Ferulic acid(FA)and p-coumaric acid(pCA)in bagasse,wheat straw,corn straw,and corncob were extracted by alkaline hydrolysis and characterized by gas chromatography(GC)and gas chromatography-mass spectrometry(GC-MS).It...Ferulic acid(FA)and p-coumaric acid(pCA)in bagasse,wheat straw,corn straw,and corncob were extracted by alkaline hydrolysis and characterized by gas chromatography(GC)and gas chromatography-mass spectrometry(GC-MS).It was found that the FA and most of the pCA in gramineous biomass could be dissociated and released after being treated with 1 M NaOH at 100℃for 4 h.The yields of pCA/FA in bagasse,wheat straw,corn straw,and corncob determined by GC-FID are 39.8/11.5,13.7/11.0,28.0/11.0,and 35.1/14.5 mg/g,respectively.The raw materials and the treated solid residues were characterized by gel-state 2D Heteronuclear Single Quantum Coherence Nuclear Magnetic Resonance(2D HSQC NMR).It was found that only a small amount of lignin was detected in the residue after alkali treatment,indicating that the alkali treatment conditions can effectively cleave the FA and pCA.Additionally,the lignin in the alkali solution was recovered and characterized by 2D HSQC NMR.The FA was not able to be detected by NMR,whereas a small amount of pCA remained in the alkali lignin.This study reveals the structural change of residual lignins during the quantitative isolation of FA and pCA,which is essential for the selective isolation of pCA/FA and valorization of residual alkali lignin.展开更多
The two kinds of rigid polyurethane （PU） foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in...The two kinds of rigid polyurethane （PU） foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.展开更多
The two kinds of rigid polyurethane(PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in we...The two kinds of rigid polyurethane(PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight.The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams.The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples.The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently.Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples.The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.展开更多
This study performed catalytic depolymerization of alkali lignin over Ni-based catalysts.Effects of different promoters(Zr and W),Ni loadings,reaction temperatures,and the addition of formic acid and catalyst on ligni...This study performed catalytic depolymerization of alkali lignin over Ni-based catalysts.Effects of different promoters(Zr and W),Ni loadings,reaction temperatures,and the addition of formic acid and catalyst on lignin conversion and products distribution were all investigated.The result showed that the highest oil yield(40.1%(mass))was obtained at 240℃over Ni_(1.2)/γ-Al_(2)O_(3) promoted by Zr and W species.Quantitative analysis indicates that Zr and W species prefer to lignin depolymerization while Ni active phase prefer to hydrodeoxygenation and hydrogenation.The interconversion of products derived from lignin depolymerization was determined by gas chromatography-mass spectrometer,which demonstrated that phenolic compounds were dominant products in all lignin derived bio-oils,wherein the proportion of vanillin was highest(65.7%)at 180℃,while that of alkyl guaiacols increased with the increase of temperature(from 12.45%at 180℃ to 66.67%at 240℃).Residual lignin obtained after lignin depolymerization was also investigated for detecting differences on functional groups,wherein the disappearing peaks at 1511 cm^(-1)(stretching of aromatic rings),1267,1215 and 1035 cm^(-1)(vibrations of guaiacyl and syringyl units)were detected by Fourier transform infrared spectrometry.Additionally,the higher O/C ratio measured by elemental analysis also confirmed that alkali lignin was depolymerized effectively under mild conditions.展开更多
Alkali lignin was processed by plasma and then used in modification of phenol formaldehyde resin in this study.Chemical structural changes of lignin which was processed by plasma as well as bonding strength,tensile pr...Alkali lignin was processed by plasma and then used in modification of phenol formaldehyde resin in this study.Chemical structural changes of lignin which was processed by plasma as well as bonding strength,tensile property,curing performance and thermal property of the prepared phenol formaldehyde resin which was modified by the plasma processed lignin were analyzed.Results demonstrated that:(1)Alkali lignin was degraded after the plasma processing.The original groups were destroyed,and the aromatic rings collected abundant free radicals and oxygen-containing functional groups like hydroxyls,carbonyls,carboxyls and acyls were introduced into increase the reaction activity of lignin significantly.(2)The introduction of alkali lignin decreased the free formaldehyde content and increased bonding strength and toughness of the prepared phenol formaldehyde resin,especially after the introduction of lignin treated with plasma.(3)The introduction of alkali lignin led to high curing temperature for the prepared phenol formaldehyde resin,but that was reduced by the plasma processed alkali lignin.(4)The introduction of alkali lignin could also increase thermal stability of phenol formaldehyde resin,but that was modified by plasma processed alkali lignin was better than the unprocessed lignin.Based on the results,the plasma processed lignin was used to modify phenol formaldehyde resin,which could increase the strength and toughness of phenol formaldehyde resin significantly.展开更多
