본 연구에서는 제올라이트 촉매를 이용한 바이오연료의 개질을 위해 촉매열분해와 수첨이성화 반응을 수행하였다. 촉매열분해와 수첨이성화 반응을 위한 모델물질로 바이오매스 구성성분과 n-dodecane을 각각 사용하였다. Unilamellar mesoporous MFI nanosheets (UMN)를 사용하여 바이오매스 구성성분의 촉매열분해를 수행하였고 대표적인 메조포러스 물질인 Al-SBA-15를 사용한 촉매열분해와 비교하였다. 바이오매스 구성성분의 촉매열분해는 microscale pyrolyzer-GC/MS를 사용하여 수행하였다. 촉매열분해 결과 상대적으로 강한 acidity를 보이는 UMN에서 ...
본 연구에서는 제올라이트 촉매를 이용한 바이오연료의 개질을 위해 촉매열분해와 수첨이성화 반응을 수행하였다. 촉매열분해와 수첨이성화 반응을 위한 모델물질로 바이오매스 구성성분과 n-dodecane을 각각 사용하였다. Unilamellar mesoporous MFI nanosheets (UMN)를 사용하여 바이오매스 구성성분의 촉매열분해를 수행하였고 대표적인 메조포러스 물질인 Al-SBA-15를 사용한 촉매열분해와 비교하였다. 바이오매스 구성성분의 촉매열분해는 microscale pyrolyzer-GC/MS를 사용하여 수행하였다. 촉매열분해 결과 상대적으로 강한 acidity를 보이는 UMN에서 바이오오일 개질 효과가 크게 나타났다. 셀룰로오스와 헤미셀룰로오스의 열분해로 생성되는 levoglucosan과 ketones, alcohols, cyclocompounds는 촉매에 의해 furans와 aromatics로 전환되었다. 리그닌의 열분해로 생성되는 phenolics는 촉매에 의해 alkylphenols과 aromatics로 전환되었다. 바이오오일의 개질 효과는 촉매량이 증가할수록 크게 나타났다. 바이오매스 구성성분 중 함량이 높은 리그닌과 셀룰로오스를 선택하여 각각 2 단계 촉매열분해와 혼합 촉매열분해를 수행하였다. 리그닌의 2 단계 촉매열분해는 고정층 반응기에서 수행하였으며 NZ (natural zeolite)를 1단계 직접접촉, HZSM-5를 2단계 간접접촉 촉매로 사용하였다. 2단계 촉매열분해와 HZSM-5 만을 사용한 촉매열분해를 수행하고 aromatics 생성 및 coke 수율을 비교하였다. 2단계 촉매열분해를 하였을 때 NZ의 영향으로 aromatics 생성이 증가하였고 coke 수율은 감소하였다. 바이오오일 개질 및 coke 감소효과는 NZ의 양이 증가하고 HZSM-5 반응온도가 증가할 때 크게 나타났다. 셀룰로오스를 반탄화하고 PP (polypropylene)와 혼합 촉매열분해를 수행하였다. 반탄화 셀룰로오스와 PP의 혼합 촉매열분해는 pyrolyzer-GC/MS/FID/TCD를 사용하여 수행하였다. 반탄화 과정에서 구조가 변한 반탄화 셀룰로오스의 촉매열분해는 셀룰로오스의 촉매열분해보다 높은 aromatics 수율을 나타냈다. PP와의 혼합 촉매열분해에서 반탄화 셀룰로오스는 상대적으로 적은 양의 촉매와 PP를 사용하여도 synergy effect를 나타냈다. Pt가 담지된 Y 제올라이트를 사용하여 n-dodecane의 수첨이성화 반응을 수행하였다. 제올라이트의 acidity를 silylation, ion-exchange, 다양한 SiO2/Al2O3 비를 사용하여 조절하였다. Pt의 담지량도 0.1-1.0 wt%로 변경하였다. 수첨이성화 반응 결과 Pt/HY(80), Pt/HY(5.1)-0.288, Pt/NaY(5.1)-IE1를 사용하였을 때 상대적으로 높은 효율을 나타냈으며 Pt의 담지량이 증가하였을 때 활성이 증가하는 경향을 보였다. 이원기능촉매를 사용한 수첨이성화 반응의 온도와 압력조건도 최적화하였다.
