JOURNAL OF THE ENERGY INSTITUTE
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2025
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IF 6.2
Xiaomeng Kang,Mingqin Xue,Xue Wu,Xiaohui Yang,Minghao Zhou
Catalytic upgrading of lignin-derived bio-oil to value-added chemicals was of great significance for the utilization of biomass resources. Hydrodeoxygenation (HDO) was widely regarded as a promising pathway for the upgrading of lignin-derived bio-oil. And the key to this issue was to develop effective and sustainable catalysts. In this study, a series of lignin-derived carbon-based highly effective catalysts were synthesized through a one-step hydrothermal method for the catalytic HDO of lignin and its derivatives. Then, lignin-MOF-derived catalysts (nCo-TPA/C-T) were successfully applied to the catalytic HDO of lignin-derived phenolics. All catalysts were characterized in detail to investigate the relationships between physicochemical properties and their catalytic performances. The results demonstrated that the catalyst 2Co-TPA/C-500 exhibited excellent catalytic activity in the conversion of vanillin (VAN) to 2-methoxy-4-methylphenol (MMP) in mild condition (160 °C, 0.5 MPa N 2 , and 1 h), without the presence of external hydrogen. The conversion of VAN was up to nearly 100 %, with a high selectivity of MMP (about 94.5 %). It was confirmed that the excellent catalytic performance was related to types of organic ligands, metal-ligand ratio, catalyst calcination temperature, etc. The catalysts also exhibited good activity for other lignin-derived phenols. This work could offer a useful strategy for the catalytic upgrading of lignin-derived phenolics into value-added chemicals.
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2025
·
IF 3.9
Jian Wei,Yucui Hou,Tianqi Huang,Aohua Zheng,Shuhang Ren,Weize Wu
Identifying the source of products in lignin hydro-liquefaction oil is crucial for assessing the lignin conversion efficiency. The utilization of hydrogen donor solvents (HDSs) complicates the determination of whether polycyclic aromatic hydrocarbons (PAHs) derive from lignin or HDS. Thus, identifying the source of PAHs in the oil can improve our understanding of lignin structures and enhance its utilization. To address this challenge, 1,2,3,4-tetrahydroquinoline (THQ) was used as an HDS to trace products within the oil. The results showed that (1) lignin could be completely liquefied in THQ under optimal conditions: a THQ/lignin mass ratio of 0.5, a reaction temperature of 450 °C, an initial H2 pressure of 8 MPa, a reaction time of 4 h, and a molybdenum sulfide/lignin mass ratio of 1; (2) PAHs with 2–6 rings were identified in the oil and confirmed to derive solely from lignin through qualitative and quantitative analyses via GC–MS rather than THQ.
研究领域:
能源化学
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环境科学
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生物质转化
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高影响因子
MOLECULES
·
2024
·Vol. 29
·期 2
·347
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IF 4.2
Fangli Du,Xuequan Xian,Peiduo Tang,Yanming Li
A sulfonyl-chloride-modified lignin-based porous carbon-supported metal phthalocyanine catalyst was prepared and used to replace the traditional Fenton’s reagent for lignin degradation. The catalyst underwent a detailed characterization analysis in terms of functional group distributions, surface area, morphological structure, via FT-IR, XPS, BET, and SEM. The catalyst possessed a specific surface area of 638.98 m2/g and a pore volume of 0.291 cm3/g. The prepared catalyst was studied for its ability of oxidative degradation of lignin under different reaction conditions. By optimizing the reaction conditions, a maximum liquid product yield of 38.94% was obtained at 135 °C with 3.5 wt% of catalyst and 15 × 10−2mol/L H2O2; at the same time, a maximum phenols selectivity of 32.58% was achieved. The compositions and properties of liquid products obtained from lignin degradation using different catalyst concentrations were studied comparatively via GC-MS, FT-IR,1H-NMR, and EA. Furthermore, the structure changes of solid residues are also discussed.