Lignin is an abundant renewable macromolecular material in nature,and degradation of lignin to improve its hydroxyl content is the key to its efficient use.Alkali lignin(AL)was treated with Brønsted acidic deep e...Lignin is an abundant renewable macromolecular material in nature,and degradation of lignin to improve its hydroxyl content is the key to its efficient use.Alkali lignin(AL)was treated with Brønsted acidic deep eutectic solvent(DES)based on choline chloride and p-toluenesulfonic acid at mild reaction temperature,the structure of the lignin before and after degradation,as well as the composition of small molecules of lignin were analyzed in order to investigate the chemical structure changes of lignin with DES treatment,and the degradation mechanism of lignin in this acidic DES was elucidated in this work.FTIR and NMR analyses demonstrated the selective cleavage of the lignin ether linkages in the degradation process,which was in line with the increased content of phenolic hydroxyl species.XPS revealed that the O/C atomic ratio of the regenerated lignin was lower than that of the AL sample,revealing that the lignin underwent decarbonylation during the DES treatment.Regenerated lignin with low molecular weight and narrow polydispersity index was obtained,and the average molecular weight(Mw)decreased from 17680 g/mol to 2792 g/mol(130°C,3 h)according to GPC analysis.The lignin-degraded products were mainly G-type phenolics and ketones,and small number of aldehydes were also generated,the possible degradation pathway of lignin in this acidic DES was proposed.展开更多
Waterborne polyurethane(WPU) binder was synthesized by refined alkali lignin(RAL) with 4,4′-diphenylmethane diisocyanate(MDI).Fourier transform infrared spectroscopy(FTIR) was used to clarify the group change of raw ...Waterborne polyurethane(WPU) binder was synthesized by refined alkali lignin(RAL) with 4,4′-diphenylmethane diisocyanate(MDI).Fourier transform infrared spectroscopy(FTIR) was used to clarify the group change of raw materials-alkali lignin(AL),MDI,and product WPU,and laser particle analyzer was used to analyze the particle size of WPU.The results were as follows: AL could react with MDI to produce WPU binder.The reaction extent,the dispersion,and dispersion stability of WPU were influenced by/ratio.The WPU synthesized by AL,polyethylene glycol(PEG) and MDI was used as a binder in pigment dyeing process.In this process,the influence factors,such as binders made by different ratio of materials,the concentration of binder,curing temperature,and curing time were analyzed respectively.展开更多
Depolymerization of lignin is an important step to obtain lignin monomer for the synthesis of functional bio-polymers.In this paper,catalytic degradation/depolymerization of an alkali lignin was investigated in a supe...Depolymerization of lignin is an important step to obtain lignin monomer for the synthesis of functional bio-polymers.In this paper,catalytic degradation/depolymerization of an alkali lignin was investigated in a supercritical ethanol system.The process conditions were optimized in terms of lignin monomer yield,and the liquid products and solid residue were characterized.Results show that the conversion rate of the alkali lignin was improved in both the Ni7Au3 catalyzed and Nickel-catalyzed systems with supercritical ethanol as the solvent.The maximum lignin conversion rate was 69.57%and 68%respectively for the Ni7Au3 and Nickel-based catalysis systems.Gas chromatography/mass spectroscopy(GC/MS)analysis indicated that the catalytic depolymerization products of alkali lignin were mainly monomeric phenolic compounds such as 2-methoxyphenol.The highest yield of 2-methoxyphenol(84.72%)was achieved with Ni7Au3 as the catalyst.展开更多
This paper summarizes the possible application of lignin extraction from black liquor and the development of lignin extraction technology.Lignin extraction from black liquor is an important,economical method to resolv...This paper summarizes the possible application of lignin extraction from black liquor and the development of lignin extraction technology.Lignin extraction from black liquor is an important,economical method to resolve the bottleneck associated with the recovery boiler and achieve the targeted capacity expansion in pulp mills.A few of key issues must be taken into cosideration when lignin extraction technology is adopted on the industrial scale.展开更多
