Journal of Environmental Chemical Engineering
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2021
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IF 5.909
Putrakumar Balla,Prem Kumar Seelam,Ravi Balaga,Rajendiren Rajesh,Vijayanand Perupogu,Tong Xiang Liang
Sustainable catalysis is the key for the future progress toward biorefinery and bioeconomy. In this work, we designed and developed an inexpensive and eco-friendly Ni@C catalyst for selective hydrogenation of biomass-based platform molecules. A facile synthesized Ni nanoparticles encapsulated in a stabilized carbon support derived from a sacrificial agent copolymer-gel was investigated in the hydrogenation of furfural (FA) to tetrahydrofurfuryl alcohol (THFOL) and levulinic acid (LA) to γ-valeralactone (GVL). The aim is to study the two different reactions over a highly stabilized Ni nanoparticles embedded in the carbon matrix. The Ni@C was found to be active and selective in multi-catalyzed hydrogenation reactions. The Ni nanoparticles with small and ultra-fine sizes are highly dispersed over the carbon matrix. This was concluded through high-resolution micrography images (SEM, TEM) and XRD patterns. In both reactions, a complete conversion of furfural and levulinic acid was achieved with maximum selectivity over the Ni@C catalyst. The effect of reaction temperature, solvent type, reaction time, and H 2 pressure were also studied. Overall, optimized reaction conditions were determined, and the Ni@C is easily reusable and exceptionally durable in the studied reaction cycles. The apparent activation energies for FA hydrogenation to THFOL and LA hydrogenation to GVL are 15.4 kJ/mol and 33.6 kJ/mol, respectively.
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高影响因子
FUEL
·
2021
·
IF 6.609
Rulu Huang,Yao Liu,Junhua Zhang,Junnan Wei,Lincai Peng,Xing Tang
Both value-added utilization of agricultural waste to prepare catalytic materials and selective conversion of biomass-based carbonyl compounds are hot topics. Herein, sugarcane bagasse ( SB ), a main by-product of cane sugar manufacturing industry, was directly assembled with HfCl 4 and methanesulfonic acid (MSA) via a one-step hydrothermal method for scalable preparation of Hf-containing coordination complex (Hf@ SB -MSA). Characterization results revealed that the coordination between Hf 4+ and phenolic hydroxyl, alcohol hydroxyl, carboxyl groups in SB resulting in the formation of Lewis acid (LA) and Lewis base (LB) sites, while sulfonic group in MSA providing Brønsted acid (BA) sites. The cooperative role of LA, BA and LB in Hf@ SB -MSA delivered prominent catalytic performance for catalytic transfer hydrogenation (CTH) of levulinic acid (LvA) to γ-valerolactone (GVL) with isopropanol as solvent and H-donor at mild reaction conditions (GVL yield was up to 99.1%). Heterogeneity and recycling experiments further revealed the good recyclability of Hf@ SB -MSA, which can be easily separated from the reaction mixture by filtration and repetitively used at least five reaction runs without an obvious loss of activity. More gratifyingly, Hf@ SB -MSA also displayed superior universality for the CTH of various carbonyl compounds to their corresponding alcohols with yields up to 90%.
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Journal of Environmental Chemical Engineering
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2021
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IF 5.909
Xi Cheng,Qingge Feng,Dachao Ma,Hongcheng Chen,Xu Zeng,Feifan Xing,Jiayang Teng
To eco-friendly catalyze glucose to levulinic acid, recyclable acid catalyst has been researched. The synthesis process of propyl sulfonic acid functionalized SBA-15 was improved and the hydrophobic treatment was performed. The structure and functional groups of materials were characterized by X-ray diffraction, transmission electron microscopy , N 2 adsorption–desorption isotherms, elemental analysis, Fourier transform infrared spectroscopy , X-ray photoelectron spectroscopy and simultaneous thermal analysis. The catalytic activity , recyclability and hydrothermal stability of CH 3 -SBA-15-SO 3 H material were researched. The highest yield of levulinic acid at 61.56% was obtained at 180 ℃ for 2.5 h in γ-GVL-water solvent system, and the yield of levulinic acid was only decreased by 2% after 4 times reuse. The high degree of silicon polycondension and hydrophobic surface of CH 3 -SBA-15-SO 3 H were the key to maintain the hydrothermal stability. The CH 3 -SBA-15-SO 3 H solid acid had great potential in development and utilization of biomass resources .
