JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2024
·Vol. 99
·期 4
·922-930
·
IF 2.8
Dingshuo Zhang,Heqian Zhang,Yue Li,Daolai Sun,Jianhua Lv
BACKGROUND Levulinic acid is an important platform chemical derivable from lignocellulosic biomass. In this work, the hydrogenolysis of levulinic acid to produce 1,4-pentanediol was performed over some Co-based non-noble catalysts. The relationship between the catalyst properties and the catalytic activity was investigated, and the effects of the reaction conditions on the catalytic activity were studied. RESULTS The Co/ZrO 2 catalyst prepared by a coprecipitation method showed a high catalytic performance in the hydrogenolysis of levulinic acid to form 1,4-pentanediol. The calcination of Co/ZrO 2 significantly affected the catalytic activity, and a high calcination temperature of 750 °C could promote the formation of 1,4-pentanediol. Meanwhile, the reduction of Co/ZrO 2 at 400 °C in an H 2 flow was beneficial for producing 1,4-pentanediol, and the Co species after the reduction existed as the forms of Co 2+ and Co 0 . A high H 2 pressure and a moderate reaction temperature of 200 °C were beneficial for producing 1,4-pentanediol, and a high 1,4-pentanediol selectivity of 85.6% with a complete conversion of levulinic acid was obtained over the Co/ZrO 2 catalyst at 200 °C under an H 2 pressure of 7 MPa. CONCLUSION The Co species in the 400 °C-reduced Co/ZrO 2 catalyst existed as the forms of Co 2+ and Co 0 . It was proposed that the synergistic effect of Co 2+ and Co 0 contributed to the effective formation of 1,4-pentanediol from levulinic acid. © 2024 Society of Chemical Industry (SCI).
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2024
·
IF 3.8
Ruixue Zhang,Weiyao Yang,Hongda Zhang,Le Sang,Zhiping Zhao
This work presents the efficient, safe, and continuous production of 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) from inulin in micropacked bed reactors (μPBRs) over HND-580. Through optimization reaction conditions, the highly selective production of fructose and LA from aqueous inulin and HMF from an inulin DMSO-water mixed solution can be achieved with respect to other reactor technologies. The highest yields of 89% for fructose, 81% for HMF, and 84% for LA can be obtained within a reaction time of 7.26 min. Polysaccharide inulin is used as the reaction substrate, and the space-time yield (STY) of HMF and LA in μPBRs is at least an order higher than that in conventional batch reactors. Subsequently, an intrinsic kinetic model for inulin conversion is established. The most predicted values show good agreement with the experimental results with a relative error of ±20%.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Jun Jiang,Teng Li,Kexin Huang,Guangyu Sun,Jing Zheng,Jinlong Chen,Weiran Yang
As a bio-based platform chemical, it is desirable to convert levulinic acid (LA) to varieties of value-added biochemicals. n-Butane, mainly from nonrenewable fossil resources, is a basic chemical to produce some important chemicals, such as butadiene and ethylene. In this paper, 95.5% yield of n-butane was obtained from LA in one-step over base-treated Pt/C at around 300 °C in 4 h. The reaction pathway was confirmed to be the hydrodeoxygenation of LA to valeric acid (VA) and then the VA decarboxylation to n-butane by kinetic studies. Base-treated Pt/C had better reactivity due to its improved decarboxylation activity. Detailed characterization of the catalyst revealed that the Pt particle size is the key reason for the activity improvement, and further studies showed that Pt nanoparticles with a size of 2–4 nm showed the highest decarboxylation activity. This is the first report on the direct conversion of LA to n-butane.
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ChemCatChem
·
2015
·Vol. 7
·期 8
·1372-1379
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IF 4.556
Xing Tang,Xianhai Zeng,Zheng Li,Weifeng Li,Yetao Jiang,Lei Hu,Shijie Liu,Yong Sun,Lu Lin
Graphical In situ generated catalyst system: HCl/ZrO(OH) 2 catalysts are prepared in situ by the autonomous decomposition of ZrOCl 2 ⋅ 8 H 2 O in levulinic acid (LA)/2-butanol solution. The esterification of LA was catalyzed in tandem with hydrocyclization to γ-valerolactone (GVL) by Meerwein–Ponndorf–Verley reduction. This is the first report of HCl/ZrO(OH) 2 catalysts prepared in situ by the autonomous decomposition of ZrOCl 2 ⋅ 8 H 2 O in levulinic acid (LA)/2-butanol solution, which catalyzed the esterification of LA in tandem with hydrocyclization to γ-valerolactone (GVL) by Meerwein–Ponndorf–Verley (MPV) reduction without the use of external H 2 . A maximum GVL yield of 92.4 % from neat LA and a GVL formation rate of 1092.2 μmol g −1 min −1 were achieved in 2-butanol at 240 °C in 2 h. The in situ generated ZrO(OH) 2 was characterized comprehensively and its unexpected catalytic efficiency was attributed mainly to its extremely high surface area. A crude LA stream from the acid hydrolysis of cellulose was extracted into 2-butanol and subjected to this catalyst system to give a GVL yield of 82.0 % even in the presence of humins.