Tertiary amino alkali lignin( TA-AL) was successfully synthesized by a two-step approach; its application as an adsorbent for nitrate and phosphate ions in effluents was investigated. TA-AL was characterized by FT-IR,...Tertiary amino alkali lignin( TA-AL) was successfully synthesized by a two-step approach; its application as an adsorbent for nitrate and phosphate ions in effluents was investigated. TA-AL was characterized by FT-IR,zeta potential,SEM,and elemental analysis. Kinetic and equilibrium adsorption isotherms were determined to investigate the adsorption capacity of TAAL. The results revealed that TA-AL had a very strong adsorption capacity towards anions; the value of p HPZC( PZC,point of zero charge) was about 9. 2.The adsorption of nitrate and phosphate ions was related to effluent p H and initial anion concentration. The maximum absorption of nitrate and phosphate ions was about 26. 9 and 18. 4 mg / g when the initial concentration of the ions was 50 mg / L. The adsorption kinetics conformed to the pseudo-second-order kinetic equation,and the equilibrium data were suitably expressed by the Freundlich model. The regeneration studies confirmed that the lignin-based material was a promising adsorbent for nitrate and phosphate ions in water.展开更多
基金grateful for the financial support for this work from the National Natural Science Foundation of China(31870560,22108088)the State Key Laboratory of Pulp and Paper Engineering(South China University of Technology),No.202105.
文摘Ferulic acid(FA)and p-coumaric acid(pCA)in bagasse,wheat straw,corn straw,and corncob were extracted by alkaline hydrolysis and characterized by gas chromatography(GC)and gas chromatography-mass spectrometry(GC-MS).It was found that the FA and most of the pCA in gramineous biomass could be dissociated and released after being treated with 1 M NaOH at 100℃for 4 h.The yields of pCA/FA in bagasse,wheat straw,corn straw,and corncob determined by GC-FID are 39.8/11.5,13.7/11.0,28.0/11.0,and 35.1/14.5 mg/g,respectively.The raw materials and the treated solid residues were characterized by gel-state 2D Heteronuclear Single Quantum Coherence Nuclear Magnetic Resonance(2D HSQC NMR).It was found that only a small amount of lignin was detected in the residue after alkali treatment,indicating that the alkali treatment conditions can effectively cleave the FA and pCA.Additionally,the lignin in the alkali solution was recovered and characterized by 2D HSQC NMR.The FA was not able to be detected by NMR,whereas a small amount of pCA remained in the alkali lignin.This study reveals the structural change of residual lignins during the quantitative isolation of FA and pCA,which is essential for the selective isolation of pCA/FA and valorization of residual alkali lignin.
文摘The two kinds of rigid polyurethane （PU） foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.
基金The key project of "11th Five-Year Plan" in Heilongjiang Province (No. GB06B501-3)
文摘The two kinds of rigid polyurethane(PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight.The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams.The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples.The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently.Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples.The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.
基金financially supported by the National Natural Science Foundation of China ( 21774059)the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions
文摘This study performed catalytic depolymerization of alkali lignin over Ni-based catalysts.Effects of different promoters(Zr and W),Ni loadings,reaction temperatures,and the addition of formic acid and catalyst on lignin conversion and products distribution were all investigated.The result showed that the highest oil yield(40.1%(mass))was obtained at 240℃over Ni_(1.2)/γ-Al_(2)O_(3) promoted by Zr and W species.Quantitative analysis indicates that Zr and W species prefer to lignin depolymerization while Ni active phase prefer to hydrodeoxygenation and hydrogenation.The interconversion of products derived from lignin depolymerization was determined by gas chromatography-mass spectrometer,which demonstrated that phenolic compounds were dominant products in all lignin derived bio-oils,wherein the proportion of vanillin was highest(65.7%)at 180℃,while that of alkyl guaiacols increased with the increase of temperature(from 12.45%at 180℃ to 66.67%at 240℃).Residual lignin obtained after lignin depolymerization was also investigated for detecting differences on functional groups,wherein the disappearing peaks at 1511 cm^(-1)(stretching of aromatic rings),1267,1215 and 1035 cm^(-1)(vibrations of guaiacyl and syringyl units)were detected by Fourier transform infrared spectrometry.Additionally,the higher O/C ratio measured by elemental analysis also confirmed that alkali lignin was depolymerized effectively under mild conditions.
