ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Yu Zhang,Huai Liu,Rui Zhang,Wenlong Jia,Junhua Zhang,Lincai Peng
Simultaneous utilization of lignocellulose-related glucose and xylose to produce methyl levulinate (ML), a versatile industrial commodity, is important to fully expend biomass components. We herein report a promising catalytic protocol involving the Hβ zeolite in dimethoxymethane (DMM) and methanol (MeOH) cosolvent that enables the coconversion of glucose and xylose to ML under one-pot conditions. ML yield as high as 56% with a turnover frequency (TOF) of over 3.2 h–1 can be accomplished at 150 °C. Isomerization–dehydration of glucose/xylose represents the primary reaction path, whereas the production of glycosides through etherification constitutes the secondary reaction path. The suggested catalytic mechanism is the preferential adsorption of C–O–C and C–OH groups at different acid sites, which leads to the emergence of two distinct pathways for the conversion of glucose/xylose into ML. Hβ-25, featuring a high concentration of Lewis and Brønsted acid sites, facilitates two distinct pathways for the conversion of glucose/xylose into ML. DMM functions as a hydroxymethylation reagent in the conversion of xylose to ML and promotes the isomerization of glycosides via ether exchange reactions. This contribution devises an efficient strategy for producing ML from glucose and xylose while elucidating the reaction mechanism of a tailored monolithic catalytic system.
研究领域:
生物化学
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催化化学
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DOI
高影响因子
Reaction Chemistry & Engineering
·
2025
·
IF 3.1
Yanhong Quan,Yesu Zhang,Jun Ren
Different types of sulfonated styrene resins (SSRs) were applied to the ethanolysis of furfuryl alcohol (FA) to ethyl levulinate (EL). The catalytic performance results showed that the SSR-2 catalyst prepared through sulfonation at 60 °C for 5 h demonstrated the best activity with 100% FA conversion and 97% EL selectivity under the reaction conditions of 126 °C, 2.2 h, and 0.12 g catalyst dosage, which was dramatically superior to the previous results. Notably, the SSR-2 catalyst maintained excellent stability over five cycles, which was attributed to the synergistic effect of the stable, three-dimensional crosslinked network structure of the styrene-based resins and the appropriate SO3H groups, effectively alleviating the leaching problem of the active groups. Innovatively, Response Surface Methodology (RSM) was used to optimize the reaction conditions of FA ethanolysis over the SSR-2 catalyst and the catalyst dosage was identified as the most crucial factor for the production of EL, focusing on the effects of reaction temperature, reaction time and catalyst dosage on EL selectivity. Moreover, the predicted EL selectivity of 97.4% obtained from RSM matched well with the experimental value of 97% under the optimal reaction conditions, paving the way for catalyst engineering in EL production from FA ethanolysis.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Jinghua Wang,Jiangang Wang,Hongyou Cui
Levulinic acid and its esters are promising biomass-derived chemicals. However, high-yield synthesis of them from cellulose is still very challenging. This paper presents a novel formylation-mediated pretreatment strategy for efficiently converting cellulose to methyl levulinate (ML). This strategy is not only straightforward but also notably enhances ML selectivity, especially at high substrate loadings. Mechanism studies show that the cellulose formylation has multiple functions: (1) it reduces the cellulose crystallinity, increases the solubility in the reaction media and thus accelerates the subsequent reactions; (2) the released formic acid from formylated cellulose helps catalyze the cleavage of glucosidic bonds; and (3) more stable intermediates due to the existence of formyl group can suppress the formation of humins. Under optimized reaction conditions, a maximum ML yield of 92.9 % was achieved at a formylated cellulose (CF) loading of 2.5 wt%. Notably, even when the CF loading was increased to 10 wt%, an ML yield of 84.8 % could still be obtained. A rough economic assessment that only took the raw material and energy consumption into account demonstrates that the formylation-mediated process has a lower total input cost and can achieve a 110.4 % profit margin as compared the benchmark due to the higher substrate loading employed and more MF produced from the formyl groups. This research provides a new approach for the large-scale production of levulinates from cellulose.
