FUEL
·
2018
·
IF 4.908
Hui-Chao Hu,Shaokai Zhang,Tong Zeng,Yiying Lin,Liulian Huang,Lihui Chen,Yonghao Ni
In this paper, a robust method based on solvent-volume controlled full evaporation headspace gas chromatography technique (FE HS-GC) was developed to high throughput quantify γ-valerolactone (GVL) concentration in sample solution. The results showed that the full evaporation of GVL can be achieved by the equilibration process in headspace sampler at 150 °C for 5 min. For eliminating the matrix effect and pressure effect on GVL quantification, the sample volume added in headspace vial should be controlled within 15 μL. The present method was proved that has a very high precision (error < 1.11%), high precision (recoveries from 95.6% to 102.1%), and an excellent limit of quantification (153 mg/L). The present method was applied in valuation of GVL yield in a heterogeneous catalytic system and its recovery in a GVL-based biomass pretreatment process, and has given some valuable information. The present method is simple, rapid, efficient, and can be an excellent tool for screening reaction medium and catalysts in GVL synthesis and its related biorefinery processes.
研究领域:
分析化学
·
生物工程
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2017
·
IF 0
Yongdi Xie,Fan Li,Jianjia Wang,Ruiying Wang,Haijun Wang,Xiang Liu,Yongmei Xia
The synthesis of γ-valerolactone (GVL) from catalytic transfer hydrogenation (CTH) of levulinic acid (LA) and its esters is attracting more and more attention due to its wide application in additive, solvent, and precursor. Herein, a novel Zirconium trimetaphosphate (Zr-TMPA) was successfully synthesized and characterized by Fourier transform infrared, N 2 adsorption-desorption, powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and NH 3 /CO 2 -TPD. The as-synthesized Zr-TMPA was used to catalyze the CTH reaction of EL to GVL using isopropanol as the hydrogen donor and solvent. Experimental results shown that Zr-TMPA could catalyze the CTH reaction and 96.2% GVL yield could be achieved at 160 °C for 8 h. Key to this success was attributed to the acid sites and basic sites of the prepared catalyst (Zr-TMPA). Finally, a possible reaction mechanism was proposed.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 32
·14406-14413
·
IF 3.591
Yubo Liu,Guoqiang Ding,Guoping Zhao,Haohao She,Yulei Zhu,Yong Yang
Combining glucose dehydration and the subsequent hydrogenation in one pot is a preferable approach for process development as such a method allows in situ generation of the reactive intermediate to undergo further reaction without extra energy-intensive separation. Herein, phosphotungstic acid and various types of titania (anatase, rutile, P25) supported Ru-based catalysts were considered as the dehydration and hydrogenation catalysts, respectively. Modulating the different reactant media (N2, H2), various products were obtained with GBL–H2O as the solvent. A considerable yield (42%) of levulinic acid (LA) and γ-valerolactone (GVL) (40%) were obtained in nitrogen and subsequent hydrogen. Ru/TiO2 (rutile) was the favorable hydrogenation catalyst among the three types of Ru/TiO2. Meanwhile, a certain amount of sorbitol (36%) was obtained in pure hydrogen. The hydrogenation of glucose is more likely to occur than the glucose dehydration. The physicochemical properties of the catalysts were characterized by XRD, BET, TPR, STEM and in situ CO/FT-IR, and the results show that well-dispersed Ru particles are located on the rutile crystallites, which facilitated the hydrogenation of LA. A strong metal support interaction (SMSI) was responsible for the various microstructure properties and the different hydrogenation reactivity. This work allows a better understanding of the reaction paths of glucose conversion.