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GREEN CHEMISTRY
·
2020
·Vol. 22
·期 13
·4240-4251
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IF 9.48
Jinghua Wang,Hongyou Cui,Yong Wang,Rongrong Zhao,Yujiao Xie,Ming Wang,Weiming Yi
An efficient approach for the synthesis of levulinic acid (LA) by converting cellulose in a biphasic system consisting of molten salt hydrate (MSH), (LiCl·3H2O) and methyl isobutyl ketone (MIBK) using NbOPO4/HZSM-5 as the catalyst was reported. A series of molten salt hydrates (LiBr·3H2O, LiCl·3H2O, ZnCl2·3H2O, CaCl2·3H2O and Ca(NO3)2·3H2O) were evaluated in terms of their cellulose dissolvability and catalytic activity without any additional catalyst in the conversion of cellulose to LA. Among them, LiBr·3H2O, LiCl·3H2O and ZnCl2·3H2O were capable of dissolving and swelling cellulose and demonstrated excellent performance in cellulose conversion to LA even without any additional catalyst. High temperature favors the formation of LA while low temperature is beneficial to saccharides and 5-hydroxymethylfurfural (HMF). Using NbOPO4/HZSM-5, an efficient conversion of cellulose to LA was achieved in a biphasic system, affording a LA yield as high as 94.0%. The partition coefficient of HMF between the MIBK and LiCl·3H2O phases increased notably when the temperature was increased, proving that a biphasic solvent restrained the secondary reaction of HMF to humins. The reaction mechanism study based on the investigation of converting glucose, fructose and HMF to LA found that the side reactions of saccharides to humins are the key factors affecting the selectivity of LA in the investigated reaction system. Therefore, it is crucial to match the cellulose hydrolysis reaction with the subsequent reactions to maintain saccharides including glucose and fructose at low concentrations for highly efficient conversion of cellulose to LA.
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CELLULOSE
·
2019
·Vol. 27
·期 3
·1451-1463
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IF 3.917
Zhou Lipeng,Gao Dongting,Yang Jingru,Yang Xiaomei,Su Yunlai,Lu Tianliang
Abstract Conversion of cellulose to chemicals is an economic and environmental route for biomass utilization. In this work, efficient conversion of cellulose to alkyl levulinates and levulinic acid was realized by oxidation pretreatment combined with alcoholysis over Al 2 (SO 4 ) 3 catalyst. Proper pre-oxidation conditions including oxidation temperature and time are important. By pre-oxidation, part of hydroxymethyl groups on cellulose was converted to carboxyl groups which provide the Brønsted acid sites near the glycosidic bonds to improve the depolymerization of cellulose to monosaccharide. Al 2 (SO 4 ) 3 ·18H 2 O can play both Brønsted and Lewis acid roles in methanol and catalyze the conversion of monosaccharide to alkyl levulinates and levulinic acid. After pre-oxidation at optimized conditions, cellulose can be converted into methyl levulinate and levulinic acid over Al 2 (SO 4 ) 3 in methanol efficiently, and total yield of methyl levulinate and levulinic acid can reach 66.8% at 180 °C for 3 h. Furthermore, the simple and cheap Al 2 (SO 4 ) 3 catalyst is recyclable which is important for the practical application. Graphic abstract
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FUEL
·
2023
·
IF 7.4
Jingyang Zhang,Yucheng Lin,Sibo Zhao,Wei Chen,Qiulin Ma,Liyang Ma,Chun Chang
Levulinic acid (LA), regarded as one of the top twelve biomass-based platform chemicals, has been extensively studied by numerous researchers. In this study, a high LA concentration and yield were obtained through an enhanced in situ feeding strategy with a high loading of furfural residue (FR). The effects of batch process, one-time feeding and two-time feeding strategy on the hydrolysis performance (LA yield and concentrations, as well as intermediate glucose yield and concentrations) were investigated. The humin-based byproducts generated during different processes were also characterized by SEM, FT-IR and XRD analysis. The best results of one-time feeding strategy were obtained at 3 wt% H 2 SO 4 , 170 °C for 60 min with an initial FR concentration of 15% supplemented to 20% at 0th min. Under these conditions, the LA concentration and yield reached 30.00 g/L and 15% (51.1 mol%), respectively. Furthermore, a hybrid model integrated with the shrinking core model and a quasi-first-order kinetic model was adopted to elucidate the kinetic behavior of LA production from highly concentrated substrates through batch and feeding processes. The results indicated that a one-time feeding strategy can lower the activation energy required for FR degradation to glucose to 96.6 kJ/mol ( R 2 > 0.97). Similarly, the activation energy for the conversion of glucose to 5-hydroxymethylfurfural (5-HMF) and the subsequent formation of LA from 5-HMF were reduced to 80.9 kJ/mol ( R 2 > 0.97) and 23.3 kJ/mol ( R 2 > 0.97), respectively. Notably, the reaction rate of glucose to form humins was slightly reduced. This research helps to optimize the LA yield and concentration directly via an enhanced in situ feeding approach, providing valuable process operation and kinetic information for the industrial LA production from FR.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2018
