The microwave assisted liquefaction process of wheat straw alkali lignin was investigated to obtain monophenolic compounds as the precursor of bio-fuel. It is found that the total yield of monophenolic compounds is si...The microwave assisted liquefaction process of wheat straw alkali lignin was investigated to obtain monophenolic compounds as the precursor of bio-fuel. It is found that the total yield of monophenolic compounds is significantly improved under microwave irradiation, reaching 15.77% under a relatively mild liquefaction condition of 10 wt% H2SO4 as the catalyst, 10 wt% phenol as the hydrogen-donor reagent at 120 ℃ for 40 rain. Compared with conventional thermal liquefaction process, microwave irradiation promotes the cleavage of C-C bonds, which gives an extra 29% of Caryl-Cα bond cleavage, and increases the yield of monophenolic compounds from 0.92% to 13.61% under the same conditions. The excessive temperature and prolonged time under microwave irradiation will promote the recondensation of degraded lignin fragments, so the key to obtain high yield of monophenolic compounds is to avoid the recondensation reaction. The selected solid catalyst promotes the dissociation of methoxy groups, and the addition of phenol into liquefaction can only slightly improve the yield of monophencolic compounds.展开更多
Photocatalytic selective transform native lignin into valuable chemicals is an attractive but challenging task.Herein,we report a mesoporous sulfur-doped carbon nitride(MSCN-0.5)which is prepared by a facile one-step ...Photocatalytic selective transform native lignin into valuable chemicals is an attractive but challenging task.Herein,we report a mesoporous sulfur-doped carbon nitride(MSCN-0.5)which is prepared by a facile one-step thermal condensation strategy.It is highly active and selective for the cleavage Cα-Cβbond inβ-O-4 lignin model compound under visible light radiation at room temperature,achieving 99%substrate conversion and 98%Cα-Cβbond cleavage selectivity.Mechanistic studies revealed that the Cβ-H bond of lignin model compounds activated by holes and generate key Cβradical intermediates,further induced the Cα-Cβbond cleavage by superoxide anion radicals(·O2-)to produce aromatic oxygenates.Waste Camellia oleifera shell(WCOS)was taken as a representative to further understand the reaction mechanisms on native lignin.33.2 mg of monophenolic compounds(Vanillin accounted for 22%and Syringaldehyde for 34%)can be obtained by each gram of WCOS lignin,which is 2.5 times as that of the pristine carbon nitride.The present work offers useful guidance for designing metal-free heterogeneous photocatalysts for Cα-Cβbond cleavage to harvest monophenolic compounds.展开更多
To understand the catalytic conversion of lignin into high-value products,lignin depolymerization was performed using a layered polymetallic oxide(CuMgAlO_(x))catalyst.The effects of the conversion temperature,hydroge...To understand the catalytic conversion of lignin into high-value products,lignin depolymerization was performed using a layered polymetallic oxide(CuMgAlO_(x))catalyst.The effects of the conversion temperature,hydrogen pressure,and reaction time were studied,and the ability of CuMgAlO_(x)to break the C–O bond was evaluated.The CuMgAlO_(x)(Mg/Al=3:1)catalyst contained acidic sites and had a relatively homogeneous elemental distribution with a high pore size and specific surface area.Theβ-O-4 was almost completely converted by disassociating the C–O bond,resulting in yields of 14.74%ethylbenzene,47.58%α-methylphenyl ethanol,and 36.43%phenol.The highest yield of lignin-derived monophenols was 85.16%under reaction conditions of 280℃ and 3 Mpa for 4 h.As the reaction progressed,depolymerization and condensation reactions occurred simultaneously.Higher temperatures(>280℃)and pressures(>3 Mpa)tended to produce solid char.This study establishes guidelines for the high-value application of industrial lignin in the catalytic conversion of polymetallic oxides.展开更多
Lignin is considered an ideal natural material for the production of sustainable monophenols.In this study,a microwave-assisted depolymerization(MAD)strategy was developed.The introduction of solvent vapors in the dyn...Lignin is considered an ideal natural material for the production of sustainable monophenols.In this study,a microwave-assisted depolymerization(MAD)strategy was developed.The introduction of solvent vapors in the dynamic vapor flow reaction system was performed to enhance the lignin conversion efficiency.The results showed that no liquid products were generated from the MAD of lignin without solvent vapors.With the introduction of solvents(CH_(3)OH,HCHO,HCOOH,and CH_(2)Cl_(2)),liquid products appeared(especially with CH_(2)Cl_(2),which had the highest yield of 41.9 wt%).Results from gas chromatography/mass spectrometry of liquid products showed that seven kinds of compounds,including guaiacols,phenols,syringols,methoxyphenyls,heterocycles,esters,and aromatics were identified.CH_(2)Cl_(2) can significantly enhance the production of monophenols(guaiacols,phenols,and syringols).The introduction of these solvent vapors can also facilitate the generation of porous char with high Brunauer-Emmett-Teller specific surface areas.Some carbon nanospheres deposited on the surface of the char were obtained with the assistance of CH_(2)Cl_(2).This study provides a facile method for the utilization of lignin in the field of bio-based fine chemicals.展开更多
基金supported by the National Basic Research Program of China(2012CB215302)Guangdong Provincial Natural Science Fund(9151064101000082)
文摘The microwave assisted liquefaction process of wheat straw alkali lignin was investigated to obtain monophenolic compounds as the precursor of bio-fuel. It is found that the total yield of monophenolic compounds is significantly improved under microwave irradiation, reaching 15.77% under a relatively mild liquefaction condition of 10 wt% H2SO4 as the catalyst, 10 wt% phenol as the hydrogen-donor reagent at 120 ℃ for 40 rain. Compared with conventional thermal liquefaction process, microwave irradiation promotes the cleavage of C-C bonds, which gives an extra 29% of Caryl-Cα bond cleavage, and increases the yield of monophenolic compounds from 0.92% to 13.61% under the same conditions. The excessive temperature and prolonged time under microwave irradiation will promote the recondensation of degraded lignin fragments, so the key to obtain high yield of monophenolic compounds is to avoid the recondensation reaction. The selected solid catalyst promotes the dissociation of methoxy groups, and the addition of phenol into liquefaction can only slightly improve the yield of monophencolic compounds.