研究领域:
化学工程
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环境科学
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DOI
PubMed
高影响因子
FUEL
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2024
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IF 6.7
Yuqaio Ma,Xinping Ouyang,Lisha Zhao,Lifeng Li,Xueqing Qiu
The lignin-first strategy is a crucial approach for highly efficient depolymerization of lignin to produce aromatic monomers as the condensation of lignin occurred during the separating process which increased the difficulty in depolymerization. In this work, a cobalt atom clusters supported on nitrogen-doped carbon catalysts (Co/NC-15) was prepared by adjusting the dosage of melamine to control the morphology, structure, and pyridinic nitrogen content of the catalysts. DFT calculations based on lignin model showed that the doping of nitrogen increased the adsorption energy of the lignin on the supports and decreased the dissociation energy of C-O bonds. Under lignin first strategy, Co/NC-15 exhibited good ability to break C-O bonds at 220 °C of mild condition, in which 84.32 wt% of lignin in lignocellulosic biomass was converted into 40.62 wt% of aromatic monomers, while 84.02 wt% of cellulose was preserved. The atom clusters Co/NC-15 exhibited good catalytic activity to lignin depolymerization due to efficient cleavage of C-O bonds, and hence showed the promising prospect in potential industrial application.
研究领域:
生物化学
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催化化学
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高影响因子
GREEN CHEMISTRY
·
2025
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IF 9.2
Yaling Zhao,Deqing Zhao,Jingpeng He,Kaibin Ma,Jiatian Zhu,Jianrong Liu,Yongqi Zhang,Qinqin Xia,Ting Li
A lignin-first separation strategy can help improve the economic and environmental benefits of biorefinery. However, the self-condensation of lignin remains an insurmountable bottleneck in its isolation and valorization process. Therefore, the challenge of lignin separation is how to achieve a highly uncondensed lignin with high yield and high purity. In this work, we developed a ternary deep eutectic solvent (DES) based on polyhydric alcohols, which can be used to treat moso bamboo at 80–90 °C to obtain highly uncondensed lignin which is light-colored and highly active. The uncondensed lignin exhibits a high β-O-4 retention rate, up to 52.82/100Ar, accounting for 90.24% of the β-O-4 content in the raw material. At the same time, the maximum yield and purity of uncondensed lignin can reach 33.6% and 95.5%, respectively. Furthermore, through DFT theoretical calculations, we have proved that the lignin protection strategy by 1,2-propanediol is achieved by grafting the hydroxyl functional group to the α position of the benzylic carbocation intermediate, thus revealing the intrinsic mechanism by which polyol effectively blocks lignin condensation. The lignin-first fractionation strategy based on ternary deep eutectic solvents with polyhydric alcohols and Lewis acids overcomes the defects of lignin condensation that is inevitable during lignin separation and depolymerization. It obtains highly uncondensed lignin with high yield and high purity, and provides a new idea for biorefinery under the lignin-first separation strategy.
研究领域:
生物化学
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材料科学
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可再生资源工程
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高影响因子
INDUSTRIAL CROPS AND PRODUCTS
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2024
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IF 5.6
Xialin Ji,Xiaoke Tian,Mengqing Zhou,Changzhou Chen,Jianchun Jiang
In this study, different kinds of lignin, including enzymatic hydrolysis of lignin (EHL), alkaline lignin (AL), kraft lignin (KL) and sodium lignosulfonate (LS) were investigated as precursor to prepare Ni@BTC@X (X= EHL, AL, KL, LS) catalysts using a traditional hydrothermal method with Ni-MOF for HDO upgrading of lignin derivative vanillin (VAN) to generate high value chemical 2-methoxy-4-methylphenol (MMP). The catalytic performance of these catalysts was investigated under different reaction conditions, and it was explored that the conversion of VAN was close to 100 % and the MMP yield was close to 90 % under the optimal conditions (Ni@BTC@LS catalyst, 220 ℃, 4 h, isopropanol, 2 MPa N 2 ). Various physical-chemical characterization results verified that the effects of active sites Ni, porous structure of lignin biochar support and electronic properties of the catalysts played a significiant role in HDO of lignin derived VAN. Additionally, synergistic effect of the highly homogeneously dispersed oxygen vacancies and acidic sites also promoted the VAN conversion efficiency. This work developed a strategy combing the advantages of MOFs and biomass derived substrates for manufacturing novel lignin/MOFs materials in the catalytic field.
