Humins,as a group of by-products formed through the condensation and coupling of fragment intermediates during lignocellulosic biomass refining,can cause numerous negative effects such as the wastage of carbon resourc...Humins,as a group of by-products formed through the condensation and coupling of fragment intermediates during lignocellulosic biomass refining,can cause numerous negative effects such as the wastage of carbon resources,clogging of reactor piping,deactivation of catalyst,and barriers to product separation.Elucidating the generation mechanism of humins,developing efficient inhibitors,and even utilizing them as a resource,both from the perspective of atom economy and safe production,constitutes a research endeavor replete with challenges and opportunities.Orbiting the critical issue of humins structure and its generation mechanism from cellulose and hemicellulose resources,the random condensation between intermediates such as 5-hydroxymethylfurfural,furfural,2,5-dioxo-6-hydroxyhexanal,and 1,2,4-benzenetriol etc.were systematically summarized.Additionally,the presence of lignin in real biorefining processes further promotes the formation of a special type of humins known as"pseudo-lignin".The influences of various factors,including raw materials,reaction temperature and time,acid-base environment,as well as solvent systems and catalysts,on the formation of humins were comprehensively analyzed.To minimize the formation of humins,the design of efficient solvent systems and catalysts is crucial.Furthermore,this review investigates the approaches to value-added applications of humins.The corresponding summary could provide guidance for the development of the humins chemistry.展开更多
The formation of humins hampers the large-scale production of 5-hydroxymethylfurfural(HMF)in biorefinery.Here,a detailed reaction network of humin formation at the initial stage of fructose-to-HMF dehydration in water...The formation of humins hampers the large-scale production of 5-hydroxymethylfurfural(HMF)in biorefinery.Here,a detailed reaction network of humin formation at the initial stage of fructose-to-HMF dehydration in water is delineated by combined experimental,spectroscopic,and theoretical studies.Three bimolecular reaction pathways to build up soluble humins are demonstrated.That is,the intermolecular etherification of β-furanose at room temperature initiates the C12 path,whereas the C-C cleavage of a-furanose at 130-150℃ leads to C11 path,and that of open-chain fructose at 180℃ to C11' path.The successive intramolecular dehydrations and condensations of the as-formed bimolecular intermediates lead to three types of soluble humins.We show that the C12 path could be restrained by using HCl or AlCl_(3) catalyst,and both the C12 and C110 paths could be effectively inhibited by adding THF as a co-solvent or accelerating heating rate via microwave heating.展开更多
Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectrosc...Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC …展开更多
Lignite-derived humin(CHM)was extracted from raw coal in Heihe City,China,producing calcium-modifed lignite-derived humin(Ca-CHM)by Ca(OH)_(2).The physical and chemical performances of CHM and Ca-CHM were analyzed wit...Lignite-derived humin(CHM)was extracted from raw coal in Heihe City,China,producing calcium-modifed lignite-derived humin(Ca-CHM)by Ca(OH)_(2).The physical and chemical performances of CHM and Ca-CHM were analyzed with SEM,^(13)C spectra and XPS techniques.The results show that Ca-CHM exhibited weaker aliphatic,more aromatic polar compared with CHM,which improves the adsorption capacity for Cd(Ⅱ).XPS analysis indicates that Ca(Ⅱ)has been loaded onto Ca-CHM successfully after modifcation.This batch adsorption experiments report the adsorption performance of CHM and Ca-CHM for Cd(Ⅱ).The adsorption process of CHM and Ca-CHM for Cd(Ⅱ)conform to pseudo-second-order model,which is chemical adsorption,and the adsorption data presented good fts to the Langmuir model.The maximum adsorption amount(Q_(m))of Cd(Ⅱ)onto CHM and Ca-CHM by the Langmuir model is 15.29 mg/g and 41.84 mg/g,respectively.Based on the results of SEM,^(13)C spectra,and XPS analysis,we concluded that the main adsorption mechanism of Ca-CHM on Cd(Ⅱ)was ion exchange of Cd(Ⅱ)for Ca(Ⅱ),static-adsorbed and surface complexation.Therefore,Ca(Ⅱ)can be loaded on the surface of Ca-CHM by chemical modifcation,improving the adsorption capacity of materials in aqueous solutions.展开更多