基金supported by National Natural Science Foundation of China(No.31800481)Yunnan Fundamental Research Key Projects(No.2019FA012)+2 种基金Science-Technology Support Foundation of Guizhou Province of China(Nos.[2019]2308,[2020]1Y125)Forestry Department Foundation of Guizhou Province of China(No.[2018]13)Cultivation Project of Guizhou University of China(No.[2019]37).
文摘Alkali lignin was processed by plasma and then used in modification of phenol formaldehyde resin in this study.Chemical structural changes of lignin which was processed by plasma as well as bonding strength,tensile property,curing performance and thermal property of the prepared phenol formaldehyde resin which was modified by the plasma processed lignin were analyzed.Results demonstrated that:(1)Alkali lignin was degraded after the plasma processing.The original groups were destroyed,and the aromatic rings collected abundant free radicals and oxygen-containing functional groups like hydroxyls,carbonyls,carboxyls and acyls were introduced into increase the reaction activity of lignin significantly.(2)The introduction of alkali lignin decreased the free formaldehyde content and increased bonding strength and toughness of the prepared phenol formaldehyde resin,especially after the introduction of lignin treated with plasma.(3)The introduction of alkali lignin led to high curing temperature for the prepared phenol formaldehyde resin,but that was reduced by the plasma processed alkali lignin.(4)The introduction of alkali lignin could also increase thermal stability of phenol formaldehyde resin,but that was modified by plasma processed alkali lignin was better than the unprocessed lignin.Based on the results,the plasma processed lignin was used to modify phenol formaldehyde resin,which could increase the strength and toughness of phenol formaldehyde resin significantly.
基金This project was supported by the Forestry Department Foundation of Guizhou Province of China(No.[2018]13)Natural Science Foundation of Guizhou Province(Nos.Qiankehe[2020]1Y125,[2019]1170)+2 种基金the Scientific and Technological Research Project of Guizhou Province(Nos.Qiankehe NY[2019]2325,[2019]2308)Education Department Foundation of Guizhou Province of China(Nos.QianJiaoHe KY Zi[2017]003,[2017]136)the Science and Technology Plan of Guizhou Province(No.Qiankehe Platform Talent[2017]5788).
文摘Lignin is an abundant renewable macromolecular material in nature,and degradation of lignin to improve its hydroxyl content is the key to its efficient use.Alkali lignin(AL)was treated with Brønsted acidic deep eutectic solvent(DES)based on choline chloride and p-toluenesulfonic acid at mild reaction temperature,the structure of the lignin before and after degradation,as well as the composition of small molecules of lignin were analyzed in order to investigate the chemical structure changes of lignin with DES treatment,and the degradation mechanism of lignin in this acidic DES was elucidated in this work.FTIR and NMR analyses demonstrated the selective cleavage of the lignin ether linkages in the degradation process,which was in line with the increased content of phenolic hydroxyl species.XPS revealed that the O/C atomic ratio of the regenerated lignin was lower than that of the AL sample,revealing that the lignin underwent decarbonylation during the DES treatment.Regenerated lignin with low molecular weight and narrow polydispersity index was obtained,and the average molecular weight(Mw)decreased from 17680 g/mol to 2792 g/mol(130°C,3 h)according to GPC analysis.The lignin-degraded products were mainly G-type phenolics and ketones,and small number of aldehydes were also generated,the possible degradation pathway of lignin in this acidic DES was proposed.