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2023
·Vol. 29
·期 52
·e202300950
·
IF 4.3
Fukun Li,Ronghe Yang,Zheng Tian,Ziting Du,Jinhang Dai,Xingmin Wang,Ning Li,Jie Zhang
Graphical Microwave-assisted one pot cascade transformation of furfural to γ-valerolactone catalyzed by Sc(OTf) 3 . γ-Valerolactone (GVL) is considered as a star biochemical which can be used as a green solvent, fuel additive and versatile organic intermediate. In this study, metal triflate (M(OTf) n ) was utilized as the catalyst for one-pot transformation of furfural (FF) to GVL in alcohol media under microwave irradiation. Alcohol plays multiple functions including solvent, hydrogen donor and alcoholysis reagent in this cascade reaction process. And process efficiency of GVL production from FF upgrading is strongly related to the effective charge density of selected catalyst and the reduction potential of selected alcohol. Complex (OTf) n -M−O(H)R, presenting both Brønsted acid and Lewis acid, is the real catalytic active species in this cascade reaction process. Among various catalysts, Sc(OTf) 3 exhibited the best catalytic activity for GVL production. Various reaction parameters including the Sc(OTf) 3 amount, reaction temperature and time were optimized by the response surface methodology with the central composite design (RSM-CCD). Up to 81.2 % GVL yield and 100 % FF conversion were achieved at 143.9 °C after 8.1 h in the presence of 0.16 mmol catalyst. This catalyst exhibits high reusability and can be regenerated by oxidative degradation of humins. In addition, a plausible cascade reaction network was proposed based on the distribution of product.
研究领域:
化学工程
·
生物化工
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FUEL
·
2022
·
IF 8.035
Tianliang Lu,Xianfeng You,Yanlong Zong,Yongming Xu,Xiaomei Yang,Lipeng Zhou
Production of γ-valerolactone (GVL) from ethyl levulinate (EL) was studied by catalytic transfer hydrogenation (CTH) strategy under mild conditions. Hydrothermally synthesized Sn-Beta zeolites with high crystallinity show high catalytic activity and selectivity. With isopropanol as hydrogen source, 97.1 % GVL yield with 100 % selectivity was given under 110 °C. Crystallization time for synthesis of Sn-Beta showed great effect on the catalytic performance. Sn-Beta- x d catalysts with longer crystallization time (≥7 days) have high crystallinity and better catalytic performance. Firstly, longer crystallization time is necessary for the formation of large amount of Lewis acid sites which catalyze the conversion of EL to GVL. Secondly, high level of silanol groups in Sn-Beta has negative effect on the catalytic performance. High crystallinity means the amount of silanol groups in Sn-Beta- x d at a low level which is favorable for this CTH reaction. Meanwhile, this is why hydrothermally synthesized Sn-Beta shows higher catalytic activity than post-synthesized Sn-Beta in the conversion of EL to GVL. Furthermore, the catalyst was reusable.
研究领域:
化学工程
·
催化材料
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2020
·Vol. 10
·期 13
·4412-4423
·
IF 5.721
Qiang Liu,Zhenbo Zhao,Masahiko Arai,Chao Zhang,Ke Liu,Ruhui Shi,Peixuan Wu,Zhuangqing Wang,Weiwei Lin,Haiyang Cheng,Fengyu Zhao
The transformation of γ-valerolactone (GVL) into 1,4-pentanediol (1,4-PDO) and 2-methyltetra-hydrofuran (2-MTHF) in the presence of H2, one of the useful biomass conversion and utilization processes, was investigated with monometallic Cu/Al2O3 and bimetallic ZnCu/Al2O3 catalysts. A 10 wt% Cu-loaded monometallic catalyst produced 1,4-PDO and 2-MTHF in comparable quantities at a medium conversion (∼50%). When Zn was added in a range of Zn/Cu molar ratios of up to 2, in contrast, the catalysts yielded 1,4-PDO in a high selectivity of about 97% at low and high conversion levels. In addition, the 1,4-PDO selectivity over the ZnCu/Al2O3 catalysts remained almost unchanged during recycled runs. That is, the addition of Zn to Cu/Al2O3 switched the product selectivity and improved the catalyst stability and reusability. Furthermore, the physicochemical properties of the catalysts were characterized by several methods including XRD, TEM, TPR, XPS, FTIR of adsorbed pyridine, and so on. On the basis of those results, the relationships between the catalytic performance (activity, selectivity, and reusability) and the catalyst structural features were discussed.