The differences in XRD patterns, elemental compositions, FT-IR spectra and TG-DSC curves of extract residues obtained by NaOH, and NaOH assisted with anthraguinone （AQ） extraction procedures were studied. The extrac...The differences in XRD patterns, elemental compositions, FT-IR spectra and TG-DSC curves of extract residues obtained by NaOH, and NaOH assisted with anthraguinone （AQ） extraction procedures were studied. The extract residues are mainly comprised of humin fractions associated with inorganic minerals. XRD analysis shows that there is no typical peak of organic carbon because those organic humin fractions appear as a highly disordered substance. The peak of quartz is dominant. The elementary analysis shows that assistant AQ in NaOH solution can break the link of organic humic substances with inorganic minerals. And aromatization degree of humin fractions obtained by NaOH is smaller than that obtained by NaOH assisted with AQ. FT-IR analysis displays that various groups exist in those two humin fractions obtained by different extraction procedures. There are some differences in FT-IR curves between two humin fractions. TG-DSC analysis shows that thermal decomposition occurs during the heating of testing samples. By contrast, the humin fractions associated with inorganic minerals obtained by NaOH possess a higher thermal decomposition range.展开更多
Humin(HM) is the main organic matter component to af fect the migration and transformation of polycyclic aromatic hydrocarbons(PAHs) in soil. The study on infl uence of the morphology change of inorganic ions on the a...Humin(HM) is the main organic matter component to af fect the migration and transformation of polycyclic aromatic hydrocarbons(PAHs) in soil. The study on infl uence of the morphology change of inorganic ions on the adsorption of PAHs in soil and its organic matter is still rare at microscopic scale. In this paper, yellow soil humin(YS-HM) and lime soil humin(LS-HM) were chosen as samples, then Fe^(3+) and Ca^(2+) were added into samples to facilitate the precipitation by changing the existing conditions of ions, and the mechanism by which inorganic precipitation changed adsorption capacity of karst soil was analyzed from the microscopic scale. The results showed that the adsorption capacity of HM reduced with the inorganic precipitation increasing. The precipitation of Ca^(2+)and Fe^(3+) both reduced the adsorption capacity of YS-HM and LS-HM by 61.71% and 71.83% on average, respectively. The results of scanning electron microscope-energy dispersive spectrometry(SEM-EDS) and pore analysis showed that the HM porosity decreased after formation of Ca^(2+) and Fe^(3+) precipitation. According to the value of Freundlich parameter n, it may be because the precipitation or colloid of Ca^(2+) and Fe^(3+) fi lled micropores and covers high-energy adsorption sites of the HM. This research provides theoretical support for studying the PAHs migration and bioavailability of Calcium-rich in karst soil.展开更多
Humins are common undesirable sideproducts during many acid-catalyzed reactions in renewable biomass platform conversion. However, few studies have been reported to the efficient utilization of humins.For the first ti...Humins are common undesirable sideproducts during many acid-catalyzed reactions in renewable biomass platform conversion. However, few studies have been reported to the efficient utilization of humins.For the first time, the selective catalytic conversion of biomass-derived humins into cyclic hydrocarbons with high conversion rate and selectivity is presented using a home-made Ru/W-P-Si-O bifunctional catalyst. The multistage polymerization structure of humins was studied through controlled experiments.Results show that the CAC bond network can be efficiently depolymerized at a mild reaction temperature of 340–380 °C, catalyzed by the cooperative catalysis of nano-Ru particles and porous strong Lewis solid acid. Particularly, 95.4% conversion of humins was achieved under the optimal condition with up to 88.3%yield of cyclic hydrocarbons. The detailed composition after liquefaction was also analyzed. This study paves the way for the efficient production of cyclic and aromatic hydrocarbons from furan-derived humin polymer through Lewis acid-catalyzed Diels–Alder reactions between furan rings.展开更多
Exploring new strategies to incorporate the concepts of green chemistry and defect engineering into new architectures to address the problem of severe electromagnetic wave(EMW)pollution is challenging.In this work,by ...Exploring new strategies to incorporate the concepts of green chemistry and defect engineering into new architectures to address the problem of severe electromagnetic wave(EMW)pollution is challenging.In this work,by using a by-product of catalytic conversion of biomass as a carbon source,we prepare two-dimensional(2D)Co_(9)S_(8)-coated humins-derived carbon nanomaterials with a yolk-shell structure.The EMW attenuation ability is finally optimized by controlling the morphology and defects of the