본 연구에서는 제올라이트 촉매를 이용한 바이오연료의 개질을 위해 촉매열분해와 수첨이성화 반응을 수행하였다. 촉매열분해와 수첨이성화 반응을 위한 모델물질로 바이오매스 구성성분과 n-dodecane을 각각 사용하였다. Unilamellar mesoporous MFI nanosheets (UMN)를 사용하여 바이오매스 구성성분의 촉매열분해를 수행하였고 대표적인 메조포러스 물질인 Al-SBA-15를 사용한 촉매열분해와 비교하였다. 바이오매스 구성성분의 촉매열분해는 microscale pyrolyzer-GC/MS를 사용하여 수행하였다. 촉매열분해 결과 상대적으로 강한 acidity를 보이는 UMN에서 바이오오일 개질 효과가 크게 나타났다. 셀룰로오스와 헤미셀룰로오스의 열분해로 생성되는 levoglucosan과 ketones, alcohols, cyclocompounds는 촉매에 의해 furans와 aromatics로 전환되었다. 리그닌의 열분해로 생성되는 phenolics는 촉매에 의해 alkylphenols과 aromatics로 전환되었다. 바이오오일의 개질 효과는 촉매량이 증가할수록 크게 나타났다. 바이오매스 구성성분 중 함량이 높은 리그닌과 셀룰로오스를 선택하여 각각 2 단계 촉매열분해와 혼합 촉매열분해를 수행하였다. 리그닌의 2 단계 촉매열분해는 고정층 반응기에서 수행하였으며 NZ (natural zeolite)를 1단계 직접접촉, HZSM-5를 2단계 간접접촉 촉매로 사용하였다. 2단계 촉매열분해와 HZSM-5 만을 사용한 촉매열분해를 수행하고 aromatics 생성 및 coke 수율을 비교하였다. 2단계 촉매열분해를 하였을 때 NZ의 영향으로 aromatics 생성이 증가하였고 coke 수율은 감소하였다. 바이오오일 개질 및 coke 감소효과는 NZ의 양이 증가하고 HZSM-5 반응온도가 증가할 때 크게 나타났다. 셀룰로오스를 반탄화하고 PP (polypropylene)와 혼합 촉매열분해를 수행하였다. 반탄화 셀룰로오스와 PP의 혼합 촉매열분해는 pyrolyzer-GC/MS/FID/TCD를 사용하여 수행하였다. 반탄화 과정에서 구조가 변한 반탄화 셀룰로오스의 촉매열분해는 셀룰로오스의 촉매열분해보다 높은 aromatics 수율을 나타냈다. PP와의 혼합 촉매열분해에서 반탄화 셀룰로오스는 상대적으로 적은 양의 촉매와 PP를 사용하여도 synergy effect를 나타냈다. Pt가 담지된 Y 제올라이트를 사용하여 n-dodecane의 수첨이성화 반응을 수행하였다. 제올라이트의 acidity를 silylation, ion-exchange, 다양한 SiO2/Al2O3 비를 사용하여 조절하였다. Pt의 담지량도 0.1-1.0 wt%로 변경하였다. 수첨이성화 반응 결과 Pt/HY(80), Pt/HY(5.1)-0.288, Pt/NaY(5.1)-IE1를 사용하였을 때 상대적으로 높은 효율을 나타냈으며 Pt의 담지량이 증가하였을 때 활성이 증가하는 경향을 보였다. 이원기능촉매를 사용한 수첨이성화 반응의 온도와 압력조건도 최적화하였다.
In this study, catalytic upgrading of biofuel was performed via catalytic pyrolysis and hydroisomerization using zeolite catalyst. Biomass components and n-dodecane were used as a model compound in catalytic pyrolysis of biomass and hydroisomerization of biomass-derived fuel, respectively. Unila...
In this study, catalytic upgrading of biofuel was performed via catalytic pyrolysis and hydroisomerization using zeolite catalyst. Biomass components and n-dodecane were used as a model compound in catalytic pyrolysis of biomass and hydroisomerization of biomass-derived fuel, respectively. Unilamellar mesoporous MFI nanosheets (UMN) was applied for catalytic pyrolysis of biomass components. Al-SBA-15, a representative mesoporous catalyst, was also applied for comparison. The experiments were carried out using microscale pyrolyzer-GC/MS. UMN showed higher catalytic activities for bio-oil upgrading compared to Al-SBA-15 since UMN contains strong Brønsted acid sites. The main products of pyrolysis such as levoglucosan derived from cellulose, and ketones, alcohols and cyclocompounds produced from xylan were converted into furans and aromatics via catalytic pyrolysis. Phenolics from lignin pyrolysis were converted to alkylphenols and aromatics by catalytic pyrolysis. Meanwhile, bio-oil quality was improved by increase of catalyst amount. Among biomass components, lignin and cellulose were selected for two-stage catalytic pyrolysis and catalytic co-pyrolysis, respectively. The two-stage catalytic pyrolysis of lignin was conducted using a fixed bed reactor. NZ (natural zeolite) and HZSM-5 were used for in-situ (1st stage) and ex-situ (2nd stage) catalytic pyrolysis, respectively. The overall performance of the catalytic pyrolysis of lignin was evaluated by comparing lignin conversion, aromatic formation, and deposited coke amount obtained from the two-stage catalytic pyrolysis with those from a single-stage catalytic pyrolysis with ex-situ HZSM-5. Compared to the single-stage catalytic pyrolysis, the two-stage catalytic pyrolysis resulted in higher yield of aromatics with smaller amount of coke due to the pre-catalytic effect of natural zeolite. These positive effects caused by the use of two-stage catalysts were maximized by increasing the amount of in-situ natural zeolite and the temperature of ex-situ HZSM-5 catalyst bed, up to 600 ℃ . Catalytic co-pyrolysis of torrefied cellulose and PP (polypropylene) was investigated using pyrolyzer-GC/MS/FID/TCD. HZSM-5 and HBeta with various SiO2/Al2O3 ratios were used as catalyst. The ratios of torrefied cellulose to PP and catalyst to sample were also changed. The structural change of cellulose caused by torrefaction led to improved catalytic conversion of cellulose during the catalytic