Reaction Chemistry & Engineering
·
2025
·
IF 3.1
Xue Luo,Jiahui Liu,Danhui Li,Lili Zhao,Hualiang An
Cyclopentanone self-condensation to 2-cyclopentylidenecyclopentanone is one of the key steps in synthesizing high-density fuels. In this study, MgAl-LDO(NO3−) catalysts, prepared via coprecipitation, demonstrated good catalytic performance. Meanwhile, Mg2Al-LDO(NO3−) catalysts with different Mg/Al ratios were explored. Characterization by XRD, NH3-TPD and CO2-TPD revealed that Mg2Al-LDO(NO3−) possessed appropriate acid–base active sites, correlating with its enhanced catalytic performance. Under optimized reaction conditions, cyclopentanone conversion reached 85.9% with 98.8% selectivity toward 2-cyclopentylidenecyclopentanone. Furthermore, the reusability of the catalyst was investigated. XRD, SEM, and N2 adsorption–desorption analyses indicated that structural changes in the Mg2Al-LDO(NO3−) catalyst led to its deactivation. GC-MS analysis of the reaction system identified the primary by-product as 2,5-dicyclopentylidenecyclopentanone. Based on these findings, a plausible reaction network is proposed.
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高影响因子
ENERGY & FUELS
·
2020
·
IF 3.421
Qiang Liu,Xinghua Zhang,Qi Zhang,Qiying Liu,Chenguang Wang,Longlong Ma
In this work, high-density jet fuel range cycloalkanes were synthesized in high yields (∼80%) by solvent-free aldol condensation of cyclopentanone and furfural followed by hydrodeoxygenation (HDO). Sodium-promoted magnesium–aluminum mixed oxides (Na–MgAlO) exhibited a high catalytic activity in the aldol condensation of cyclopentanone and furfural under a solvent-free condition. Furfural conversion of 99.4% with almost 100% selectivity for 2-(2-furylmethylidene) cyclopentanone and 2,5-bis(2-furylmethylidene) cyclopentanone were obtained over the 5.7%Na–MgAlO catalyst under mild conditions (80 °C, 2 h). The Na–MgAlO catalysts were characterized by multiple technologies, such as N2 physisorption, powder X-ray diffraction, Fourier transform infrared spectra, and CO2 temperature-programmed desorption, and so on. It was found that the high catalytic activity for aldol condensation of cyclopentanone and furfural was clearly related to the amount and strength of basicity of Na–MgAlO catalysts. Finally, the condensation products were converted to jet fuel range cycloalkanes by HDO over Pd/C and HZSM-5 catalysts. The density, heating value, and freezing point of the HDO liquid products were 0.83 g/cm3, 43.1 MJ/Kg, and −27.7 °C, respectively. The results suggest that these cycloalkanes are promising as blending components for jet fuel.
研究领域:
能源化学
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催化化学
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Huang Liu,Yangfei Liu,Minghao Liu,Hailong Liu
Water/diesel-cyclopentylamine and water/diesel-cyclopentanone emulsions were used to store natural gas during hydrate formation. First, cyclopentylamine (-amine) and cyclopentanone (-anone) were tested as thermodynamic promoters for CH4 hydrate formation in water/diesel (w/o) emulsions. The kinetics of CH4 hydrate formation in the w/o-amine and w/o-anone emulsions were then investigated. It was found that the promotional effect of both cyclopentylamine and cyclopentanone on CH4 storage in the hydrate phase was much better than that of cyclopentane, with the highest gas storage amount reaching 201.7 m3/m3, which is close to the ideal value (220 m3/m3), and the water-to-hydrate conversion ratio was higher than 90%. The main hydration reaction process was completed in 50 min, with the reaction rate reaching 2.3 mmol/min, which is higher than that reported for aqueous solutions. It should be noted that this was the first time that cyclopentylamine was tested and it showed good thermodynamic and kinetic stimulation effects on gas hydrate formation. The suitable CH4 hydrate formation conditions including the additional amount of promoters, temperature, pressure, and water cut range were determined to be approximately 20 wt %, 274.15–278.15 K, 5.0–6.0 MPa, and 20 wt %, respectively. The storage and transport pressure for the formed hydrate products could be decreased to less than 1 MPa. The significant gas storage amount was further supported by laser Raman analysis, which confirmed that the CH4 molecules were trapped in the small and large cages of the formed SII hydrate. Meanwhile, the formed hydrate/diesel slurries exhibited good dispersion features.