composite material through the pyrolysis temperature.As expected,with the synergy of conductive loss/interfacial polarization and defects regulating,the composite material achieves a reflection loss(RL)value of−51.4 dB in Ku-band and the effective absorption bandwidth(EAB)can be as high as 5.92 GHz(12.08–18.00 GHz)at 1.8 mm ultra-thin coating thickness.A strong absorption capacity in the low-frequency C-band(6.4 GHz)reaches RL value of−49.9 dB and a thickness of 3.50 mm,which grants it the characteristic of convertible microwave absorption from high frequency to low frequency.Taking account of the facile synthesis and tunable absorption properties,the encouraging findings shed light on exploring waste-turned-microwave absorbents with promising practical applications.展开更多
Studies were conducted to characterize soil humin by acid hydrolysis. Two humin samples collected from two different types of soil, namely chernozem and laterite, which are widespread over a vast area from the north t...Studies were conducted to characterize soil humin by acid hydrolysis. Two humin samples collected from two different types of soil, namely chernozem and laterite, which are widespread over a vast area from the north to south of China, were hydrolyzed under reflux with 0.5M H\-2SO\-4 or 3M H\-2SO\-4 for 4 h. The results showed that \{25%-29%\} of organic carbon and \{46%-54%\} of organic nitrogen could be hydrolyzed by \{0.5M\} H\-2SO\-4; \{36%-40%\} of organic carbon and \{93%-97%\} of organic nitrogen hydrolyzed by 3M H\-2SO\-4. The C/N ratio in hydrolyzed organic matter is lower than that in soil humin and that in organic matter hydrolyzed by 3M H\-2SO\-4 is lower than that in organic matter hydrolyzed by \{0.5M\} H\-2SO\-4. The proportion of nitrogen hydrolyzed from humin is markedly larger than that from the original soil and also markedly larger than that from humic acid fraction. Only \{3%-7%\} of nitrogen in humin exists in a relatively stable form, which is not easy to hydrolyze. There is little nitrogen that occurs in the form of heterocyclic rings in humin. Incubation experiments showed that the newly formed organic matter can be hydrolyzed more easily.展开更多
文摘Humins,as a group of by-products formed through the condensation and coupling of fragment intermediates during lignocellulosic biomass refining,can cause numerous negative effects such as the wastage of carbon resources,clogging of reactor piping,deactivation of catalyst,and barriers to product separation.Elucidating the generation mechanism of humins,developing efficient inhibitors,and even utilizing them as a resource,both from the perspective of atom economy and safe production,constitutes a research endeavor replete with challenges and opportunities.Orbiting the critical issue of humins structure and its generation mechanism from cellulose and hemicellulose resources,the random condensation between intermediates such as 5-hydroxymethylfurfural,furfural,2,5-dioxo-6-hydroxyhexanal,and 1,2,4-benzenetriol etc.were systematically summarized.Additionally,the presence of lignin in real biorefining processes further promotes the formation of a special type of humins known as"pseudo-lignin".The influences of various factors,including raw materials,reaction temperature and time,acid-base environment,as well as solvent systems and catalysts,on the formation of humins were comprehensively analyzed.To minimize the formation of humins,the design of efficient solvent systems and catalysts is crucial.Furthermore,this review investigates the approaches to value-added applications of humins.The corresponding summary could provide guidance for the development of the humins chemistry.
基金the National Natural Science Foundation of China(No.21875149)111 project(B17030)the Basal Research Fund of the Central University.
文摘The formation of humins hampers the large-scale production of 5-hydroxymethylfurfural(HMF)in biorefinery.Here,a detailed reaction network of humin formation at the initial stage of fructose-to-HMF dehydration in water is delineated by combined experimental,spectroscopic,and theoretical studies.Three bimolecular reaction pathways to build up soluble humins are demonstrated.That is,the intermolecular etherification of β-furanose at room temperature initiates the C12 path,whereas the C-C cleavage of a-furanose at 130-150℃ leads to C11 path,and that of open-chain fructose at 180℃ to C11' path.The successive intramolecular dehydrations and condensations of the as-formed bimolecular intermediates lead to three types of soluble humins.We show that the C12 path could be restrained by using HCl or AlCl_(3) catalyst,and both the C12 and C110 paths could be effectively inhibited by adding THF as a co-solvent or accelerating heating rate via microwave heating.
