity, Tafel slope, 개회로 전압을 측정한 결과, 합금촉매의 활성이 순수한 백금촉매보다 크게 향상되었음을 알 수 있었다.

A synthesis of Dimer acid was studied from a tall oil fatty acid. Catalytic activity measured as reactant conversion in a autoclave reactor increase in accordance with the acidity. The optimization of process conditions were tested by an experimental design method. Optimization synthetic conditions of dimer acid and were reaction of tall oil fatty acid during 2 hour at 250℃, used of 7.3 wt% active clay and 1.2~1.4wt% water, and found reation pressure 8~9Kg/cm2. The maximum conversion rate was researched 74~76%.

Conventional alkaline catalytic procedure, including sodium methoxide-methanol N, N, N', N'-tetramethyl guanidine-methanol, and acid-catalytic methods of BF3-methanol and HCI-methanol, have been applied for preparing methyl esters from the triacylglycerols of Trichosanthes kirilowiil seeds containing conjugated trienoic acids. The alkaline catalytic methods produce the methyl esters quantitatively without isomerization of the conjugated trienoic acids, but the acid-catalytic ones destroy almost the molecules of conjugated trienoic acids during transesterification of the triacylglycerols although the molar ratios of monoenoic and dienoic acids (non-conjugated) to saturated acids are in good agreement with those obtained from the alkaline methods.

This study investigated the optimal sequential hydrolysis conditions by comparing with reducing sugar yield ofsequential hydrolysis of Laminaria japonica processing residue. After acid-catalyzed hydrothermal hydrolysis, sequentialenzymatic hydrolysis was performed with single enzymes such as Celluclast® 1.5L, Saczyme, and Alginate Lyase, andtheir mixture. As a result, the yield of reducing sugar by sequential hydrolysis with the mixed enzymes was the highest,but there would be an economical problem with excessive enzyme loading. Therefore, considering the reducing sugaryield and economics, it is thought that hydrolysis by the mixed enzymes has no advantage, thus, using the Celluclast®1.5L in the sequential hydrolysis was practically more appropriate. The optimal sequential hydrolysis conditions ofLaminaria japonica processing residue were determined to be 8% v/w of enzyme injection, 42.6oC of reaction temperature,pH 4.1, and 26 hours of reaction time after acid-catalyzed hydrothermal hydrolysis (0.108 N-HCl, 144oC of reactiontemperature, and 22 minute of reaction time).

To investigate optimal condition of acid-catalyzed hydrothermal hydrolysis of Laminaria japonica, the main constituentsof Laminaria japonica such as cellulose, alginic acid and mannitol were hydrolyzed using acid-catalyzed hydrothermalreaction. Then, we proposed the re-designed experimental method including the predicted optimal conditions of the mainconstituents and performed acid-catalyzed hydrothermal hydrolysis of Laminaria japonica. The coefficients ofdetermination (R2) of Y5 (yield of reducing sugar from Laminaria japonica) were 0.877. P values of Y5 were 0.002,indicating significance, within 1% (p<0.01). The optimum reaction condition for acid-catalyzed hydrothermal hydrolysisof Laminaria japonica determined by the response surface methodology is 143.65oC of reaction temperature, 22min ofreaction time, hydrochloric acid concentration 0.108N, resulting in a production rate of 115.62mg/g-Laminaria japonica.

Acid hydrolysis of cellulose using hydrothermal reaction was conducted to maximize reducing sugar concentration and the response surface methodology (RSM) was applied to study the effects of independent variables, such as reaction temperature (116 ~ 184oC), reaction time (12 ~ 28 min) and hydrochloric acid concentration (HCl, 0.0159 ~ 0.1841 N) on reducing sugar concentration and production yield from the cellulose. With the optimum conditions of the acid-catalyzed hydrothermal hydrolysis, the reducing sugar (RS) was obtained as 369.14 mg-RS/g-cellulose in 172.77oC of the reaction temperature, 28.41 min of the reaction time and 0.067 N of the hydrochloric acid concentration. The glucose (Glu) was obtained as 281.94 mg-Glu/g-cellulose in 154.70oC of the reaction temperature, 11.59 min of the reaction time and 0.184 N of the hydrochloric acid concentration.

Characteristics of the transesterification reaction between triglycerides in soy bean oil and methanol were investigated in the presence of acid catalysts. such as sulfuric acid and PTS (p-toluene sulfonic acid). Concentrations of diglyceride and monoglyceride which were intermediates in the reaction mixtures, were far below 10% of triglyceride under any reaction conditions. Thus, conversion of the reaction could be determined from the concentration of triglyceride. Dried PTS had more superior catalytic power than sulfuric acid for transesterification reaction between soy bean oil and methanol. When transesterification reaction of soy bean oil was catalyzed by 1 wt% of PTS at methanol stoichiometric mole ratio of 2 and 65℃, final conversion reached 95% within 48 hours. If FAME (fatty acid methyl ester) was added into reaction mixture of soy bean oil, methanol and PTS catalyst, it converted reaction mixture into homogeneous phase, and substantially increased reaction rate. When reaction mixture was freely boiling which had equal volumetric amount of FAME to soy bean oil, methanol stoichiometric mole ratio of 2 and 1 wt% of PTS, final conversion achieved value of 94% and temperature approached to 110℃ within 2 hours.