研究领域:
化学工程
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能源科学
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高影响因子
Journal of Energy Chemistry
·
2023
·
IF 13.1
Xinghua Zhang,Miaojia Song,Jianguo Liu,Qi Zhang,Lungang Chen,Longlong Ma
In this work, a “cyclopentanone-vanillin” strategy was proposed for the preparation of jet fuel range cycloalkanes from lignocellulose-derived ketones and lignin-derived aldehydes via aldol condensation and hydrodeoxygenation (HDO). Ethanolamine lactate ionic liquid (LAIL) exhibited excellent catalytic activity in the aldol condensation of cyclopentanone and vanillin. Desired mono-condensation and bi-condensation products were obtained with yield of 95.2% at 100 °C. It is found that the synergy effects between amino group of ethanolamine and hydroxyl group of lactic acid play a key role in the aldol condensation. The condensation products were converted into cycloalkanes by HDO over 5%Pd/Nb 2 O 5 catalyst. The density of the obtained HDO products is 0.89 g/cm 3 and the freezing point is lower than −60 °C. These results suggest that the resulted cycloalkanes can be used as additives to improve the density and low-temperature fluidity of the jet fuels.
研究领域:
生物化学
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能源化学
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高影响因子
RSC Advances
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2019
·Vol. 9
·期 7
·3661-3668
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IF 3.049
Lei Ao,Wei Zhao,Yin-shuang Guan,Ding-kai Wang,Kai-shuai Liu,Tian-tian Guo,Xing Fan,Xian-yong Wei
The aldol-condensation reaction of biomass-derived furfural and cyclopentanone coupled with hydrogenation/hydrodeoxygenation is a promising route for the production of renewable high-quality diesel or jet fuel. In this paper, we focus on the heterogeneously catalyzed aldol condensation of furfural with cyclopentanone, in order to maximize the yield of 2,5-bis(2-furylmethylidene)cyclopentan-1-one (F2C, a C15 fuel precursor). Experiments were conducted over a series of solid-base catalysts and it was found that potassium fluoride impregnated alumina shown the highest catalytic efficiency. We further investigated the effect of different parameters on the performance of KF/γ-Al2O3, including KF loading amount, solvent, reaction time and temperature. Over KF/γ-Al2O3 with a 33% KF loading amount, the aldol reaction achieved an F2C molar yield up to 95.4% at 333 K within 2 h. Under the nearly optimal condition, the separated solid product is almost F2C with a purity of 100%, providing a high-quality biofuel precursor for the next processing step.
研究领域:
化学工程
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可再生能源
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催化化学
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DOI
PubMed
高影响因子
MEASUREMENT SCIENCE and TECHNOLOGY
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2020
·Vol. 31
·期 9
·095102
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IF 1.857
Qianchun Zhang,Qin Zhou,Yan Wang,Yun Wu,Li Jiang,Yuguo Zheng,Junyi Liang
We report that cyclopentanone on the surface of nanosized dysprosium oxide (nano-Dy2O3) has strong chemiluminescence emission. A cyclopentanone gas sensor was built based on this phenomenon with a response time of 3 s and a recovery time of 10 s. The cataluminescence characteristics and factors affecting the signal intensity of cyclopentanone sensor were investigated in detail including selecting the appropriate sensing material, detection wavelength, working temperature, and air flow rate. Under these optimized conditions, the calibration curve of the cataluminescence intensity versus cyclopentanone vapor concentration was linear over 0.100–15.0 μg ml−1 with a correlation coefficient (R2) of 0.9973; the limit of detection was 17 mg m−3 (signal/noise = 3). The relative standard deviation (RSD, n = 10) was 1.86% for ten replicates. The selectivity was significantly higher for the target analyte. The sensor was then used to analyze cyclopentanone in spiked samples and organic laboratory environment sample. The results show satisfactory recoveries of 93.3%–108% and RSDs of 7.9%–8.6% indicating that the developed sensor has the potential for the rapid analysis of cyclopentanone.
