Advanced Sustainable Systems
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2022
·Vol. 6
·期 3
·2100321
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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.
研究领域:
化学工程
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催化科学
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材料科学
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产品关联
DOI
高影响因子
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.
研究领域:
生物化学
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生物质能
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催化化学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2022
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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.
研究领域:
生物化学
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可再生资源与环境
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DOI
高影响因子
Nanomaterials
·
2022
·Vol. 12
·期 21
·3870
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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
研究领域:
化学工程
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催化科学
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生物燃料合成
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产品关联
DOI
PubMed
高影响因子
FUEL PROCESSING TECHNOLOGY
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2023
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IF 7.5
Wansi Lin,Lincai Peng,Huai Liu,Junhua Zhang
Zirconium-derived catalyst with abundant Lewis acid-base pairs has earned it a place of prominence for the catalytic upgrade of bio-based carbonyls to valuable chemicals and fuels through catalytic transfer hydrogenation (CTH) reaction. However, the low catalytic efficiency of Zr-based catalysts urgently needs to be improved to meet the criterion for their industrial deployment. In this contribution, tungstophosphoric acid (HPW) was demonstrated as an effective modifier to the electronic structure of the pristine polyacrylonitrile and lignin-supported Zr nanofiber (Zr-Lig@PAN) to boost the CTH of levulinic acid (LA) into γ-valerolactone (GVL). Especially, an impressive GVL formation rate of 32.5 mmol·g −1 ·h −1 was implemented over Zr/HPW 0.75g -Lig@PAN, significantly prevailing over the previous reported Zr-based catalysts for the CTH of LA or its ester to GVL. Mechanistic investigations well demonstrated that the superior electron-accept ability of HPW allowed the construction of electron-deficient Zr sites, which is beneficial to the adsorption and activation of LA and isopropanol, thus boosting the CTH reaction. These findings open up a new avenue to design efficient Zr-based catalysts for the CTH reaction by elaborately tuning the electronic structure of the catalyst in the presence of a second metal.
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
高影响因子
Biomass Conversion and Biorefinery
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2023
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IF 4
Zhao Shiqiang,Gui Gang,Zhang Weihong,Chen Wei,Zhao Sibo,Xu Guizhuan,Chang Chun
Levulinic acid (LA) is an important biobased platform chemical, which can be produced from carbohydrates via acid hydrolysis. However, the LA concentaration is usually low via the batch process, which is not conducive to its subsequent separation and purification. In this study, we improved the LA production by using novel fed-batch hydrolysis. Compared with the batch process, the LA yield of the one-time feeding process and two-time feeding process increased to 38.66% and 40.60% from 27.80%, the LA concentration increased to 49.83 g/L and 52.33 g/L from 35.83 g/L, respectively. The feasibility of using the waste solid residue generated during the LA production as filler was further investigated. The polyurethane foam was prepared with the incorporation of solid residue, and the compressive strength of the biobased polyurethane foam composites increased by 32.08% with the addition of 5% solid residue. The characterization of the biobased polyurethane foam indicated the solid residue can be used for polyurethane foam enhancement. This study provided a novel method for the efficient and clean production of LA and high-value utilization of the waste produced in the process.
研究领域:
生物化学工程
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材料科学
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产品关联
DOI
高影响因子
Polymers
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2024
·Vol. 16
·期 3
·361
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IF 4.7
Zeyu You,Min Yu,Renli Fu,Xiaoan Nie,Jie Chen
Herein, a bio-based plasticizer ketalized tung oil butyl levulinate (KTBL) was developed using methyl eleostearate, a derivative of tung oil, and butyl levulinate. KTBL can be used as an auxiliary plasticizer to partially replace traditional plasticizer. The plasticizer has a ketone structure, an ester base, and a long linear chain. It was mixed with dioctyl phthalate (DOP), and the effect of the plasticizer KTBL as an auxiliary plasticizer on the plasticization of poly(vinyl chloride) (PVC) was studied. Their compatibility and plasticizing effect were evaluated using dynamic–mechanical thermal analysis (DMA), mechanical property analysis, and thermogravimetric analysis (TGA). The results demonstrate that when the KTBL to DOP ratio is 1:1, the blended sample with KTBL exhibits superior mechanical performance compared to pure DOP, resulting in an increased elongation at break from 377.47% to 410.92%. Moreover, with the increase in KTBL content, the durability is also significantly improved. These findings suggest that KTBL can serve as an effective auxiliary plasticizer for PVC, thereby reducing the reliance on DOP.Keywords:renewable origin;ketal;methyl eleostearate;plasticizer;poly(vinyl chloride)
研究领域:
材料科学
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化学工程
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CARBOHYDRATE POLYMERS
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2021
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IF 9.381
Feng He,Jinhui Chen,Zhiwei Gong,Qinqin Xu,Wang Yue,Haibo Xie
In this study, an economically competitive and sustainable levulinic acid-based protic ionic liquids were identified to be good solvents for the dissolution pretreatment of cellulose towards enhanced enzymatic hydrolysis . The influences of protic ionic liquids species, dissolution pretreatment time, and pretreatment temperature on the physico-chemical structures of cellulose were systematically investigated by various analytical techniques. The findings indicate that the pretreatment efficiency was correlated to the basicity of the organic bases, and the presence of ketone group in the levulinate anion with particular hydrogen bonding forming ability via keto–enol tautomerism. The DBN derived protic ionic liquids exhibited best performance at 100 °C in 1 h, as evidenced by a 94% glucose yield. This solvent system was also suitable for the dissolution pretreatment of corn stover-based lignocellulosic biomass for sugars production, although a higher temperature and longer pretreatment time was required. Furthermore, the solvent system could be recycled and reused.
