Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

doi:10.1016/j.cjche.2023.09.002

Chinese Journal of Chemical Engineering ›› 2024, Vol. 65 ›› Issue (1): 200-211.DOI: 10.1016/j.cjche.2023.09.002

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Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

Li Qiu¹, Chao Li¹, Shu Zhang², Shuang Wang³, Bin Li³, Zhenhua Cui⁴, Yonggui Tang⁴, Obid Tursunov⁵, Xun Hu¹

1 School of Material Science and Engineering, University of Jinan, Jinan 250022, China;
2 Joint International Research Laboratory of Biomass Energy and Materials, College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China;
3 School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013, China;
4 Shandong BASAN Graphite New Material Plant, Zibo 255311, China;
5 Department of Power Supply and Renewable Energy Sources, National Research University TIIAME, Tashkent 100000, Uzbekistan

Received:2023-06-25 Revised:2023-09-04 Online:2024-04-17 Published:2024-01-28
Contact: Xun Hu,E-mail:xun.hu@outlook.com
Supported by:
This work was supported by the National Natural Science Foundation of China (51876080) and the Program for Taishan Scholars of the Shandong Province Government.

Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

Li Qiu¹, Chao Li¹, Shu Zhang², Shuang Wang³, Bin Li³, Zhenhua Cui⁴, Yonggui Tang⁴, Obid Tursunov⁵, Xun Hu¹

1 School of Material Science and Engineering, University of Jinan, Jinan 250022, China;
2 Joint International Research Laboratory of Biomass Energy and Materials, College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China;
3 School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013, China;
4 Shandong BASAN Graphite New Material Plant, Zibo 255311, China;
5 Department of Power Supply and Renewable Energy Sources, National Research University TIIAME, Tashkent 100000, Uzbekistan

通讯作者: Xun Hu,E-mail:xun.hu@outlook.com
基金资助:
This work was supported by the National Natural Science Foundation of China (51876080) and the Program for Taishan Scholars of the Shandong Province Government.

Abstract

Abstract: Biochar and bio-oil are produced simultaneously in one pyrolysis process, and they inevitably contact and may interact, influencing the composition of bio-oil and modifying the structure of biochar. In this sense, biochar is an inherent catalyst for pyrolysis. In this study, in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homologous volatiles in bio-oil, three char catalysts (600C, 800C, and 800AC) produced via pyrolysis of poplar wood at 600 or 800 ℃ or activated at 800 ℃, were used for catalyzing pyrolysis of homologous poplar wood at 600 ℃, respectively. The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas (yield increase by 40.2%) and aromatization of volatiles to form more light or heavy phenolics, due to its abundant oxygen-containing functionalities acting as active sites. The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization. Nevertheless, the interaction with the volatiles consumed oxygen on 600C (decrease by 50%), enhancing the aromatic degree and increasing thermal stability. The dominance of deposition of carbonaceous material of a very aromatic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores. The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of —OH, while conversion of the intermediates bearing C=O was enhanced over all the char catalysts.

Key words: Poplar wood, Catalytic pyrolysis, Char catalyst, Volatile-char interaction, Bio-oil

摘要： Biochar and bio-oil are produced simultaneously in one pyrolysis process, and they inevitably contact and may interact, influencing the composition of bio-oil and modifying the structure of biochar. In this sense, biochar is an inherent catalyst for pyrolysis. In this study, in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homologous volatiles in bio-oil, three char catalysts (600C, 800C, and 800AC) produced via pyrolysis of poplar wood at 600 or 800 ℃ or activated at 800 ℃, were used for catalyzing pyrolysis of homologous poplar wood at 600 ℃, respectively. The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas (yield increase by 40.2%) and aromatization of volatiles to form more light or heavy phenolics, due to its abundant oxygen-containing functionalities acting as active sites. The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization. Nevertheless, the interaction with the volatiles consumed oxygen on 600C (decrease by 50%), enhancing the aromatic degree and increasing thermal stability. The dominance of deposition of carbonaceous material of a very aromatic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores. The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of —OH, while conversion of the intermediates bearing C=O was enhanced over all the char catalysts.

关键词: Poplar wood, Catalytic pyrolysis, Char catalyst, Volatile-char interaction, Bio-oil

Li Qiu, Chao Li, Shu Zhang, Shuang Wang, Bin Li, Zhenhua Cui, Yonggui Tang, Obid Tursunov, Xun Hu. Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar[J]. Chinese Journal of Chemical Engineering, 2024, 65(1): 200-211.

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Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

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