Biomass Conversion and Biorefinery
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2021
·Vol. 13
·期 4
·2933-2946
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IF 4.987
Zhao Sibo,Wang Zihua,Chang Chun,Li Pan,Xu Guizhuan,Pang Shusheng
A two-stage alcoholysis was developed for improved conversion of furfural residue (FR) into levulinic acid (LA) and methyl levulinate (ML). Mixed acids including 0.01 M of H 2 SO 4 and Al 2 (SO 4 ) 3 and methanol/water (50/50 v/v%) were identified as the suitable catalyst and reaction medium. The optimum alcoholysis conditions were 198 °C and 1.5 h for the 1st stage and then 163 °C and 1.3 h for the 2nd stage, and the maximum total yield of LA and ML can reach 25.64%. The reaction kinetics and possible conversion pathways for ML and LA production were proposed. On the basis, HCOOH/H 2 O 2 pretreatment was screened for the pretreatment of FR, which increased the cellulose content of FR from 40.01 to 71.91%. The maximum total yield of LA and ML from pretreated FR was 44.96% under the optimum conditions of 195 °C and 1.9 h for the 1st stage and then 166 °C and 1.1 h for the 2nd stage, which was 16.09% higher than that of isothermal alcoholysis. The reusability tests showed that the Al 2 (SO 4 ) 3 was stable and can be reused at least 5 times. This study developed a new method for high-value utilization of FR and cleaner production of LA and ML.
研究领域:
化学工程
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE
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2021
·Vol. 102
·期 7
·2826-2834
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IF 3.639
Sibo Zhao,Xuezheng Huang,Zhenli Yan,Chun Chang,Guizhuan Xu,Chaojun Du,Youzhou Jiao,Zhiyong Chen
BACKGROUND Environmental concerns and the diminishing availability of unrenewable resources have spurred research into the use of agricultural waste as a feedstock for industrial applications. Efficient conversion of wheat straw into biobased chemicals is an important way to realize the potential value of renewable agricultural biomass. This study investigated one-pot conversion of wheat straw into two notable platform chemicals, levulinic acid (LA) and methyl levulinate (ML). RESULTS A mixed acid catalyst system, including 1% H 2 SO 4 and 0.015 mol L –1 Al 2 (SO 4 ) 3 , was an efficient catalyst for the conversion of wheat straw due to the combination of Brønsted acid and Lewis acid. A ratio of wheat straw to methanol of 5 g/50 mL was identified as the preferred solid/liquid ratio, and a methanol/H 2 O medium with 25% water content aided the simultaneous production of LA and ML from wheat straw. Under optimum conditions, the maximum total yield of LA and ML reached 23.01% at 220 °C and 3 h. The kinetics of biobased chemical formation and the reaction pathways in methanol/water were investigated. CONCLUSION The presence of water in the methanol/H 2 O medium affected the distribution of products and promoted hydrolysis reactions. The methanol/H 2 O medium not only inhibited the side reactions but also promoted the degradation of wheat straw and increased the total yield of LA and ML. This study provides a feasible method for the conversion of wheat straw to prepare biobased chemicals. © 2021 Society of Chemical Industry.
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
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Kai Sun,Yuewen Shao,Cong Ming,Mengjiao Fan,Huailin Fan,Lijun Zhang,Shu Zhang,Yi Wang,Guozhu Chen,Xun Hu
Impregnation is a traditional method for preparing heterogeneous catalysts, which typically includes impregnation, calcination and reduction steps. In this study, catalyst preparation was combined with its use in catalytic hydrogenation for avoiding ex-situ catalyst-synthesis. Specifically, Cu/MgO were prepared by simply mixing CuSO 4 , MgO and the reactant to be hydrogenated such as levulinic acid (LA) or ethyl levulinate (EL) in ethanol with hydrogen. Heating of the mixture to 160 °C could obtain both synthesized Cu/MgO and hydrogenation product of gamma-valerolactone (GVL) (highest yield: 99.9%). The formation of Cu/MgO catalyst proceeded via the steps of fixing Cu 2+ by reacting with the basic sites of MgO to form Cu(OH) 2 . The metastable Cu(OH) 2 decomposed to form CuO that was reduced to Cu for catalyzing conversion of LA/EL to GVL. Such a method is very simple and applicable to prepare varied types of Cu-based catalyst by changing copper salts and supports of varied alkalinity.