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Processes
·
2025
·Vol. 13
·期 4
·1110
·
IF 2.8
Shikang Zhao,Guohong Chen,Kaiqi Zheng,Shaojie Li,Jiaqi Xu,Fanan Wang,Xueping Liu,Rengui Weng
γ-Valerolactone (GVL) is a promising bio-based platform molecule with significant potential for energy applications. The production of GVL via biomass-based levulinic acid (LA) is an important reaction. To enhance the conversion and selectivity of non-precious-metal catalysts in the LA-to-GVL process and to better understand the key factors influencing this conversion, we conducted a series of experiments. In this study, supported Cu-Ni bimetallic catalysts (Cu-Ni2/Al2O3) were prepared using layered double hydroxides (LDHs) as a precursor. Compared with Cu-Ni catalysts synthesized via the conventional impregnation method, the Cu-Ni2/Al2O3catalysts exhibit higher catalytic activity and stability. The results demonstrated that efficient conversion was achieved with isopropanol as the hydrogen donor solvent, a reaction temperature of 180 °C, and a reaction time of 1 h. The yield of GVL reached nearly 90%, with a decrease of approximately only 6% after six consecutive cycles. The Cu-Ni2/Al2O3catalyst proved to be effective for converting biomass-derived LA to GVL, offering a route that not only reduces production costs and environmental impact but also enables efficient biomass-to-energy conversion.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Licheng Song,Shigao Shen,Lexuan Zhao,Zhen Song,Zhiwen Qi,Hongye Cheng
Deterpenation of lemon essential oil is essential for improving product quality and enriching bioactive compounds but challenging due to the weak selectivity caused by mildly polar compounds like citral and limonene. In this work, an efficient extractive deterpenation process was developed using a levulinic acid (LEA)-based natural eutectic solvent (NAES). Water was identified as the optimal natural hydrogen bond acceptor, with its content modulating the strength of hydrogen bonding between NAES and the target solute citral. A 2 wt% water content was employed for citral extraction, while higher water content aided citral recovery. Furthermore, hexane was selected as the anti-extractant from 2508 solvents to enhance selectivity and reduce limonene co-extraction. After sequential extraction and back-extraction with water and hexane, followed by vacuum distillation, high-purity citral (96.2 wt%) was obtained. The hydrous LEA NAES was recovered and reused effectively. This work presents an efficient and recyclable strategy for the extractive deterpenation of lemon essential oil using NAES.
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Nanomaterials
·
2022
·Vol. 12
·期 21
·3870
·
IF 5.719
Shuolin Zhou,Lu Wu,Junzhuo Bai,Min Lei,Min Long,Keying Huang
Levulinic esters, synthesized by the esterification of biomass-derived levulinic acid with various alcohols, is an important chemical that plays an essential role in the fields of biomass fuel additives, organic synthesis, and high value-added products. In the present work, the catalytic esterification of levulinic acid with n-butyl alcohol was selected as a typical model reaction to investigate the catalytic performance of an inexpensive commercial catalyst, titanium oxide nanoparticles. The influences of reaction time, reaction temperature, and catalyst loading on the conversion of levulinic acid to n-butyl levulinate were systematically examined through single-factor experiments. Additionally, the optimization of the reaction conditions was further investigated by a Box–Behnken design in response to the surface methodology. The desired product, n-butyl levulinate, with a good yield (77.6%) was achieved under the optimal conditions (reaction time of 8 h, reaction temperature of 120 °C, and catalyst dosage of 8.6 wt.%) when using titanium oxide nanoparticles as catalysts. Furthermore, it was found that addition of water to the catalytic system facilitated the reaction process, to some extent. This study reveals that the nanosized TiO2material,as an efficient solid acid catalyst, had good catalytic performance and stability for the esterification of levulinic acid after six consecutive uses.Keywords:TiO2nanoparticles;solid acid catalyst;n-butyl levulinate;esterification;response surface methodology
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PubMed
高影响因子
Advanced Sustainable Systems
·
2022
·Vol. 6
·期 3
·2100321
·
IF 6.737
Pei-dong Wu,Hu Li,Zhen Fang
Bimetallic synergy and carbon–nitrogen doping can contribute to enhanced catalytic activity due to the strong electronic state and unique geometrical structure. In this work, a series of biomass-derived Co-M bimetallic C N doped catalysts (Co-M@Chitosan-X; M = Zr, Ni, Fe, Cu, In; X denotes the molar percentage of M) are prepared via simple oil bath reflow and annealing. The Co-Zr@Chitosan-X catalysts are determined to contain alloys (Co-Zr), metal-carbon bonds (Co-C, Zr-C), metal-nitrogen bonds (Co-N, Zr-N), and metal oxides (Co 3 O 4 , ZrO 2 ) through a series of characterizations, in which graphite-coated alloys and metal oxides are found to be the catalytically active species. The doping of the second metal results in a significant enhancement for the number of active sites in the catalyst, and the d-band center is shifted toward a deviation from the Fermi energy level. Among the tested catalysts, Co-Zr@Chitosan-20 exhibits superior catalytic activity for the reductive amination of biobased levulinic acid to 5-methyl-2-pyrrolidone in 99.3% selectivity and 92.8% yield. This non-noble metal bimetallic synergistic catalytic protocol opens an avenue for efficiently producing biomass-derived nitrogenous chemicals.