文摘Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC …
基金supported by the National Key R&D Program of China(No.2020YFC1806504)Science and Technology Innovation and venture Fund of China Coal Technology and Engineering Group(No.2020-2-CXY001)We thank the editor and anonymous reviewers for their valuable comments.
文摘Lignite-derived humin(CHM)was extracted from raw coal in Heihe City,China,producing calcium-modifed lignite-derived humin(Ca-CHM)by Ca(OH)_(2).The physical and chemical performances of CHM and Ca-CHM were analyzed with SEM,^(13)C spectra and XPS techniques.The results show that Ca-CHM exhibited weaker aliphatic,more aromatic polar compared with CHM,which improves the adsorption capacity for Cd(Ⅱ).XPS analysis indicates that Ca(Ⅱ)has been loaded onto Ca-CHM successfully after modifcation.This batch adsorption experiments report the adsorption performance of CHM and Ca-CHM for Cd(Ⅱ).The adsorption process of CHM and Ca-CHM for Cd(Ⅱ)conform to pseudo-second-order model,which is chemical adsorption,and the adsorption data presented good fts to the Langmuir model.The maximum adsorption amount(Q_(m))of Cd(Ⅱ)onto CHM and Ca-CHM by the Langmuir model is 15.29 mg/g and 41.84 mg/g,respectively.Based on the results of SEM,^(13)C spectra,and XPS analysis,we concluded that the main adsorption mechanism of Ca-CHM on Cd(Ⅱ)was ion exchange of Cd(Ⅱ)for Ca(Ⅱ),static-adsorbed and surface complexation.Therefore,Ca(Ⅱ)can be loaded on the surface of Ca-CHM by chemical modifcation,improving the adsorption capacity of materials in aqueous solutions.
基金Project(50725416) supported by the National Natural Science Funds for Distinguished Young Scholars of ChinaProjects(CX2009B035,CX2010B063) supported by Graduate Degree Thesis Innovation Foundation of Hunan Province, China
文摘The differences in XRD patterns, elemental compositions, FT-IR spectra and TG-DSC curves of extract residues obtained by NaOH, and NaOH assisted with anthraguinone （AQ） extraction procedures were studied. The extract residues are mainly comprised of humin fractions associated with inorganic minerals. XRD analysis shows that there is no typical peak of organic carbon because those organic humin fractions appear as a highly disordered substance. The peak of quartz is dominant. The elementary analysis shows that assistant AQ in NaOH solution can break the link of organic humic substances with inorganic minerals. And aromatization degree of humin fractions obtained by NaOH is smaller than that obtained by NaOH assisted with AQ. FT-IR analysis displays that various groups exist in those two humin fractions obtained by different extraction procedures. There are some differences in FT-IR curves between two humin fractions. TG-DSC analysis shows that thermal decomposition occurs during the heating of testing samples. By contrast, the humin fractions associated with inorganic minerals obtained by NaOH possess a higher thermal decomposition range.
基金The national natural science Foundations of China under Grant (41761091)The first-class discipline group of geography of Guizhou Province under Grant (N0.[2019]125)+3 种基金Youth Science and Technology Talents Growth Fund of Education Department of Guizhou Province,China (No.KY[2022] 001)Scientific Research Funds of Guiyang University,China (No.GYU-KY-[2022])The Joint Foundation of Guizhou Province under Grant (LH [2017]7348)The Doctor Foundation of Guizhou Normal University under Grant (GZNUD [2017]10)。
文摘Humin(HM) is the main organic matter component to af fect the migration and transformation of polycyclic aromatic hydrocarbons(PAHs) in soil. The study on infl uence of the morphology change of inorganic ions on the adsorption of PAHs in soil and its organic matter is still rare at microscopic scale. In this paper, yellow soil humin(YS-HM) and lime soil humin(LS-HM) were chosen as samples, then Fe^(3+) and Ca^(2+) were added into samples to facilitate the precipitation by changing the existing conditions of ions, and the mechanism by which inorganic precipitation changed adsorption capacity of karst soil was analyzed from the microscopic scale. The results showed that the adsorption capacity of HM reduced with the inorganic precipitation increasing. The precipitation of Ca^(2+)and Fe^(3+) both reduced the adsorption capacity of YS-HM and LS-HM by 61.71% and 71.83% on average, respectively. The results of scanning electron microscope-energy dispersive spectrometry(SEM-EDS) and pore analysis showed that the HM porosity decreased after formation of Ca^(2+) and Fe^(3+) precipitation. According to the value of Freundlich parameter n, it may be because the precipitation or colloid of Ca^(2+) and Fe^(3+) fi lled micropores and covers high-energy adsorption sites of the HM. This research provides theoretical support for studying the PAHs migration and bioavailability of Calcium-rich in karst soil.