研究领域:
催化
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化学工程
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
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2022
·
IF 13.7
Anon Bunrit,Teera Butburee,Meijiang Liu,Zhipeng Huang,Keerati Meeporn,Chaiyasit Phawa,Jian Zhang,Sanchai Kuboon,Huifang Liu,Kajornsak Faungnawakij,Feng Wang
Herein, we developed photo–thermo-dual catalytic strategies for the production of γ-valerolactone (GVL) from levulinic acid (LA) and its ester using platinum-loaded TiO2 as a dual-functional catalyst. Both catalytic systems were evaluated under mild reaction conditions. In the photocatalysis system, a base plays crucial roles in the conversion of LA and EL to GVL. The control experiments reveal that plausible mechanistic pathways of both systems proceed via the hydrogenation of the ketone group of LA to the corresponding alcohol as a major intermediate followed by a subsequent cyclization step to GVL. This dual-functional catalyst provides alternative strategies for the conversion of LA and its ester into GVL, which could pave the way for biomass utilization in a more effective and practical manner.
研究领域:
催化
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生物质转化
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化学工程
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可持续化学
✓ 已验证
DOI
高影响因子
Catalysts
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2020
·Vol. 10
·期 6
·692
·
IF 3.52
Yan Du,Xiao Chen,Ji Qi,Pan Wang,Changhai Liang
The electrocatalytic hydrogenation (ECH) of biomass-derived levulinic acid (LA) is a promising strategy to synthetize fine chemicals under ambient conditions by replacing the thermocatalytic hydrogenation at high temperature and high pressure. Herein, various metallic electrodes were investigated in the ECH of LA in a H-type divided cell. The effects of potential, electrolyte concentration, reactant concentration, and temperature on catalytic performance and Faradaic efficiency were systematically explored. The high conversion of LA (93%) and excellent “apparent” selectivity to valeric acid (VA) (94%) with a Faradaic efficiency of 46% can be achieved over a metallic lead electrode in 0.5 M H2SO4electrolyte containing 0.2 M LA at an applied voltage of −1.8 V (vs. Ag/AgCl) for 4 h. The combination of adsorbed LA and adsorbed hydrogen (Hads) on the surface of the metallic lead electrode is key to the formation of VA. Interestingly, the reaction performance did not change significantly after eight cycles, while the surface of the metallic lead cathode became rough, which may expose more active sites for the ECH of LA to VA. However, there was some degree of corrosion for the metallic lead cathode in this strong acid environment. Therefore, it is necessary to improve the leaching-resistance of the cathode for the ECH of LA in future research.Keywords:electrocatalytic hydrogenation;levulinic acid;valeric acid;lead
研究领域:
化学工程
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2023
·
IF 5.9
Jiao Li,Tao Li,Yang Wang,Zicheng Du,Yadan Luo,Chengrong Qin,Chen Liang,Caoxing Huang,Shuangquan Yao
It is of great significance to inhibit the repolymerization of lignin when removing hemicellulose by acid pretreatment . Adding a lignin fragment scavenger is an effective method to inhibit its repolymerization. Here, the effect of a bio-based polar aprotic solvent, levulinic acid (Lev), and γ-valerolactone (GVL) coupled pretreatment system on the separation yield of poplar biomass components was investigated. The optimum pretreatment conditions were a Lev concentration was 7.0%, reaction temperature was 170 °C, pretreatment time was 60 min, and GVL concentration was 9.0%. The separation yield of hemicellulose was 84.54%, which was a 4.53% increase over that with Lev pretreatment. The retention yield of cellulose was 89.68%. In addition, the separation efficiency was significantly improved when the pretreatment time was reduced by 40 min. The reaggregation of lignin was suppressed under the condition of maximum hemicellulose separation. In the lignin samples the content of β-O-4 was as high as 47.81%. Simultaneously, the content of phenolic and aliphatic hydroxyl increased. The results revealed that Lev/GVL pretreatment had good hemicellulose separation selectivity and excellent lignin fragment removal efficiency. This provides a new strategy for suppressing adverse effects on the lignin structure in the efficient separation of hemicellulose in pretreatment.