研究领域:
生物质转化
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催化
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绿色化学
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生物炼制
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有机合成
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DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
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2024
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IF 4.1
Ying Gao,Yong Liu,Lingling Gao,Jinxing Long
An effective strategy is proposed here for transfer hydrogenation of alkyl levulinate to γ-valerolactone (GVL) using a UiO-66 framework modified with phosphotungstate ionic liquid (UiO-66@IL(HPW)). Due to the intensive influence of ionic liquid fragment, the modification significantly enhances the catalytic activity of UiO-66@IL(HPW), leading to a complete conversion of ethyl levulinate with over 93.1% selectivity for GVL. Characterizations techniques, including XRD, N 2 absorption/desorption, SEM, FT-IR, pyridine FT-IR, NH 3 -TPD and CO 2 -TPD, confirm that while the basic structure of UiO-66-NH 2 is insignificantly changed, the introduction of the ionic liquid greatly improves the acidic/base properties of the catalyst. XAFS and XPS results reveal an intensive interaction between the N and W species in UiO-66@IL(HPW), and the formed W-N/O moiety is responsible for the enhanced catalytic activity. In addition, a plausible catalytic mechanism is proposed based upon in situ DRIFTS and density functional theory (DFT) calculations, highlighting the crucial role of ionic liquid fraction within the UiO-66 ligand. Therefore, this work would contribute to the valorization of biochemicals.
研究领域:
化学工程
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材料科学
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DOI
高影响因子
BIOMASS & BIOENERGY
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2025
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IF 5.8
Haoran Wu,Xin Wang,Jingyang Zhang,Zhen Ma,Yucheng Lin,Chun Chang,Xiuli Han
Insight into the alcoholysis kinetics of cellulosic biomass under high solid content to high-value-added ethyl levulinate (EL) is of great significance, but remains challenging due to the co-existence of homogeneous and heterogeneous processes. Herein, the alcoholysis of cellulosic biomass to EL in high solid content systems using CuSO 4 as a catalyst was investigated, employing microcrystalline cellulose (MC) as a model compound and xylose residue (XR) as a real cellulosic biomass. Under solid content of 15 %, the yield and concentration of EL from MC reached 29.50 wt% and 35.01 g/L, respectively, and the yield and concentration of EL from XR could reach 22.77 wt% and 27.01 g/L, respectively. A hybrid model consisting of a shrinking-core model and a pseudo-first-order model was established for the first time. The kinetic data analysis revealed that the reaction rate followed the order of 5-ethoxymethylfurfural → EL > glucose → ethyl glucoside > ethyl glucoside → 5-ethoxymethylfurfural > XR → glucose. Meanwhile, there is no significant dependence between the activation energies and the biomass solid content. The activation energies of XR → glucose, a rate-limiting step of the whole alcoholysis, are in the range of 91.30–94.72 kJ/mol under the condition of solid content ranging from 15 % to 25 %. The lower activation energies indicate the potential of XR as a promising raw material for EL preparation.
研究领域:
生物化学
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可再生资源工程
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DOI
高影响因子
RENEWABLE ENERGY
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2024
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IF 9
Gang Wu,Ke Wang,Shasha Liu,Shanshan Yan,Kuan Ding,Electo Eduardo Silva Lora,Yusuf Makarfi Isa,Yong Huang,Shu Zhang
Transition metal sulfides have rich Brønsted/Lewis's acid sites and various metal valence states, which have great influence on their catalytic performance. In this study, the nickel cobalt sulfides with different molar ratios of Ni to Co were synthesized by one-step solvothermal method for the highly efficient catalytic conversion of cellulose into methyl levulinate (ML). Interestingly, with the continuous incorporation of Ni, the catalytic efficiency of the catalysts increased first and then decreased. It was worth mentioning that when the ratio of Co/Ni is 1, the ML yield was the highest (39.6 wt%), much higher than CoS 2 and NiS 2 (30.5 and 30.1 wt%, respectively). Based on the characterization of the prepared catalysts, it was found that the improved catalytic performance of Ni 0.50 Co 0.50 S 2 was potentially due to the synergistic effect of lower Co 3+ /Co 2+ ratio and larger Ni 3+ /Ni 2+ ratio. Furthermore, the Ni 0.50 Co 0.50 S 2 catalyst had a great recycling performance, which still maintained 78% of the initial catalytic efficiency after reused for 5 times.