研究领域:
化学工程
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环境科学
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催化材料
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高影响因子
JOURNAL OF THE ENERGY INSTITUTE
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2021
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IF 6.186
Lin Hu,Xian-Yong Wei,Yu-Hong Kang,Xian-Hou Guo,Mei-Ling Xu,Zhi-Ming Zong
Recently high yield of cycloalkanes originates from selective hydrodeoxygenation (HDO) of lignin-derived bio-oil under mild conditions, which still encounters the great challenges. Herein, mordenite-supported ruthenium bifunctional catalyst (Ru 3% /M) was prepared by using the deposition-precipitation (DP) method for the HDO reaction of the petroleum ether-extractable portions (PEEP) from alkali catalytic ethanolysis of lignin (CEOL). Ru 3% /M catalyst was characterized systematically by XRD, XPS , FTIRS , NH 3 -TPD, N 2 -adsorption, SEM , and TEM, indicating that it had the moderate acid sites and uniform Ru nanoparticles dispersion. The synthesized catalyst was further tested for the HDO performance of diphenyl ether, oxybis(methylene)dibenzene, and anisole, respectively. Results showed that three lignin model compounds can be converted to high yield of cycloalkanes under 160 °C and 3 MPa H 2 in n -hexane. This catalyst showed the high catalytic activity for diphenyl ether HDO reaction, the conversion decreased slightly to 87.6% after five recycle times. Furthermore, catalyst feed mass was the key factor for HDO reaction of raw PEEP from CEOL, promoting the HDO reaction process to produce high yield of cycloalkanes. Interestingly, the mass ratio between catalyst feed and raw PEEP was 1, thus 74.36% relative content (RC) of cycloalkanes can be obtained. The upgraded PEEP from CEOL has potential to be used as clean liquid fuels.
研究领域:
化学工程
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可再生能源
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催化科学
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高影响因子
INDUSTRIAL CROPS AND PRODUCTS
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2019
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IF 4.191
Wenlong Xiong,Dongjie Yang,Md. Asraful Alam,Jingliang Xu,Yuanyuan Li,Huan Wang,Xueqing Qiu
In this work, cationic lignin derivatives were synthesized by grafting reaction of lignin and 3-chloro-2-hydroxypropyltrimethylammonium chloride. Then the synthesized cationic lignins were used to prepare lignin/silica nanocomposites (LSNCs) via a green co-precipitation method. The following characterizations, particle size distribution, SEM, TEM, XRD, FT-IR, XPS, static contact angle, specific surface area, and pore size distribution, were employed to understand the dispersity, morphology, crystal structure, and textural property of different LSNCs. The results showed that lignin with low content of cationic quaternary ammonium (QA) groups couldn’t support the formation of uniform LSNCs, while lignin with moderate content of QA groups leaded to the formation of uniform LSNCs with a core-shell structure, lignin/silica hybrids in inner side and thin layer of lignin on surface. When the content of QA groups in lignin was high, the prepared LSNCs presented porous strawberry-like structure, lignin/silica hybrids at inside and coating layer of silica nanoparticles within 10 nm on surface.
研究领域:
材料科学
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化学工程
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高影响因子
CELLULOSE
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2022
·Vol. 29
·期 4
·2273-2287
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IF 6.123
Liu Yifan,Chen Beiqiu,Lv Yuancai,Ye Xiaoxia,Lin Chunxiang,Liu Minghua
Residual lignin affects the physical and chemical performance of lignin-containing cellulose nanofibers (LCNFs). In this work, LCNFs were prepared from sugarcane bagasse powder (SBP) through p -toluenesulfonic acid ( p -TsOH) hydrolysis and the subsequent homogenization treatment. By adjusting the concentration of p -TsOH and hydrolysis temperature, LCNFs with lignin content of 4.69–17.53% were obtained, and the effects of lignin content on the chemical structure, crystallinity, size, hydrophobicity and thermal stability of LCNFs were systematically studied. With the increase of lignin content, the diameters and average water contact angles of LCNFs were increased (from 169.65 to 781.56 nm and 39.74–86.16°, respectively), while the crystallinities were decreased. The thermal stabilities of LCNFs were decided both by lignin content and the crystallinity. The by-product lignin nanoparticles (LNPs) with an average diameter of 50–500 nm were generated with LCNFs, further improving the resource utilization value of SBP. This study provides theoretical and experimental basis for the subsequent processing of films with different hydrophobic properties and materials with higher mechanical properties and thermal stability. Graphical abstract
研究领域:
材料科学
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化学工程
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高影响因子