研究领域:
生物化学
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可再生资源与环境科学
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DOI
高影响因子
ChemistrySelect
·
2024
·Vol. 9
·期 40
·e202403878
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IF 1.9
Haifeng Liao,Jianwei Guo
Graphical Three kinds of heteropoly acid-based ionic liquids with different Hammett acidity were prepared for the catalytic conversion of cellulose to levulinic acid, and the effects of different solvent systems on the catalytic reactions were investigated. The results showed that higher Hammett acidity was beneficial to increase the yield of levulinic acid, and GVL/H 2 O bi-phase solvent system was helpful to extract the product to the organic phase and promote the formation of levulinic acid. Levulinic acid is an important chemical intermediate, which has many applications in organic synthesis, industry, agriculture, and medicine. In this word, three kinds of heteropoly acid based ionic liquids ([IMPS]H 2 PW 12 O 40 、[PyPS] H 2 PW 12 O 40 [TEAPS] H 2 PW 12 O 40) were used to catalyze the one-pot conversion of cellulose to levulinic acid. [IMPS]H 2 PW 12 O 40 has the highest catalytic activity due to its strong Hammett acidity ( H 0 ). In addition, the effect of biphasic solvent systems on the conversion of cellulose to levulinic acid was also studied. The results showed that the GVL/H 2 O system could effectively promote the conversion of cellulose and increase the yield of levulinic acid. The yield of levulinic acid could reach 52.6% and the conversion rate of cellulose was 91.2% at 180 °C for 180 min under the GVL/H 2 O volume ratio of 1:1 with [IMPS]H 2 PW 12 O 40 as a catalyst at 1 Mpa N 2 and cellulose as raw material. And [IMPS]H 2 PW 12 O 40 can be recycled up to five times without significant performance loss. This study provides a promising method for efficiently converting cellulose and other biomass resources to levulinic acid extraction.
研究领域:
化学工程
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生物质能
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有机合成
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产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
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2019
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IF 4.507
Haonan Qu,Bingyi Liu,Guohua Gao,Yiming Ma,Yanmei Zhou,Hua Zhou,Li Li,Yonghong Li,Shengjian Liu
Levulinic acid (LA) is a versatile key building block in the conversion of carbohydrates and it is an important basic chemical with various potential uses. MIL-100(Fe) loading with insoluble lysine functionalized phosphotungstic acid (Lys-PM 2 ) as heterogeneous catalysts have been synthesized for the conversion of glucose to LA in water. The optimized yield of LA is obtained by using Lys-PM 2 to catalyze glucose conversion is comparable to the majority of effective catalysts. The highest yield of LA (57.9%) is obtained at 150 °C for 9 h with 100 mg glucose and 25 mg Lys-PM 2 , since the Brønsted acidity and Lewis acidity of Lys-PM 2 . And the catalyst is able to recycle at least four times. It demonstrates the potential of Lys-PM 2 for the conversion of biomass.
研究领域:
催化化学
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绿色化学
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生物质能源
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有机转化
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材料化学
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可持续化学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2018
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IF 6.14
Chao Wang,Qilin Zhang,Yanglei Chen,Xueming Zhang,Feng Xu
The economically viable synthesis of levulinic acid (LA), a promising and valuable renewable biomass-derived platform for bioproducts, with high carbon efficiency is a challenge. A direct and highly effective catalytic system for conversion of xylose residues (XRs) into LA under mild conditions by using FeCl3 as catalyst and cheaply available NaCl as promoter has been developed. The NaCl solution exhibits high carbon efficiency in LA (68.0 mol %) when compared with the non-NaCl systems (48.5 mol %) due to the moderate increase of the acidity and the higher viscosity of the NaCl system than water. The experimental results demonstrated that the presence of NaCl caused no distinctive changes on reaction pathways but increased the dissolution rate and the hydrolysis rate of XRs cellulose. Moreover, further integration of our degradation process with a reactive extraction step makes energy-efficient separation of LA. The NaCl solutions easily and efficiently extracted LA into LA-derived solvent 2-methyltetrahydrofuran from aqueous solutions. The efficiency and integration of the reaction process presented a great potential for LA production from renewable biomass with the aid of concentrated seawater.
研究领域:
生物质化学
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催化化学
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2016
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IF 5.267
Ye-Zhi Qin,Min-Hua Zong,Wen-Yong Lou,Ning Li
Valorization of biomass-based platform chemicals into high value-added products has attracted increasing attention recently. In this work, upgrading of 5-hydroxymethylfurfual (HMF) and levulinic acid, two important biomass-based platform chemicals, to HMF levulinate via a green and efficient enzymatic approach was reported. Novozym 435 was found to be the best biocatalyst for the enzymatic esterification. The enzymatic esterification progressed smoothly in t-butanol, 2-methyl-2-butanol, and cyclopentyl methyl ether as well as in the ecofriendly biomass-derived 2-methyltetrahydrofuran (2-MeTHF), while no enzymatic reaction occurred in deep eutectic solvents. When HMF concentration was up to 500 mM, a good conversion of 72% was achieved in 2-MeTHF. The reaction temperature exerted a significant effect on the enzymatic esterification. When the reaction temperature is below 40 °C, high HMF conversions (>85%) were obtained. Besides, significant inactivation of the enzyme was observed at more than 50 °C, resulting in poor conversions.
研究领域:
生物化学
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可再生资源工程
✓ 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）