研究领域:
化学工程
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催化
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可再生能源
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DOI
高影响因子
APPLIED ENERGY
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2024
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IF 10.1
Haiyang Liu,Zhen Ma,Xueli Liu,Yuan Wu,Weihong Zhang,Shiqiang Zhao,Wei Chen,Chun Chang
The development of novel biobased chemicals is of great research significance in promoting the high-value utilization of lignocellulosic biomass. Methyl levulinate glycerol ketal (MLK) as a novel biobased chemical can be used as a solvent and applied in the fields of polyurethane and coatings. In this paper, the process of continuous preparation of MLK from methyl levulinate (ML) and glycerol (GLY) was studied. The effects of different factors on the yield of MLK and the conversion of GLY were investigated, and the optimum reaction conditions were reaction temperature 140 °C, catalyst HZSM-5 0.50 g, ML to GLY molar ratio 4:1 and weight hourly space velocity (WHSV) of 1.34 h −1 . Under these conditions, the conversion of GLY was 97.00% and the yield of MLK reached 94.70%. The kinetic experiments were further carried out at the temperature range of 130 °C to 150 °C, and the kinetic results showed that the activation energy and the pre-exponential factor were 64.26 kJ·mol −1 and 9.05 × 10 9 mol·g −1 ·s −1 , respectively. Meanwhile, the production efficiency in the continuous process was 1.91 g·h −1 with a turnover frequency (TOF) of 9.00 h −1 , suggesting a higher catalytic efficiency and catalytic activity than that in the batch process. On this basis, a process simulation of the continuous MLK preparation process was further conducted, and the techno-economic evaluation of the process was performed to provide a theoretical reference for the development of the biobased MLK process.
研究领域:
化学工程
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可再生资源利用
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催化科学
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产品关联
DOI
高影响因子
FUEL
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2024
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IF 6.7
Wenli Zhang,Yijie Zhou,Zhenzhen Wu,Cheng Pan,Qunpeng Cheng,Guozhi Fan
A porous sulfonic acid-functionalized zirconium-based metal–organic framework possessing both Lewis acid and Brønsted acid sites (UiO-66-SO 3 H) was synthesized and tested for the selective conversion of furfural (FUR) to isopropyl levulinate (IPL) through one-pot cascade reaction. UiO-66-SO 3 H exhibited excellent catalytic performance, and the conversion of FUR as well as the yield and selectivity of IPL reached 96.4 %, 86.0 %, and 89.2 %, respectively. UiO-66-SO 3 H could be simply recovered and reused, but the catalytic performance was significantly decreased. The FUR conversion and IPL yield dropped to 73.8 % and 65.1 %, respectively, after 1 cycle, and the reason for the decrease in the catalyst activity were also investigated. It was found that the decrease was mainly caused by the loss of some −SO 3 H groups, and the cyclic performance of UiO-66-SO 3 H could be restored by supplementing a small amount of BDC-SO 3 Na. A plausible mechanism for the selective synthesis of IPL from FUR was proposed, wherein both Lewis acid and Brønsted acid sites played important roles. This work provides guidance for the selective conversion of FUR into IPL, and the high-valued utilization of biomass and its derivatives.
研究领域:
化学工程
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催化科学
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可再生资源利用
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DOI
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2019
·Vol. 94
·期 10
·3073-3083
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IF 2.659
Jing Gu,Jun Zhang,Denian Li,Haoran Yuan,Yong Chen
BACKGROUND Catalytic upgrading of biomass into various alkyl levulinates has gained wide attention recently. Particularly, ethyl levulinate (EL) shows great potential as gasoline additive and substitute of biodiesel fuels. RESULTS Hyper-cross-linked organic polymer based carbonaceous materials with large surface areas and strong Brϕnsted acidity were synthesized and developed as highly efficient solid acids for the direct transformation of biomass derived carbohydrates into biofuel candidate ethyl levulinate (EL). Controllable Brunauer–Emmett–Teller (BET) surface area and proper acid density of as-prepared carbonaceous materials were demonstrated to be crucial for the successful synthesis of EL. Among the catalysts, α,α′-dichloro- p -xylene derived hyper-cross-linked organic carbocatalyst (HDS-3.6) exhibited the best results for EL formation with the optimal yield of 70.3% at a temperature of 423 K, which was comparable with those of frequently-used solid acids such as commercial Amberlyst-15 and metal oxides. The presence of dimethyl sulfoxide (DMSO) in the catalytic system facilitated the production of intermediates 5-hydroxymethylfurfural (HMF) and 5-ethoxymethylfurfural. Notably, the hyper-cross-linked organic polymers with abundant Brϕnsted acid sites were much more effective in the catalytic synthesis of levulinate esters from ketoses. CONCLUSION The prepared hyper-cross-linked organic polymers were efficient and robust catalysts to produce various biomass derived alkyl levulinates with high activity and stability. © 2019 Society of Chemical Industry