FUEL
·
2022
·
IF 8.035
Minghao Zhou,Chengjun Tang,Jing Li,Haihong Xia,Peng Liu,Junming Xu,Changzhou Chen,Jianchun Jiang
Ni-based MOFs catalysts are promising candidates that can be used to achieve biomass valorization following the process of selective hydrogenolysis process. Here we report a spherical NiCo-based MOFs catalyst, which provides a larger BET surface to enhance 2-phenoxy-1-phenylethan-1-ol molecules enrichment and promote the hydrogenolysis on spherical NiCo-based MOFs catalyst surface. In addition, the synergistic interaction between Ni and Co species also shows great effect on catalytic hydrogenolysis of 2-phenoxy-1-phenylethan-1-ol molecules and enzymatic lignin. The yields of ethylcyclohexane and cyclohexanol are dramatically improved to more than 90 mol% over Ni3Co1-based MOFs catalyst under nitrogen atmosphere. Various lignin dimers derivatives are investigated over Ni3Co1-based MOFs catalyst, which indicates oxygen-containing functional groups played a critical role in the hydrogenolysis process. Isopropanol is used as solvent in the hydrogenolysis of 2-phenoxy-1-phenylethan-1-ol molecules and enzymatic lignin. 21% of H 2 is observed in the GC/MS, suggesting that it is a catalytic transfer hydrogenolysis process. Catalytic hydrogenolysis of enzymatic lignin is also carried out under 280 ℃ over optimal Ni3Co1-based MOFs catalyst for 6 h, giving highest lignin oil yield (75.6 wt%) and lower O/C ratio (0.17). This work can be extended to different biomass valorizations to promote the catalytic behavior of spherical MOFs catalysts.
研究领域:
催化化学
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生物质能
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材料科学
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高影响因子
CARBOHYDRATE POLYMERS
·
2023
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IF 11.2
Jiran Dong,Jinsong Zeng,Pengfei Li,Jinpeng Li,Bin Wang,Jun Xu,Wenhua Gao,Kefu Chen
Lignin-containing cellulose nanopapers are emerging multifunctional materials in the fields of coatings, films, and packaging. However, the forming mechanism and properties of nanopapers with various lignin content have not been thoroughly studied. In this work, a mechanically strong nanopaper was fabricated based on lignin-containing cellulose micro- and nano-hybrid fibrils (LCNFs). The influence of lignin content and fibrils morphology on the formation process of nanopapers was investigated to understand the strengthening mechanism of nanopapers. LCNFs with high lignin content provided nanopapers with intertwined micro- and nano-hybrid fibrils layers with small layer spacing, while LCNFs with low lignin content offered nanopapers interlaced nanofibrils layers with large layer spacing. Although lignin was expected to interfere with hydrogen bonds between fibrils, the uniformly distributed lignin contributed to the stress transfer between fibrils. Due to the good coordination between microfibrils, nanofibrils and lignin (as network skeleton, filler and natural binder, respectively), the well-designed LCNFs nanopapers with lignin content of 14.5 % showed excellent mechanical properties, including tensile strength (183.8 MPa), Young's modulus (5.6 GPa) and elongation (9.2 %). This work deeply reveals the relationship between lignin content, morphology and strengthening mechanism of nanopapers, and providing theoretical guidance for employing LCNFs as structural and reinforcing materials to design robust composites.
研究领域:
材料科学
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林业工程
·
生物质材料
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DOI
PubMed
高影响因子
MATERIALS LETTERS
·
2023
·
IF 3
Xiaobao Li,Xiaolin Ma,Xuejuan Zhao
To improve the dispersion and crystallization of layered double hydroxides (LDHs), black liquor lignin was used as both the carrier and the intercalation modifier agent to prepare lignin–MgAl layered double hydroxide (Lignin-LDH) composites by a hydrothermal method. Fourier-transform infrared spectroscopy showed that the amount of NO 3 − inserted into the LDH interlayers decreased significantly with the increase of the lignin content. X-ray diffraction revealed that the crystallization of LDH in the Lignin-LDH composites was enhanced by the hydrothermal treatment, and the crystal structure of the LDH was more disordered with the increase of the lignin content. Thermogravimetric analysis showed that hydrothermal treatment and the addition of lignin were beneficial for enhancing the thermal stability of the Lignin-LDH composites. The basal spacing of the LDH was unchanged based on Bragg equation calculations. Based on the infrared and thermogravimetric analysis results, it can be inferred that the molecules of dissolved hydroxyl compounds were inserted into the LDH interlayers. Scanning electron microscopy showed that the hydrothermal treatment promoted the growth of LDH crystals, and the increase of the lignin amount resulted in the dispersion of LDH in lignin and a decrease of the LDH thickness.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
危险品化学品经营许可证（带存储）