研究领域:
催化化学
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生物质转化
·
材料科学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2015
·
IF 3.942
Jian He,Hu Li,Ye-Min Lu,Yan-Xiu Liu,Zhi-Bing Wu,De-Yu Hu,Song Yang
A series of Al–Zr mixed oxides with different molar ratios were prepared by co-precipitation method and utilized to catalyze conversion of ethyl levulinate (EL) to γ -valerolactone (GVL). Those as-prepared catalysts were characterized by XRD, SEM, N 2 adsorption–desorption, XPS, TG, NH 3 -TPD, CO 2 -TPD and pyridine-IR. The introduction of Al into ZrO 2 was demonstrated to enlarge surface areas, as well as increase the number of acid and base sites that were catalytically active for transfer hydrogenation. Effects of Al–Zr molar ratio, calcination temperature, reaction temperature and time, catalyst dosage, and alcohols used as hydrogen donors on the catalytic performance were investigated. A high GVL yield of 83.2% at EL conversion of 95.5% could be achieved at 220 °C in 4 h over Al 7 Zr 3 -300 using 2-propanol as hydrogen donor and solvent. Poisoning experiments verified that acid–base sites played a synergic role in producing GVL from EL. Moreover, the Al–Zr mixed oxide catalyst was able to be reused for several times with a slight loss in its catalytic activity.
研究领域:
催化化学
·
可再生化学
✓ 已验证
DOI
高影响因子
RENEWABLE ENERGY
·
2026
·
IF 9.1
Jianan Liu,Wei Wang,Xinran Ji,Aimin Li,Lei Zhang
Efficient conversion of lignocellulosic biomass into furan-based chemicals is crucial for sustainable biorefineries. This study presents a synergistic catalytic system combining ferric chloride (FeCl 3 ) with a γ-valerolactone (GVL)/H 2 O co-solvent, revealing the pivotal role of trace water in enhancing furfural production. Under optimized conditions (H 2 O:GVL = 2:28, 180 °C), the system achieved an apparent furfural yield of 109.5 %, calculated based on the theoretical furfural yield from the xylan content of corncob. Mechanistic insights elucidated that Fe 3+ disrupts biomass–solvent interactions, thus facilitating hemicellulose and cellulose depolymerization. The significant 5-HMF yield highlights the system capacity to effectively hydrolyze cellulose into glucose and subsequently convert it via Fe 3+ -catalyzed aldose–ketose isomerization and dehydration pathways. Isotopic labeling with [1– 13 C] and [6– 13 C] glucose confirmed that Fe 3+ catalyzes aldose–ketose isomerization, a critical step steering sugar conversion toward furanic compounds. Furthermore, 2D-HSQC NMR and TG-FTIR-GC/MS analyses revealed that the FeCl 3 –GVL/H 2 O system promoted lignin depolymerization into low-molecular-weight aromatics for enhancing lignin valorization. Together, these findings reveal that trace water lowers the activation energy to accelerate sugar release and modulates the hydrogen-bonding network to stabilize furfural, while the GVL-rich phase stabilizes reactive intermediates, suppressing side reactions and improving furfural selectivity. Compared to conventional mineral acid systems, the FeCl 3 –GVL/trace-water system offers superior selectivity and efficiency under optimized conditions for biorefinery of lignocellulosic biomass.
