초록 ▼

바이오항공유 제조를 위한 기존 상용공정과 차별화된 통합형 바이오항공유 제조기술을 다음과 같이 개발하였음. 대표적인 비식용유지 중의 하나인 자트로파유를 대상으로, (1) 고활성 및 장수명을 갖는 비수첨 탈산소 반응용 W/Pt/TiO2 촉매 및 최적 운전 조건 확보 (탈산소도 99% 이상), (2) 수첨업그레이딩을 위한 고성능의 PtMg/HY 촉매 및 최적 운전 조건 확보 (이성화율 73% 이상), (3) 자트로파 유의 hydrolysis의 부산물인 글리세롤의 스팀리포밍을 통한 바이오수소 생산용 Ni-Mg-Al계 촉매 개발 (수소 수율

바이오항공유 제조를 위한 기존 상용공정과 차별화된 통합형 바이오항공유 제조기술을 다음과 같이 개발하였음. 대표적인 비식용유지 중의 하나인 자트로파유를 대상으로, (1) 고활성 및 장수명을 갖는 비수첨 탈산소 반응용 W/Pt/TiO2 촉매 및 최적 운전 조건 확보 (탈산소도 99% 이상), (2) 수첨업그레이딩을 위한 고성능의 PtMg/HY 촉매 및 최적 운전 조건 확보 (이성화율 73% 이상), (3) 자트로파 유의 hydrolysis의 부산물인 글리세롤의 스팀리포밍을 통한 바이오수소 생산용 Ni-Mg-Al계 촉매 개발 (수소 수율 89.5 %), (4) 자트로파 부산물의 열분해유로부터 방향족 화합물 생산을 위한 GaMg/ZSM-5 촉매 (방향족 함량 40% 이상)를 개발하였음. 수소소비량을 최소화한 벤취급 바이오항공유 제조 공정을 통해(항공유분 수율 55%), 시제품을 20리터 생산하였으며 ASTM 규격시험을 수행한 결과 8개 항목에 대해 합격하였음.

( 출처: 보고서 요약서 3p )

Abstract ▼

Ⅳ. Results
- Crude Jatropha oil, one of several non-edible oils, was used for production of bio-jet fuel. Pretreatment including hydrolysis and deoxygenation reaction was essential step to produce bio-jet fuel. Based on the results of the batch test for the selection of optimal catalyst, W/Pt/TiO