基金supported financially by the National Natural Science Foundation of China (No. 21972056)Natural Science Foundation of Inner Mongolia, China (Nos. 2018LH02009 and 2019BS02012)+1 种基金Science Foundation of High Education Institutes of Inner Mongolia, China (No. NJZY20071)Science Foundation Inner Mongolia University of Technology (No. ZZ201804)。
文摘Humins are common undesirable sideproducts during many acid-catalyzed reactions in renewable biomass platform conversion. However, few studies have been reported to the efficient utilization of humins.For the first time, the selective catalytic conversion of biomass-derived humins into cyclic hydrocarbons with high conversion rate and selectivity is presented using a home-made Ru/W-P-Si-O bifunctional catalyst. The multistage polymerization structure of humins was studied through controlled experiments.Results show that the CAC bond network can be efficiently depolymerized at a mild reaction temperature of 340–380 °C, catalyzed by the cooperative catalysis of nano-Ru particles and porous strong Lewis solid acid. Particularly, 95.4% conversion of humins was achieved under the optimal condition with up to 88.3%yield of cyclic hydrocarbons. The detailed composition after liquefaction was also analyzed. This study paves the way for the efficient production of cyclic and aromatic hydrocarbons from furan-derived humin polymer through Lewis acid-catalyzed Diels–Alder reactions between furan rings.
基金financially supported by the Jilin Province Science and Technology Development Plan(No.20210509035RQ).
文摘Exploring new strategies to incorporate the concepts of green chemistry and defect engineering into new architectures to address the problem of severe electromagnetic wave(EMW)pollution is challenging.In this work,by using a by-product of catalytic conversion of biomass as a carbon source,we prepare two-dimensional(2D)Co_(9)S_(8)-coated humins-derived carbon nanomaterials with a yolk-shell structure.The EMW attenuation ability is finally optimized by controlling the morphology and defects of the composite material through the pyrolysis temperature.As expected,with the synergy of conductive loss/interfacial polarization and defects regulating,the composite material achieves a reflection loss(RL)value of−51.4 dB in Ku-band and the effective absorption bandwidth(EAB)can be as high as 5.92 GHz(12.08–18.00 GHz)at 1.8 mm ultra-thin coating thickness.A strong absorption capacity in the low-frequency C-band(6.4 GHz)reaches RL value of−49.9 dB and a thickness of 3.50 mm,which grants it the characteristic of convertible microwave absorption from high frequency to low frequency.Taking account of the facile synthesis and tunable absorption properties,the encouraging findings shed light on exploring waste-turned-microwave absorbents with promising practical applications.
文摘Studies were conducted to characterize soil humin by acid hydrolysis. Two humin samples collected from two different types of soil, namely chernozem and laterite, which are widespread over a vast area from the north to south of China, were hydrolyzed under reflux with 0.5M H\-2SO\-4 or 3M H\-2SO\-4 for 4 h. The results showed that \{25%-29%\} of organic carbon and \{46%-54%\} of organic nitrogen could be hydrolyzed by \{0.5M\} H\-2SO\-4; \{36%-40%\} of organic carbon and \{93%-97%\} of organic nitrogen hydrolyzed by 3M H\-2SO\-4. The C/N ratio in hydrolyzed organic matter is lower than that in soil humin and that in organic matter hydrolyzed by 3M H\-2SO\-4 is lower than that in organic matter hydrolyzed by \{0.5M\} H\-2SO\-4. The proportion of nitrogen hydrolyzed from humin is markedly larger than that from the original soil and also markedly larger than that from humic acid fraction. Only \{3%-7%\} of nitrogen in humin exists in a relatively stable form, which is not easy to hydrolyze. There is little nitrogen that occurs in the form of heterocyclic rings in humin. Incubation experiments showed that the newly formed organic matter can be hydrolyzed more easily.