研究领域:
化学工程
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催化科学
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可再生资源转化
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DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
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2020
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IF 4.982
Chaonan Tao,Lincai Peng,Junhua Zhang,Liang He
Efficient production of fuels and chemicals from lignocellulosic biomass is the main goal of biorefinery processes. Herein, the metal-modified heteropolyacids with tunable Lewis and Brønsted acid sites were designed as the monolithic multifunctional catalyst for valorizing cellulose and lignocellulosic biomass to alkyl levulinate, a versatile platform molecule. Among them, Al-exchanged two protons of H 4 SiW 12 O 40 (Al 2/3 H 2 SiW 12 O 40 ) was found to be uniquely effective. The kinetic behavior describing the conversion of cellulose to ethyl levulinate was investigated to monitor the process, and compared between parent H 4 SiW 12 O 40 and Al 2/3 H 2 SiW 12 O 40 to understand the mechanistic role of Al 3+ . The introduction of Al 3+ substantially facilitated cellulose depolymerization and glucose-to-fructose isomerization , leading to a high rate and product selectivity. The estimated activation energies for cellulose degradation and glucopyraoside alcoholysis decreased by 50.6 kJ/mol and 40.9 kJ/mol, respectively. 50–72% yields of ethyl levulinate were accomplished from cellulosic biomasses such as pine wood, eucalyptus, bamboo, bagasse and Napier grass. Al 2/3 H 2 SiW 12 O 40 allowed cellulose conversion in various linear alcohols producing high-yield alkyl levulinate, and could be reused multiple times with a good stability. This study opens a reliable and promising avenue for one-pot transformation of cellulose and raw lignocellulosic biomass to ester compounds.
研究领域:
生物化学
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可再生资源工程
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DOI
高影响因子
MOLECULES
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2019
·Vol. 24
·期 10
·1881
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IF 3.06
Geng Zhao,Ming Liu,Xinkui Xia,Li Li,Bayin Xu
In this study, a carbon-based solid acid was created through the sulfonation of carbon obtained from the hydrothermal pretreatment of glucose. Additionally, ethyl levulinate, a viable liquid biofuel, was produced from furfuryl alcohol using the environmentally benign and low-cost catalyst in ethanol. Studies for optimizing the reaction conditions, such as reaction time, temperature, and catalyst loading, were performed. Under the optimal conditions, a maximum ethyl levulinate yield of 67.1% was obtained. The recovered catalyst activity (Ethyl levulinate yield 57.3%) remained high after being used four times, and it was easily regenerated with a simple sulfonation process. Moreover, the catalyst was characterized using FT-IR, XRD, SEM, elemental analysis, and acid-base titration techniques.Keywords:furfuryl alcohol;ethanol;ethyl levulinate;carbon-based solid acid
研究领域:
化学工程
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可再生资源与环境科学
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2017
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IF 9.446
Lingyun Jiang,Lipeng Zhou,Jinyu Chao,Huiting Zhao,Tianliang Lu,Yunlai Su,Xiaomei Yang,Jie Xu
Conversion of biomass derived carbohydrates to alkyl levulinates is an important process due to the wide application of alkyl levulinates as chemicals and biofuel additives. Efficient conversion of cheap and abundant glucose to alkyl levulinates over easily separated and regenerated solid catalyst is highly desirable. Here, the transformation of glucose to methyl levulinate (MLE) was studied over dual solid acid catalysts. The synergistic effect of solid Brønsted (B) acid and solid Lewis (L) acid was observed. A combined catalyst system consisting of both B acid and L acid was found to be more efficient for the production of MLE from glucose. 62% yield of MLE was given over the combined catalyst of SO 4 2− /ZrO 2 and Sn-Beta prepared by postsynthesis method at 170 °C for 24 h. The roles of L acid sites of SO 4 2− /ZrO 2 and Sn-Beta, and B acid sites of SO 4 2− /ZrO 2 were discussed in detail. Alternative biomass-derived carbohydrates also gave moderate to good yields of MLE. Recyclability studies indicated that the combined catalyst system can be reused without significant change in the yield of MLE, proving its easy recovery and thermal stability during regeneration.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）