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IF 3.525
Haojie Wang,Chun Chen,Haimin Zhang,Guozhong Wang,Huijun Zhao
Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity, selectivity and stability in catalytical conversion. Herein, we report a facile one-pot carbothermal route to in-situ controllable synthesize heterogeneous bimetallic Ni 3 Fe NPs@C nanocatalyst. The X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and N 2 adsorption-description results reveal that the Ni 3 Fe alloy nanoparticles are evenly embedded in carbon matrix. The as-prepared Ni 3 Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid (LA) to γ-valerolactone (GVL) via both direct hydrogenation (DH) and transfer hydrogenation (TH). In DH of LA, the bimetallic catalyst achieved a 93.8% LA conversion efficiency with a 95.5% GVL selectivity and 38.2 mmol g −1 h −1 GVL productivity (under 130 °C, 2MPa H 2 within 2 h), which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts, respectively. In addition, the identical catalyst displayed a full conversion of LA with almost 100% GVL selectivity and 167.1 mmol g −1 h −1 GVL productivity at 180 °C within 0.5 h in TH of LA. Under optimal reaction conditions, the DH and TH catalytic performance of 500-Ni 3 Fe NPs@C(3:1) catalyst for converting LA to GVL is comparable to the state-of-the-art noble-based catalysts. The demonstrated capability of bimetallic catalyst design approach to introduce dual-catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2012
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IF 2.237
Weina Liu,Yucui Hou,Weize Wu,Zhenyu Liu,Qingya Liu,Shidong Tian,Kenneth N. Marsh
Cellulose is the most widely distributed source of biomass, and its efficient conversion to a variety of chemicals is important for a sustainable future. In this work, sulfur dioxide (SO2) dissolved in hot water has been demonstrated to be an efficient catalyst for the selective conversion of cellulose to chemicals such as glucose and levulinic acid. The selectivity of products can be tuned by the SO2 concentration, temperature, and reaction time. SO2 acts both as a supply of H+ ions through ionization of H2SO3 when dissolved in water and as a Lewis acid catalyst that breaks the hydrogen bonds in cellulose. Importantly, SO2 in the reaction mixture can be recovered completely by stream stripping, thus avoiding the formation of acidic wastewater. This work provides a new, efficient, and environmentally benign way to convert cellulose to chemicals.
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JOURNAL OF CHEMICAL THERMODYNAMICS
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2024
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IF 2.2
Dongmei Xu,Hailin Sun,Nan An,Jun Gao,Lianzheng Zhang,Yixin Ma,Yinglong Wang
Levulinic acid (LA) is a crucial bio-based chemical with extensive industrial applications. Due to its significant share in the cost of production, the development of efficient techniques for the separation of LA is essential. Traditional separation using sulphuric acid raises environmental and cost concerns, making liquid–liquid extraction a more sustainable and cost-effective alternative. liquid–liquid equilibrium (LLE) investigation was carried out for two ternary mixtures of water + LA + isopropyl ether / methyl tert -butyl ether (MTBE) at two temperatures and 101.3 kPa. The results indicated that the solvent MTBE, as an extractant, showed a higher partition coefficient and selectivity for LA than isopropyl ether, demonstrating its superior effectiveness in recovering LA. The interaction insights between LA and the extractants were explored using quantum chemistry calculations, which aligned well with the collected results. The ascertained LLE data was modeled using the NRTL equation, achieving the RMSD values below 0.01, demonstrating a good concordance between the collected data and computed values. The fitted NRTL model parameters are conducive to the designing and optimizing the LA separation process.