pyrolysis over HZSM-5. In catalytic co-pyrolysis of cellulose and PP, cellulose torrefaction showed to be efficient for higher yield of aromatics, and this synergy effect of cellulose torrefaction was more considerable at lower catalyst and PP amounts. Platinum containing zeolite Y catalysts were applied for hydroisomerization of n-dodecane. Acidity was controlled by silyation, ion-exchange and various SiO2/Al2O3 ratios. Platinum content was changed within the range of 0.1-1.0 wt%. The results of hydroisomerization showed that Pt/HY(80), Pt/HY(5.1)-0.288 and Pt/NaY(5.1)-IE1 had higher activity for n-dodecane hydroisomerization compared to other catalysts such as Pt/HY(5.1, 200) Pt/HY(80)-0.096 and Pt/NaY(5.1). Catalytic activity was increased with increasing platinum content. Besides, hydroisomerization reaction temperature and pressure were also optimized.
In this study, catalytic upgrading of biofuel was performed via catalytic pyrolysis and hydroisomerization using zeolite catalyst. Biomass components and n-dodecane were used as a model compound in catalytic pyrolysis of biomass and hydroisomerization of biomass-derived fuel, respectively. Unilamellar mesoporous MFI nanosheets (UMN) was applied for catalytic pyrolysis of biomass components. Al-SBA-15, a representative mesoporous catalyst, was also applied for comparison. The experiments were carried out using microscale pyrolyzer-GC/MS. UMN showed higher catalytic activities for bio-oil upgrading compared to Al-SBA-15 since UMN contains strong Brønsted acid sites. The main products of pyrolysis such as levoglucosan derived from cellulose, and ketones, alcohols and cyclocompounds produced from xylan were converted into furans and aromatics via catalytic pyrolysis. Phenolics from lignin pyrolysis were converted to alkylphenols and aromatics by catalytic pyrolysis. Meanwhile, bio-oil quality was improved by increase of catalyst amount. Among biomass components, lignin and cellulose were selected for two-stage catalytic pyrolysis and catalytic co-pyrolysis, respectively. The two-stage catalytic pyrolysis of lignin was conducted using a fixed bed reactor. NZ (natural zeolite) and HZSM-5 were used for in-situ (1st stage) and ex-situ (2nd stage) catalytic pyrolysis, respectively. The overall performance of the catalytic pyrolysis of lignin was evaluated by comparing lignin conversion, aromatic formation, and deposited coke amount obtained from the two-stage catalytic pyrolysis with those from a single-stage catalytic pyrolysis with ex-situ HZSM-5. Compared to the single-stage catalytic pyrolysis, the two-stage catalytic pyrolysis resulted in higher yield of aromatics with smaller amount of coke due to the pre-catalytic effect of natural zeolite. These positive effects caused by the use of two-stage catalysts were maximized by increasing the amount of in-situ natural zeolite and the temperature of ex-situ HZSM-5 catalyst bed, up to 600 ℃ . Catalytic co-pyrolysis of torrefied cellulose and PP (polypropylene) was investigated using pyrolyzer-GC/MS/FID/TCD. HZSM-5 and HBeta with various SiO2/Al2O3 ratios were used as catalyst. The ratios of torrefied cellulose to PP and catalyst to sample were also changed. The structural change of cellulose caused by torrefaction led to improved catalytic conversion of cellulose during the catalytic pyrolysis over HZSM-5. In catalytic co-pyrolysis of cellulose and PP, cellulose torrefaction showed to be efficient for higher yield of aromatics, and this synergy effect of cellulose torrefaction was more considerable at lower catalyst and PP amounts. Platinum containing zeolite Y catalysts were applied for hydroisomerization of n-dodecane. Acidity was controlled by silyation, ion-exchange and various SiO2/Al2O3 ratios. Platinum content was changed within the range of 0.1-1.0 wt%. The results of hydroisomerization showed that Pt/HY(80), Pt/HY(5.1)-0.288 and Pt/NaY(5.1)-IE1 had higher activity for n-dodecane hydroisomerization compared to other catalysts such as Pt/HY(5.1, 200) Pt/HY(80)-0.096 and Pt/NaY(5.1). Catalytic activity was increased with increasing platinum content. Besides, hydroisomerization reaction temperature and pressure were also optimized.
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