研究领域:
生物质能
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2023
·
IF 5.3
Kaifeng Lu,Yifan Wang,Lingjun Zhu,Bo Xing,Shurong Wang
The conversion of biomass-derived saccharides into platform chemicals is of immense importance for biorefineries. This study demonstrated the potential of using heteropoly acid as a catalyst in a green solvent system composed of γ-valerolactone and water for the production of levulinic acid from biomass-derived saccharides. The effects of heteropoly acids with different central heteroatoms (P and Si) and addendum atoms (W and Mo) on the catalytic conversion of glucose to levulinic acid in the γ-valerolactone–water system were studied. According to the experimental results, silicotungstic acid had the highest catalytic activity. In comparison to other catalysts, silicotungstic-acid-catalyzed glucose conversion could obtain the highest levulinic acid yield under the same reaction conditions, which was mainly attributed to the lower ratio of Brønsted/Lewis acid of silicotungstic acid. In optimal circumstances, 87.7% levulinic acid was obtained by glucose conversion at 190 °C and 60 min. Meanwhile, non-protonic polar solvent γ-valerolactone could promote the slight conversion of glucose to pentose, producing about 9% furfural. In addition, a kinetic model was established to further evaluate the reaction process of glucose conversion to levulinic acid and furfural. The green reaction system was also appropriate for other saccharides. In this study, a new approach could be provided to efficiently convert saccharides into platform chemicals.
研究领域:
生物化学
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可再生资源与环境工程
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
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2020
·
IF 6.274
Han Chen,Qiong Xu,Du Zhang,Wenzhu Liu,Xianxiang Liu,Dulin Yin
A series of mesoporous nickel catalysts with different molar ratios of citric acid and nickel nitrate were synthesized via a simple two-step method by solid-state grinding and in-situ reduction; these catalysts were further employed for the catalytic transfer hydrogenation of levulinate esters to γ-valerolactone (GVL) with 2-propanol as the hydrogen donor. The effects of C 6 H 8 O 7 /Ni molar ratios , catalyst dosage, reaction temperature and time on the catalytic performance were investigated. An excellent GVL selectivity of 99.1% and an ethyl levulinate (EL) conversion of 100% could be achieved at 180 °C in 6 h over Ni-1.0 catalyst with a 1.0:1 M ratio of C 6 H 8 O 7 /Ni. The characterization results showed that the Ni-1.0 catalyst was composed of mesoporous metallic Ni bulk and a surface Ni–NiO composite, and the acid sites of NiO played a synergistic catalytic role in producing GVL from EL. The superior mesoporous structure and large surface area of Ni-1.0 increased the atomic utilization rate of nickel metallic active centers. Moreover, Ni-1.0 catalyst could be easily separated and reused ten times, with an EL conversion above 95% remaining in each recycle. This work provids a highly efficient and environmentally friendly catalytic procedure for the conversion of biomass into GVL, a fuel additive compound.
研究领域:
化学工程
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可再生资源与环境科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Jing Bai,Canwei Cheng,Yong Liu,Chenguang Wang,Yuhe Liao,Lungang Chen,Longlong Ma
In this work, Ni-based catalysts were prepared using the impregnation method. Ni/Al 2 O 3 showed good performance with a γ‐valerolactone (GVL) yield of 99.2% from hydrogenation of levulinic acid (LA). Among the tested bimetallic catalysts , the NiCo catalyst showed better performance than NiMn, NiMo, and NiCu catalysts for the hydrogenation of LA to GVL. Catalysts with different Ni/Co ratio were synthesized, and 15%Ni-15%Co/Al 2 O 3 shows the best performance with a GVL yield of 99.5%. The textural and chemical characteristics of the NiCo/Al 2 O 3 were determined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and H 2 temperature-programmed reduction (H 2 -TPD). This study shows that the incorporation of the Ni and Co metals formed a Ni-Co alloy, which significantly increased the activity than other Ni-based bimetallic catalysts and led to a milder condition for hydrogenation of LA to GVL. The test of reuse potential of 15%Ni-15%Co/Al 2 O 3 exhibited good stability up to 5 cycles without obvious deactivation.