基金finacially supported by the National Natural Science Foundation of China(Nos.21966023,21665018 and 51568049)the Natural Science Foundation of Jiangxi Province,China(No.20171ACB21035)Jiangxi Province Graduate Student Innovation Special Fund(No.YC2020-S513)。
文摘Photocatalytic selective transform native lignin into valuable chemicals is an attractive but challenging task.Herein,we report a mesoporous sulfur-doped carbon nitride(MSCN-0.5)which is prepared by a facile one-step thermal condensation strategy.It is highly active and selective for the cleavage Cα-Cβbond inβ-O-4 lignin model compound under visible light radiation at room temperature,achieving 99%substrate conversion and 98%Cα-Cβbond cleavage selectivity.Mechanistic studies revealed that the Cβ-H bond of lignin model compounds activated by holes and generate key Cβradical intermediates,further induced the Cα-Cβbond cleavage by superoxide anion radicals(·O2-)to produce aromatic oxygenates.Waste Camellia oleifera shell(WCOS)was taken as a representative to further understand the reaction mechanisms on native lignin.33.2 mg of monophenolic compounds(Vanillin accounted for 22%and Syringaldehyde for 34%)can be obtained by each gram of WCOS lignin,which is 2.5 times as that of the pristine carbon nitride.The present work offers useful guidance for designing metal-free heterogeneous photocatalysts for Cα-Cβbond cleavage to harvest monophenolic compounds.
基金supported by the National Natural Science Fund for Distinguished Young Scholars(52125601).
文摘To understand the catalytic conversion of lignin into high-value products,lignin depolymerization was performed using a layered polymetallic oxide(CuMgAlO_(x))catalyst.The effects of the conversion temperature,hydrogen pressure,and reaction time were studied,and the ability of CuMgAlO_(x)to break the C–O bond was evaluated.The CuMgAlO_(x)(Mg/Al=3:1)catalyst contained acidic sites and had a relatively homogeneous elemental distribution with a high pore size and specific surface area.Theβ-O-4 was almost completely converted by disassociating the C–O bond,resulting in yields of 14.74%ethylbenzene,47.58%α-methylphenyl ethanol,and 36.43%phenol.The highest yield of lignin-derived monophenols was 85.16%under reaction conditions of 280℃ and 3 Mpa for 4 h.As the reaction progressed,depolymerization and condensation reactions occurred simultaneously.Higher temperatures(>280℃)and pressures(>3 Mpa)tended to produce solid char.This study establishes guidelines for the high-value application of industrial lignin in the catalytic conversion of polymetallic oxides.
基金This work was supported by the Foundation of the Key Laboratory of Pulp and Paper Science and Technology of the Ministry of Education of China(No.KF201917)the National Natural Science Foundation of China(31800497).
文摘Lignin is considered an ideal natural material for the production of sustainable monophenols.In this study,a microwave-assisted depolymerization(MAD)strategy was developed.The introduction of solvent vapors in the dynamic vapor flow reaction system was performed to enhance the lignin conversion efficiency.The results showed that no liquid products were generated from the MAD of lignin without solvent vapors.With the introduction of solvents(CH_(3)OH,HCHO,HCOOH,and CH_(2)Cl_(2)),liquid products appeared(especially with CH_(2)Cl_(2),which had the highest yield of 41.9 wt%).Results from gas chromatography/mass spectrometry of liquid products showed that seven kinds of compounds,including guaiacols,phenols,syringols,methoxyphenyls,heterocycles,esters,and aromatics were identified.CH_(2)Cl_(2) can significantly enhance the production of monophenols(guaiacols,phenols,and syringols).The introduction of these solvent vapors can also facilitate the generation of porous char with high Brunauer-Emmett-Teller specific surface areas.Some carbon nanospheres deposited on the surface of the char were obtained with the assistance of CH_(2)Cl_(2).This study provides a facile method for the utilization of lignin in the field of bio-based fine chemicals.
