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...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.展开更多
Development of pore structures of activated carbon(AC)from activation of biomass with ZnCl_(2) relies on content and structure of cellulose/hemicellulose in the feedstock.Thermal pretreatment of biomass could induce d...Development of pore structures of activated carbon(AC)from activation of biomass with ZnCl_(2) relies on content and structure of cellulose/hemicellulose in the feedstock.Thermal pretreatment of biomass could induce dehydration and/or aromatization to change the structure of cellulose/hemicellulose.This might interfere with evolution of structures of AC,which was investigated herein via thermal pretreatment of willow branch(WB)from 200 to 360℃and the subsequent activation with ZnCl_(2) at 550℃.The results showed that thermal pretreatment at 360℃(WB-360)could lead to substantial pyrolysis to form biochar,with a yield of 31.9%,accompanying with nearly complete destruction of cellulose crystals and remarkably enhanced aromatic degree.However,cellulose residual in WB-360 could still be activated to form AC-360 with specific surface area of 1837.9 m~2·g^(-1),which was lower than that in AC from activation of untreated WB(AC-blank,2077.8 m~2·g^(-1)).Nonetheless,the AC-200 from activation of WB-200 had more developed pores(2113.9 m~2·g^(-1))and superior capability for adsorption of phenol,due to increased permeability of ZnCl_(2) to the largely intact cellulose structure in WB-200.The thermal pretreatment did increase diameters of micropores of AC but reduced the overall yield of AC(26.8%for AC-blank versus 18.0%for AC-360),resulting from accelerated cracking but reduced intensity of condensation.In-situ infrared characterization of the activation showed that ZnCl_(2) mainly catalyzed dehydration,dehydrogenation,condensation,and aromatization but not cracking,suppressing the formation of derivatives of cellulose and lignin in bio-oil.The thermal pretreatment formed phenolic-OH and C=O with higher chemical innerness,which changed the reaction network in activation,shifting morphology of fibrous structures in AC-blank to“melting surface”in AC-200 or AC-280.展开更多
基金supported by the National Natural Science Foundation of China(51876080)the Program for Taishan Scholars of the Shandong Province Government。
文摘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.
基金supported by the National Natural Science Foundation of China(52276195)Program for Supporting Innovative Research from Jinan(202228072)Program of Agricultural Development from Shandong(SD2019NJ015)。
文摘Development of pore structures of activated carbon(AC)from activation of biomass with ZnCl_(2) relies on content and structure of cellulose/hemicellulose in the feedstock.Thermal pretreatment of biomass could induce dehydration and/or aromatization to change the structure of cellulose/hemicellulose.This might interfere with evolution of structures of AC,which was investigated herein via thermal pretreatment of willow branch(WB)from 200 to 360℃and the subsequent activation with ZnCl_(2) at 550℃.The results showed that thermal pretreatment at 360℃(WB-360)could lead to substantial pyrolysis to form biochar,with a yield of 31.9%,accompanying with nearly complete destruction of cellulose crystals and remarkably enhanced aromatic degree.However,cellulose residual in WB-360 could still be activated to form AC-360 with specific surface area of 1837.9 m~2·g^(-1),which was lower than that in AC from activation of untreated WB(AC-blank,2077.8 m~2·g^(-1)).Nonetheless,the AC-200 from activation of WB-200 had more developed pores(2113.9 m~2·g^(-1))and superior capability for adsorption of phenol,due to increased permeability of ZnCl_(2) to the largely intact cellulose structure in WB-200.The thermal pretreatment did increase diameters of micropores of AC but reduced the overall yield of AC(26.8%for AC-blank versus 18.0%for AC-360),resulting from accelerated cracking but reduced intensity of condensation.In-situ infrared characterization of the activation showed that ZnCl_(2) mainly catalyzed dehydration,dehydrogenation,condensation,and aromatization but not cracking,suppressing the formation of derivatives of cellulose and lignin in bio-oil.The thermal pretreatment formed phenolic-OH and C=O with higher chemical innerness,which changed the reaction network in activation,shifting morphology of fibrous structures in AC-blank to“melting surface”in AC-200 or AC-280.