基金Program of Introducing Talents of Discipline to Universities,China(No.111-2-04)
文摘Waterborne polyurethane(WPU) binder was synthesized by refined alkali lignin(RAL) with 4,4′-diphenylmethane diisocyanate(MDI).Fourier transform infrared spectroscopy(FTIR) was used to clarify the group change of raw materials-alkali lignin(AL),MDI,and product WPU,and laser particle analyzer was used to analyze the particle size of WPU.The results were as follows: AL could react with MDI to produce WPU binder.The reaction extent,the dispersion,and dispersion stability of WPU were influenced by/ratio.The WPU synthesized by AL,polyethylene glycol(PEG) and MDI was used as a binder in pigment dyeing process.In this process,the influence factors,such as binders made by different ratio of materials,the concentration of binder,curing temperature,and curing time were analyzed respectively.
基金supported by the National Key Research and Development Program of China(Grant 2016YFE0125800)the National Natural Science Foundation of China(Grant 31500492)+4 种基金China Postdoctoral Science Foundation(Grant 2017M612035)Zhejiang Provincial Natural Science Foundation of China(Grant LY16C160005)the Foundation(Grant 201601)of Tianjin Key Laboratory of Pulp&Paper(Tianjin University of Science&Technology)the open fund of State Key Laboratory of Pulp and Paper Engineering(Grant No.201605)the Science Foundation of Zhejiang Sci-Tech University(Grant No.14012079-Y).
文摘Depolymerization of lignin is an important step to obtain lignin monomer for the synthesis of functional bio-polymers.In this paper,catalytic degradation/depolymerization of an alkali lignin was investigated in a supercritical ethanol system.The process conditions were optimized in terms of lignin monomer yield,and the liquid products and solid residue were characterized.Results show that the conversion rate of the alkali lignin was improved in both the Ni7Au3 catalyzed and Nickel-catalyzed systems with supercritical ethanol as the solvent.The maximum lignin conversion rate was 69.57%and 68%respectively for the Ni7Au3 and Nickel-based catalysis systems.Gas chromatography/mass spectroscopy(GC/MS)analysis indicated that the catalytic depolymerization products of alkali lignin were mainly monomeric phenolic compounds such as 2-methoxyphenol.The highest yield of 2-methoxyphenol(84.72%)was achieved with Ni7Au3 as the catalyst.
基金supported by the State Natural Sciences Foundation(No.31270635 and No.31670582)the National Major Fundamental Research Program of China(973 Programs,No.2013CB228101)
文摘This paper summarizes the possible application of lignin extraction from black liquor and the development of lignin extraction technology.Lignin extraction from black liquor is an important,economical method to resolve the bottleneck associated with the recovery boiler and achieve the targeted capacity expansion in pulp mills.A few of key issues must be taken into cosideration when lignin extraction technology is adopted on the industrial scale.
基金the financial support from the provincial scientific and technological project(2011GGB01165)the"Independent Innovation Project of Colleges and Universities"fund by Ji'nan city,Shandong province(No.201004035-2)+1 种基金the national twelfth five-year science and technology support program(No.2014BAC13B04)the"Major Projects for Analysis and Breakthrough of Several Significant Environmental Bottleneck Issues of Economic and Social Development in Shandong Province"(SDHBPJ-ZB-06)
文摘Tertiary amino alkali lignin( TA-AL) was successfully synthesized by a two-step approach; its application as an adsorbent for nitrate and phosphate ions in effluents was investigated. TA-AL was characterized by FT-IR,zeta potential,SEM,and elemental analysis. Kinetic and equilibrium adsorption isotherms were determined to investigate the adsorption capacity of TAAL. The results revealed that TA-AL had a very strong adsorption capacity towards anions; the value of p HPZC( PZC,point of zero charge) was about 9. 2.The adsorption of nitrate and phosphate ions was related to effluent p H and initial anion concentration. The maximum absorption of nitrate and phosphate ions was about 26. 9 and 18. 4 mg / g when the initial concentration of the ions was 50 mg / L. The adsorption kinetics conformed to the pseudo-second-order kinetic equation,and the equilibrium data were suitably expressed by the Freundlich model. The regeneration studies confirmed that the lignin-based material was a promising adsorbent for nitrate and phosphate ions in water.