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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
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2024
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IF 11.2
Hongguang Zhang,Ying Zhu,Furui Hu,Wuxiang Zhang,Fuzheng Fu,Tao Gan,Zuqiang Huang,Huayu Hu,Yanjuan Zhang
ABSTRACT Water-assisted proton hopping (WAPH) plays an important role in the aqueous-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). In this study, based on a strategy of spontaneously polarized ceramic (SPCE)-reinforced WAPH, a Ni–Co/SPCE–C catalyst was constructed by high-temperature calcination of a dual mechanical activation-treated precursor. Ni–Co/SPCE–C with favorable structural characteristics, intimate interfacial compatibility, and unique spontaneous polarization effect enhanced the migration efficiency of active hydrogen and activated water to form small water clusters, contributing to outstanding catalytic activity for aqueous-phase hydrogenation of LA to produce GVL at relatively low reaction temperature and H 2 pressure. A LA conversion of 99.9% and a GVL yield of 92.3% were achieved at 160°C and 1.5 MPa H 2 over the Ni–Co/SPCE–C catalyst, which were significantly higher than those catalyzed by contrastive catalysts. A variety of tests and theoretical calculations reveal that SPCE with far-infrared emission and surface electric field was conducive to the reduction in the hydrogen spillover energy barrier, the stabilization of the transition state, and the facile exchange of H 2 and water for accelerating WAPH. Moreover, a reasonable SPCE-reinforced WAPH mechanism was proposed to explain the enhanced aqueous hydrogenation of LA. This research can provide valuable insights into the design and development of high-performance non-noble metal catalysts for aqueous hydrogenation applications.
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Catalysts
·
2025
·Vol. 15
·期 5
·416
·
IF 4
Jie Qin,Guohong Chen,Kaiqi Zheng,Jiajun Wu,Fanan Wang,Xueping Liu,Rengui Weng
2-Methyltetrahydrofuran (2-MTHF), a hydrogenated derivative of levulinic acid (LA), is a biomass-derived platform compound with diverse and significant applications as a biofuel, gasoline additive, green solvent, and pharmaceutical synthesis intermediate. This study investigates the preparation of a Cu1Ni2/Al2O3catalyst through the calcination–reduction of CuNiAl hydrotalcite as a precursor, which was subsequently utilized in the hydrogenation of LA to produce 2-MTHF. The calcination–reduction process applied to CuNiAl hydrotalcite results in a lattice confinement effect. This method not only disperses the active metal sites but also alters the bonding patterns of the active metals, thereby enhancing the activity and stability of the Cu1Ni2/Al2O3catalyst. The results indicate that complete conversion of LA and a 2-MTHF yield of 87.6% can be achieved under optimal conditions of 190 °C, 5 MPa hydrogen, and a reaction time of 5 h, demonstrating an efficient one-step conversion process. Additionally, the catalyst’s recyclability was assessed through multiple reuse tests, with a loss of activity of only 9.2% after six cycle experiments, suggesting its feasibility and reliability for industrial applications.
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GREEN CHEMISTRY
·
2021
·Vol. 23
·期 23
·9669-9682
·
IF 10.182
Wang Yue,Lihua Zhang,Lulu Deng,Yuanlong Guo,Qinqin Xu,Wei Peng,Peng Chen,Haibo Xie,Guanglong Zou,Songmiao Liang
Facile dissolution of silk fibroin by using sustainable solvents is the first challenge to be overcome towards its value-added utilization. In this study, sustainable protic ionic liquids (PILs), which were prepared by a simple solventless neutralization reaction of 1,5-diazabicyclo [4.3.0]-5-nonene (DBN) and biomass-derived levulinic acid (Lev), were identified to have good solubility to silk fibroin at mild conditions. Furthermore, the co-dissolution of silk fibroin and cellulose was investigated, and the solute-solvent interaction was elucidated by 13C NMR spectroscopy. The findings demonstrated that the strong hydrogen bonding forming ability of [DBNH][Lev] PILs partially arose from the potential keto–enol tautomerism of levulinate and endowed it with desirable solubility of cellulose and silk fibroin. The rheological properties of cellulose/silk fibroin solutions were systematically studied, indicating that the mass feed ratio of cellulose/silk fibroin significantly affected the apparent viscosity, overlap concentration (c*), activation energy, storage modulus and loss modulus. The interaction and aggregation between cellulose and silk fibroin were further elucidated by dynamic light scattering (DLS). The solution properties provided great opportunities for regenerated cellulose/silk fibroin composited membranes and fiber preparation, and a series of composite membranes were facilely prepared by sol–gel transition using ethanol as a coagulation bath. Various techniques were employed to elucidate the corrections among the structural, morphological, thermal and mechanical properties of the composited membranes and fibers, including infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and tensile tests. It was found that composited membranes (C50S50) had the best mechanical properties, with a tensile strength of 50 MPa and oxygen permeability of 0.0055 cm3 μm (m2 day atm)−1. Moreover, the composited fiber (C80S20) has desirable tensile strength of 152 MPa and an elongation at break of up to 12.8%.
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