[논문]루테늄 담지 활성탄-마그네시아 혼합 촉매 상에서 알긴산의 저분자화 연구

양승도; 김형주; 박재현; 김도희

doi:10.7464/ksct.2022.28.3.232

루테늄 담지 활성탄-마그네시아 혼합 촉매 상에서 알긴산의 저분자화 연구
Ru-based Activated Carbon-MgO Mixed Catalyst for Depolymerization of Alginic Acid 원문보기

청정기술 = Clean technology, v.28 no.3, 2022년, pp.232 - 237

양승도 (서울대학교 화학생물공학부) , 김형주 (서울대학교 화학생물공학부) , 박재현 (서울대학교 화학생물공학부) , 김도희 (서울대학교 화학생물공학부)

초록
AI-Helper

해조류 바이오매스 중 갈조류의 주요 구성 성분인 알긴산은 다양한 산업에서 널리 사용되어지며, 촉매적 저분자화를 통해 당, 당알코올, 퓨란계, 그리고 유기산과 같은 고부가가치 화합물로 전환할 수 있다. 본 연구에서는 루테늄 담지 활성탄과 마그네시아를 혼합하여 알긴산 저분자화 반응에 적용하고자 하였다. 이러한 불균일계 촉매 시스템은 생성물에 대한 분리가 용이하고 정제 과정의 간소화가 장점으로 작용한다. 반응 결과, 탄소 수 5개 이하의 저분자량 알코올 및 유기산이 생성되었으며, 최적의 반응 조건 탐색을 통해 최종적으로 1 wt% 알긴산 수용액 30 mL, 루테늄 담지 활성탄 100 mg, 마그네시아 100 mg, 반응 온도 210 ℃, 반응 시간 1 h의 반응 조건에서 29.8%의 알코올에 대한 탄소 수율과 43.8%의 알코올 포함 액상 생성물에 대한 총 탄소 수율을 확보하였다.

Abstract ▼ AI-Helper

Biorefineries, in which renewable resources are utilized, are an eco-friendly alternative based on biomass feedstocks. Alginic acid, a major component of brown algae, which is a type of marine biomass, is widely used in various industries and can be converted into value-added chemicals such as sugars, sugar alcohols, furans, and organic acids via catalytic hydrothermal decomposition under certain conditions. In this study, ruthenium-supported activated carbon and magnesium oxide were mixed and applied to the depolymerization of alginic acid in a batch reactor. The addition of magnesium oxide as a basic promoter had a strong influence on product distribution. In this heterogeneous catalytic system, the separation and purification processes are also simplified. After the reaction, low molecular weight alcohols and organic acids with 5 or fewer carbons were produced. Specifically, under the optimal reaction conditions of 30 mL of 1 wt% alginic acid aqueous solution, 100 mg of ruthenium-supported activated carbon, 100 mg of magnesium oxide, 210 ℃ of reaction temperature, and 1 h of reaction time, total carbon yields of 29.8% for alcohols and 43.8% for a liquid product were obtained. Hence, it is suggested that this catalytic system results in the enhanced hydrogenolysis of alginic acid to value-added chemicals.

주제어

표/그림 (10)

그림 Figure 1. Various value-added chemicals from alginic acid.
그림 Figure 2. Schematic diagram of batch reactor system. (PI, pressure indicator; TI, temperature indicator; SI, speed indicator; R, reaction vessel/autoclave; T, thermocouple; H, electric heater; RD, rupture disc; GS, gas sparger; CY, gas cylinder)
그림 Figure 3. Carbon yields of products obtained from hydrogenolysis of alginic acid over Ru/C mixed with various metal oxides (Reaction conditions: 1 wt% of alginic acid in 30 mL of water, 100 mg of Ru/C, 100 mg of metal oxide, 210 ℃, 2 h, 50 bar of hydrogen, 1000 rpm stirring). GA: gluconic acid, LA: lactic acid, FA: formic acid, n.d.: not detected.
표 Table 1. Characterization of Ru/C
그림 Figure 4. Carbon yields of products obtained from hydrogenolysis of alginic acid over Ru/C, Ru/C mixed with MgO, and MgO (Reaction conditions: 1 wt% of alginic acid in 30 mL of water, 210 ℃, 2 h, 50 bar of hydrogen, 1000 rpm stirring). GA: gluconic acid, LA: lactic acid, FA: formic acid.
그림 Figure 5. GPC chromatograms of raw alginic acid sodium salt and liquid-phase products obtained from hydrogenolysis of alginic acid over Ru/C, Ru/C mixed with MgO, and MgO in the range of (a) 15-31 min and (b) 32-35 min.
표 Table 2. Final reaction pressures after hydrogenolysis of alginic acid depending on catalyst
표 Table 3. Weight average molecular weight (M_w) and number average molecular weight (M_n) of raw alginate and liquid-phase products depending on catalyst
그림 Figure 6. Liquid-phase products obtained from hydrogenolysis of alginic acid over (a) Ru/C, (b) Ru/C mixed with MgO, (c) MgO.
그림 Figure 7. Carbon yields of products obtained from hydrogenolysis of alginic acid over Ru/C mixed with MgO depending on (a) MgO dosage (Reaction conditions: 1 wt% of alginic acid in 30 mL of water, 100 mg of Ru/C, 210 ℃, 2 h, 50 bar of hydrogen, 1000 rpm stirring), (b) reaction time (Reaction conditions: 1 wt% of alginic acid in 30 mL of water, 100 mg of Ru/C, 100 mg of MgO, 210 ℃, 50 bar of hydrogen, 1000 rpm stirring), (c) reaction temperature (Reaction conditions: 1 wt% of alginic acid in 30 mL of water, 100 mg of Ru/C, 100 mg of MgO, 2 h, 50 bar of hydrogen, 1000 rpm stirring). GA: gluconic acid, LA: lactic acid, FA: formic acid.