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2022
·
IF 4.654
Zhen Ge,Hongye Cheng,Guojin Zhang,Linsheng Wang,Zhiwen Qi
To achieve maximum usage and economically upgrade light cycle oil, it is necessary to separate light cycle oil components into nonaromatic and aromatic fractions. A deep eutectic solvent composed of tetrabutylphosphonium bromide and levulinic acid exhibited excellent extraction performance in separating light cycle oil components. In this work, the mechanisms of deep eutectic solvent formation and light cycle oil separation are investigated using characterization analysis and molecular dynamics simulations. Both Fourier-transform infrared spectra and molecular dynamics simulation results indicate that the main driving force for deep eutectic solvent formation is hydrogen-bonding interactions between the Br– anion of tetrabutylphosphonium bromide and the carboxyl group (−COOH) of levulinic acid. On the other hand, while the TBP+ cation of tetrabutylphosphonium bromide and the carbonyl group (−C═O) of levulinic acid are less likely to contribute to deep eutectic solvent formation, they are more likely to interact with the aromatic ring of tetralin via CH−π and π–π interactions, respectively. The results suggest that each functional group of tetrabutylphosphonium bromide and levulinic acid plays an essential role either in deep eutectic solvent formation or in aromatic compound extraction, which provides insights into the mechanism of extractive separation of light cycle oil components using deep eutectic solvents.
研究领域:
化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2020
·
IF 3.421
Yang Qu,Yuan Zhao,Shanshan Xiong,Chenguang Wang,Shurong Wang,Lingjun Zhu,Longlong Ma
5-Hydroxymethylfurfural (HMF) and levulinic acid (LA) are two important platform compounds that can be produced by the dehydration of hexoses from hydrolysis of cellulose. In this study, glucose dehydration was catalyzed by the SO42–/ZrO2 catalyst in the NaCl–THF/H2O biphasic solvent system. Complete conversion of glucose was achieved at 160 °C. The highest HMF yield and LA yield were 61.84% and 29.68%, respectively. The results showed that the conversion and product distribution were influenced by catalyst acidity, solvent composition, temperature, and time. The SO42– load greatly changed the acidity of the catalyst, thus affecting the product distribution. By changing the composition of the catalyst and the biphasic solvent system, different yields of HMF and LA could be obtained, so as to realize directional synthesis of the target products.
研究领域:
生物化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2024
·
IF 9.7
Huanhuan Zhang,Liutao Hou,Weihong Zhang,Yucheng Lin,Xueli Liu,Shiqiang Zhao,Chun Chang
The purpose of this study is to design and investigate two coupling processes for acid-catalyzed hydrolysis of corncob, achieving the simultaneous preparation of biomass-based furfural and levulinic acid (LA). Meanwhile, high concentration and yield of LA were obtained through a situ feeding strategy of pretreated furfural residue with high solids loading (20%, w/v). In Scenario A, 2-methyltetrahydrofuran was selected as the solvent for the LA extraction process compared with the neutralization process in Scenario B. Techno-economic assessment results show that Scenario A is technically feasible and cost-competitive, with an internal rate of return of 21.92%, a net present value of 121 million US dollars, a carbon efficiency of 72%, an environmental factor of 4.38, and a process mass intensity of 32.19. This study will provide new insights for fully utilizing lignocellulosic biomass to prepare renewable energy resources, comprehensively evaluating the economic feasibility, and promoting green and low-carbon development.
研究领域:
生物化学
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可再生资源
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）