✓ 已验证
DOI
高影响因子
Catalysts
·
2025
·Vol. 15
·期 6
·530
·
IF 4
Yalin Guo,Zhuang Ma,Binbin Jin,Limin Ma,Guodong Yao
The sustainable valorization of lignocellulosic biomass into high-value platform chemicals presents a crucial pathway for reducing reliance on fossil resources. Gamma (γ)-valerolactone (GVL) has gained recognition as a versatile bio-derived compound with broad applications in renewable energy systems and green chemical synthesis. While conventional GVL production strategies from carbohydrate biomass typically depend on noble metal catalysts paired with high-pressure hydrogen gas, these approaches face substantial technical barriers including catalyst costs, hydrogen storage requirements, and operational safety concerns in large-scale applications. This work develops an innovative catalytic system utilizing earth-abundant iron for in situ hydrogen generation through water splitting, integrated with Raney Ni as the hydrogenation catalyst. The designed two-stage process enables direct conversion of cellulose—first through acid hydrolysis to levulinic acid (LA) followed by catalytic hydrogenation to GVL without intermediate purification. Through systematic parameter optimization, a remarkable 61.9% overall GVL yield from cellulose feedstock was achieved. Furthermore, the methodology’s versatility was demonstrated through wheat straw conversion experiments, yielding 24.6% GVL. This integrated methodology explores a technically feasible pathway for direct cellulose-to-GVL conversion utilizing abundant water as the hydrogen source, effectively overcoming the critical limitations associated with conventional hydrogenation technologies regarding hydrogen infrastructure and process safety.
研究领域:
生物化学
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可再生能源
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Xinyu Wang,Mingyang Hu,Yun Liu
This study investigates a one-step process for the simultaneous separation of cellulose, hemicellulose, and lignin from lignocellulosic biomass using γ-valerolactone (GVL)/H 2 O pretreatment, which also converts hemicellulose to furfural (FF). A response surface methodology (RSM) was applied to optimize the process parameters. Under optimal conditions (163 °C for 1.5 h), the maximum FF yield reached 85.36 %, and cellulose purity was 80.80 %. The extracted GVL-lignin was characterized as low-molecular-weight guaiacyl-syringyl (G-S) type nanospheres with significant antioxidant activity. The conversion of hemicellulose to FF was enhanced by the synergistic interaction of Lewis acid (MgCl 2 ) and Brønsted acid (H 2 SO 4 ), which promoted the isomerization of xylose and dehydration to FF. The high-purity cellulose yielded 18.87 g/L ethanol through separate hydrolysis and fermentation (SHF), 27 times higher than untreated solids. Additionally, GVL exhibited consistent performance in lignocellulose separation after six cycles. This method offers an efficient and sustainable approach to valorize lignocellulosic biomass, advancing the production of high-value products.
研究领域:
生物化学
·
可再生资源与环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
BIOMASS & BIOENERGY
·
2024
·
IF 5.8
Xiaohong Hu,Ying Xia,Haiyong Wang,Xiuzheng Zhuang,Qiying Liu,Song Li,Qi Zhang,Longlong Ma
Until now, research on green and sustainable γ-valerolactone (GVL) pretreatment has predominantly centered on component separation efficiency, with limited attention given to the lignin structure. Nonetheless, the lignin's structure is considerably affected by the fractionation, consequently influencing its potential valorization. Herein, we conducted a holistic investigation of the structural evolution of two fractions of lignin in corn stover, obtained under pretreatment with varying GVL concentrations: GVL lignin (GVLL) originated from pretreatment liquor and cellulolytic enzyme lignin (CEL) separated from pretreated residue. Our findings indicated a general positive correlation between the molecular weight and polydispersity index of both GVLL and CEL with the increasing GVL concentration. This phenomenon is attributed to the enhanced lignin dissolution and relocation as the GVL concentration increases. Moreover, higher GVL concentrations also increased the acidity of reaction system, leading to degradation of β- O -4 linkages from 45.2 to 34.9 and 57.6 to 37.9 per 100 aromatic units in GVLL and CEL, respectively. Compared to CEL, GVLL exhibited a more remarkable phenolics yield (33.7% vs. 22.2%) during hydrodeoxygenation due to its superior purity and lower degree of polymerization. Recycling studies demonstrated the stability of GVL at lower concentrations. These findings provide valuable insights for optimizing GVL pretreatment systems.
研究领域:
化学工程
·
生物化学
·
生物质技术
·
可持续化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
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
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）