참고문헌 (12)

Park, J. I., Woo, H. C., and Lee, J. H., "Production of bio-energy from Marine Algae: Status and Perspectives." Korean Chem. Eng. Res., 46(5), 833-844 (2008).
Song, M., Pham, H. D., Seon, J., and Woo, H. C., "Marine Brown Algae: a Conundrum Answer for Sustainable Biofuels Production." Renew. Sustain. Energy. Rev., 50, 782-792 (2015).
Feng, S., Kang, K., Salaudeen, S., Ahmadi, A., He, Q. S., and Hu, Y., "Recent Advances in Algae-Derived Biofuels and Bioactive Compounds." Ind. Eng. Chem. Res., 61(3), 1232-1249 (2022).

상세보기
Jung, K. A., Lim, S. R., Kim, Y., and Park, J. M., "Potentials of Macroalgae as Feedstocks for Biorefinery." Bioresour. Technol., 135, 182-190 (2013).

상세보기
Jeon, W., Ban, C., Park, G., Yu, T. K., Suh, J. Y., Woo, H. C., and Kim, D. H., "Catalytic Hydrothermal Conversion of Macroalgae-derived Alginate: Effect of pH on Production of Furfural and Valuable Organic Acids under Subcritical Water Conditions." J. Mol. Catal. A: Chem., 399, 106-113 (2015).

상세보기
Ban, C., Jeon, W., Park, G., Woo, H. C., and Kim, D. H., "Hydrothermal Conversion of Alginate into Uronic Acids over a Sulfonated Glucose-Derived Carbon Catalyst." Chem. Cat. Chem., 9(2), 329-337 (2017).
Jeon, W., Ban, C., Park, G., Woo, H. C., and Kim, D. H., "Hydrothermal Conversion of Macroalgae-derived Alginate to Lactic Acid Catalyzed by Metal Oxides." Catal. Sci. Technol., 6(4), 1146-1156 (2016).
Jeon, W., Ban, C., Kim, J. E., Woo, H. C., and Kim, D. H., "Production of Furfural from Macroalgae-derived Alginic Acid over Amberlyst-15." J. Mol. Catal. A: Chem., 423, 264-269 (2016).

상세보기
Ban, C., Jeon, W., Woo, H. C., and Kim, D. H., "Catalytic Hydrogenation of Macroalgae-Derived Alginic Acid into Sugar Alcohols." Chem. Sus. Chem., 10(24), 4891-4898 (2017).

상세보기
Yang, S., Kim, H., and Kim, D. H. "Hydrogenolysis of Alginic Acid Over Mono and Bimetallic Ruthenium/Nickel Supported on Activated Carbon Catalysts with Basic Promoters." React. Chem. Eng., 5(9), 1783-1790 (2020).

상세보기
Yang, L., Su, J., Carl, S., Lynam, J. G., Yang, X., and Lin, H., "Catalytic Conversion of Hemicellulosic Biomass to Lactic Acid in pH Neutral Aqueous Phase Media." Appl. Catal. B, 162, 149-157 (2015).
Hausoul, P. J., Negahdar, L., Schute, K., and Palkovits, R., "Unravelling the Ru-Catalyzed Hydrogenolysis of Biomass-Based Polyols under Neutral and Acidic Conditions." Chem. Sus. Chem, 8(19), 3323-3330 (2015).

상세보기

내보내기 구분	파일저장 인쇄 메일전송
구성항목	기본정보 상세정보 관리번호, 논문명, 저널/프로시딩명, 저자 , 발행년, 권, 호, 시작페이지, 끝페이지, 발행기관 관리번호, 논문명, 대등논문명, 저자 , 저널/프로시딩명, 발행기관, 발행년, 발행언어, 권, 호, 시작페이지, 끝페이지, ISBN, ISSN, 주제분야, 키워드, 초록(한글), 초록(영문), 저자(소속기관)
저장형식	Text(ASCII format) Excel format RefWorks Direct Export RIS format (for Reference Manager, ProCite, EndNote), Scholar's Aids, Mendeley
메일정보	받는사람 (필수) @ 보내는사람 (선택) @ 제목 내용 KISTI 검색결과 이메일 서비스
안내	총 건의 자료가 검색되었습니다. 다운받으실 자료의 인덱스를 입력하세요. (1-10,000) 검색결과의 순서대로 최대 10,000건 까지 다운로드가 가능합니다. 데이타가 많을 경우 속도가 느려질 수 있습니다.(최대 2~3분 소요) 다운로드 파일은 UTF-8 형태로 저장됩니다. 파일의 내용이 제대로 보이지 않을실 때는 웹브라우저 상단의 보기 -> 인코딩 -> 자동선택 여부를 확인하십시오. ~ Text(ASCII format) Excel format

연합인증