Ⅳ. Results
- Crude Jatropha oil, one of several non-edible oils, was used for production of bio-jet fuel. Pretreatment including hydrolysis and deoxygenation reaction was essential step to produce bio-jet fuel. Based on the results of the batch test for the selection of optimal catalyst, W/Pt/TiO2 catalyst was the most effective catalyst in deoxygnation reaction of oils, triglyceride and free-fatty acids, and also in stability with no hydrogen supply conditions. In lab-scale fixed bed reaction system using crude Jatropha oil and bead-type W/Pt/TiO2 catalyst, the degree of deoxygenation was above 99 % at the initial stage and maintained the degree of deoxygenation of above 90% during more than 25 h, which is about 3 times higher than that of Pd/C catalyst (reference catalyst). In lab-scale fixed bed reaction system, the liquid yield and the degree of deoxygenation were maintained about 92% and above 87%, respectively, during more than 24 h.
- In order to produce directly bio-jet fuel, consisting of isomer and aromatic hydrocarbons as well as normal hydrocarbon, via a singl-step reaction without hydrogen supply, modified zeolite catalysts were developed. Hbeta zeolite showed the best performance for decarboxylation of stearic acid among several tested zeolites.
Mesopore development, acid site modification with phosphoric acid, NaOH, and NH₄F, and Pd impregnation made the improvement of catalyst performance. From these process, we got the optimum catalyst of decarboxylation rate over 95%. This catalyst also applied in flow reactor for stearic acid decarboxylation, and showed higher decarboxylation rate.
- In order to convert bio-oil into jet fuel, catalysts for hydrograding reaction were investigated. HY zeolite was mixed with pseudoboehmite to adjust the acid characteristics of the support for hydroupgrading catalyst. Acid characteristic of KIT-6 was adjusted through alumination. Pt was used as the active component of the catalyst. In addition, Mg was used as a promoter to improve the dispersion of Pt. PtMg/HY, PtMg/[HY+Pseudoboehmite] and PtMg/Al-KIT-6 catalysts were selected as the optimized catalysts capable of increasing the amount of branched hydrocarbon of the bio-oil derived from jatropha oil and palm oil. Consequently, the isomerization selectivity reached over 73% over the PtMg/HY catalyst in hydroupgrading of the bio-oil derived from Jatropha oil.
- In lab-scale fixed bed reaction system, one-pot hydrotreating reaction of waste oil and Jatropha oil was carried out with Pt/HY zeolite granule-type catalysts. Yield of jet fuel was 61.6% and isomerization yield in the jet fuel range was 62% for Jatropha oil. In bench-scale reaction system, the optimum isomerization yield of 74% was obtained in two-step reaction, consisting of 1^st hydroteating with sulfide NiMo/ZrO2-grannul type catalyst and 2^nd upgrading reaction with PtMg/HY-granule-type catalyst.
- Conversion and aromatic selectivity from catalytic upgrading of furfural as a representative model compound was influenced by zeolite type, catalyst particle size and amount, metal type impregnated on zeolite and reaction temperature. Moreover,the reactivity on reactant type was in the order; lignocelluloic bio-oil > Jatropha waste bio-oil > furfural > furan. Deactivation degree of metal impregnated on pellet type ZSM-5 catalyst, in which ZSM-5 catalyst showed best performance of aromatic selectivity among zeolite catalysts, from catalytic upgrading of lignocellulic bio-oil was appeared as the following order; pure ZSM-5 > Ga/ZSM-5 > GaMg/ZSM-5. In conclusion, 7wt%Ga7wt%Mg/ZSM-5 catalyst with repetitive decoking treatment used by catalytic upgrading of Jatropha waste bio-oil, as a long run test, showed about 40% aromatic selectivity in the bio-oil produced during the reaction time of 50 hours or over. Also, the bio-oil produced had heating value of 7,500 kcal/kg (higher) and 6,900 kcal/kg (lower), respectively.
- Hydrogen production through steam reforming by using aqueous glycerol derived from Jatropha oil hydrolysis was carried out with granule-type Ni-based catalysts.
In a fixed 12 wt% of Ni and Al content, Ni(12%)-Mg(0-3.0%)-Al granule type catalysts were prepared using different Mg contents. Hydrogen yield of 89.5% was obtained over Ni(12)-Mg(0.2)-Al granule type catalysts at 500 ℃ and glycerol=0.15cc/min.
- Bio-jet fuel (20 L), as a test product, was prepared via sequence reactions in two-step bench-scale reaction system and bench-scale glass packed distillation tower(jet fuel yield=55%). The bio-jet fuel passed 8 contents based on the results of ASTM specification analysis.

( 출처: SUMMARY 8p )

목차 Contents

• 표지 ... 1
• 제출문 ... 2
• 보고서 요약서 ... 3
• 요약문 ... 4
• SUMMARY ... 7
• CONTENTS ... 12
• 목차 ... 13
• 제 1장 연구과제의 개요 ... 14
• 제 1절. 연구의 필요성 ... 14
• 제 2절. 연구의 목적 및 범위 ... 19
• 제 2장 국내외 기술개발 현황 ... 23
• 제 1절. 항공유분야의 국내 기술개발 현황 ... 23
• 제 2절. 항공유분야의 국외 기술개발 현황 ... 25
• 제 3절. 세부기술별 국내/외 기술동향 ... 35
• 제 4절. 바이오항공유 특허 출원 동향 ... 50
• 제 3장 연구수행 내용 및 결과 ... 55
• 제 1절. 연차별 연구내용 및 방법 요약 ... 55
• 제 2절. 연차별 연구결과 요약 ... 58
• 제 3절. 1차년도 연구수행 결과 ... 64
• 제 4절. 2차년도 연구수행 결과 ... 95
• 제 5절. 3차년도 연구수행 결과 ... 146
• 제 4장 목표달성도 및 관련분야에의 기여도 ... 256
• 제 1절. 목표달성도 ... 256
• 제 2절. 관련분야에의 기여도 ... 257
• 제 5장 연구결과의 활용계획 ... 258
• 제 1절. 연구결과의 활용계획 ... 258
• 제 6장 연구과정에서 수집한 해외과학기술정보 ... 259
• 제 1절. 바이오항공유 세계 시장 동향 ... 259
• 제 2절. 바이오항공유 세계 특허 동향 ... 261
• 제 3절. 바이오연료 제조 촉매 설계 ... 262
• 제 7장 참고문헌 ... 265
• 부록. 연구성과 집계(최종보고서 부록) ... 271
• 끝페이지 ... 277