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INDUSTRIAL CROPS AND PRODUCTS
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2022
·
IF 6.449
Zhihui Chen,Shuaibin Zhang,Bochao Yan,Qinjie Cai,Suping Zhang
Phosphoric acid-activated lignin-based solid acid catalysts (PLSA) were prepared from lignosulfonate by phosphoric acid activation, carbonation , and sulfonation. The physicochemical properties of catalysts were determined by SEM, N 2 adsorption-desorption, FT-IR, XRD , XPS and element analysis. Masses of phosphorous-containing group were grafted on catalyst surface during phosphoric acid activation and carbonation to provide sites for subsequent -SO 3 H substitution. PLSA could efficiently convert cellulose residue into levulinic acid. The effects of reaction temperature, residue time, catalyst loading, substrate concentration, solvent and catalyst stability were investigated and optimized. Using PLSA as catalyst, 67.9 mol% LA yield was obtained from 4 g cellulosic residue at 190 ℃ in 150 min in MIBK/H 2 O-NaCl. Overall, this work provides a valuable basis for the application of lignin-based solid acid in biomass valorization.
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ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Jinhui Chen,Qinqin Xu,Feng He,Wang Yue,Gang Hu,Jianyun Gan,Haibo Xie
Economically competitive and sustainable dissolution pretreatment technology is in high demand due to the remarkable achievement in the pretreatment of lignocellulose using ionic liquids (ILs) for enhanced enzymatic hydrolysis. Herein, levulinic acid (Lev), a well-known bio-based platform chemical derived from carbohydrates, in conjunction with a series of organic superbases, was used as a raw chemical to prepare a new class of protic ILs (PILs). The findings indicated that the obtained PILs exhibited a good solubility of up to 10 wt % toward corn stover-based lignocellulose at 140 °C in 40 mins, based on which a facile and efficient dissolution pretreatment technology was developed for enhanced enzymatic hydrolysis of corn stover. The facile dissolution and regeneration of corn stover resulted in significant changes in the composition and physical–chemical structures. These changes led to significantly enhanced enzymatic hydrolysis behavior of the pretreated sample with total reducing sugar and glucose yields of 0.8 and 0.49 g/g within 48 h under optimal conditions, respectively. The Kamlet–Taft solvent parameters of the PILs were systematically evaluated, and the interaction between the lignocellulose and PILs was studied by 13C NMR, indicating that the satisfactory performance of PILs was benefited from the higher ß parameter value and the stronger interactions, particularly the existence of the extra hydrogen-bond interaction from the potential keto–enol tautomerism of the ketone groups in levulinate anions. The compositional and physicochemical changes in the lignocellulose were systematically evaluated to achieve an in-depth understanding of the dissolution activation mechanism using various characterization techniques. The findings also showed that 44.3% of lignin could be fractionated during the facile dissolution and regeneration process, together with a transformation of the crystalline structure of cellulose I to cellulose II and of the packed morphology to a porous one. The structure of the fractionated lignin was also characterized for a better understanding of the fractionation process. The study demonstrated a new sustainable dissolution pretreatment technology for enhanced enzymatic hydrolysis, which can provide significant insights into the design of new solvents for biomass dissolution and processing.
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NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 32
·14406-14413
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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.
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Catalysts
·
2020
·Vol. 10
·期 9
·1096
·
IF 3.52
Ligang Luo,Xiao Han,Qin Zeng
A series of Ni-Fe/SBA-15 catalysts was prepared and tested for the catalytic hydrogenation of levulinic acid to γ-valerolactone, adopting methanol as the only hydrogen donor, and investigating the synergism between Fe and Ni, both supported on SBA-15, towards this reaction. The characterization of the synthesized catalysts was carried out by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), H2-TPD (hydrogen temperature-programmed desorption), XPS (X-ray photoelectron spectroscopy), and in situ FT-IR (Fourier transform–infrared spectroscopy) techniques. H2-TPD and XPS results have shown that electron transfer occurs from Fe to Ni, which is helpful both for the activation of the C=O bond and for the dissociative activation of H2molecules, also in agreement with the results of the in situ FT-IR spectroscopy. The effect of temperature and reaction time on γ-valerolactone production was also investigated, identifying the best reaction conditions at 200 °C and 180 min, allowing for the complete conversion of levulinic acid and the complete selectivity to γ-valerolactone. Moreover, methanol was identified as an efficient hydrogen donor, if used in combination with the Ni-Fe/SBA-15 catalyst. The obtained results are promising, especially if compared with those obtained with the traditional and more expensive molecular hydrogen and noble-based catalysts.Keywords:biomass ester derivatives;solvothermal processing;levulinic acid;γ-valerolactone;Ni-Fe bimetallic catalysts
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