研究领域:
分析化学
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材料科学
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高影响因子
MOLECULES
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2021
·Vol. 26
·期 19
·5736
·
IF 4.412
Chunhua Wang,Zhiquan Yu,Yuhao Yang,Zhichao Sun,Yao Wang,Chuan Shi,Ying-Ya Liu,Anjie Wang,Karen Leus,Pascal Van Der Voort
Upgrading furfural (FAL) to cyclopentanone (CPO) is of great importance for the synthesis of high-value chemicals and biomass utilization. The hydrogenative ring-rearrangement of FAL is catalyzed by metal-acid bifunctional catalysts. The Lewis acidity is a key factor in promoting the rearrangement of furan rings and achieving a high selectivity to CPO. In this work, highly dispersed Pd nanoparticles were successfully encapsulated into the cavities of a Zr based MOF, UiO-66-NO2, by impregnation using a double-solvent method (DSM) followed by H2reduction. The obtained Pd/UiO-66-NO2catalyst showed a significantly better catalytic performance in the aforementioned reaction than the Pd/UiO-66 catalyst due to the higher Lewis acidity of the support. Moreover, by using a thermal treatment. The Lewis acidity can be further increased through the creating of missing-linker defects. The resulting defective Pd/UiO-66-NO2exhibited the highest CPO selectivity and FAL conversion of 96.6% and 98.9%, respectively. In addition, the catalyst was able to maintain a high activity and stability after four consecutive runs. The current study not only provides an efficient catalytic reaction system for the hydrogenative ring-rearrangement of furfural to cyclopentanone but also emphasizes the importance of defect sites.Keywords:Pd/UiO-66-NO2;furfural;hydrogenative ring-rearrangement;cyclopentanone;double-solvent method
研究领域:
催化化学
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材料科学
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DOI
PubMed
高影响因子
Molecular Catalysis
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2023
·
IF 4.6
Xiaoqing Zhang,Yuewen Shao,Kai Sun,Mengjiao Fan,Shu Zhang,Xun Hu
Nickel-based catalysts are widely used in hydrogenation of varied types of organics. However, the nickel catalyst, like Ni/SiO 2 , lacks selectivity for hydrogenation of C=C and C=O. This is undesirable in some scenarios, such as conversion of biomass-derived furfuryl alcohol (FA) to cyclopentanone (CPO), a fine chemical, in which the C=C in furan ring of FA needs to be retained. In this study, introduction of sulfur species to Ni/SiO 2 catalyst via loading NiSO 4 was adopted to inhibit hydrogenation of furan ring in FA, aiming to achieve conversion of FA to CPO via ring-opening route. The results indicated that NiSO 4 was reduced to Ni x S y , which further reacted with metallic Ni, forming Ni 3 S 2 species and introducing the acidic sites with high-strength. The co-existence of Ni x S y and metallic Ni species effectively hindered hydrogenation of furan ring in FA, reducing tetrahydrofurfuryl alcohol (THFA) yield from 97% over Ni/SiO 2 to 0 over the NiS x /SiO 2 catalysts and shifting the major product to CPO. Nonetheless, the enhanced acidic sites along with the introduction of NiSO 4 catalyzed polymerization of reaction intermediates, competing with the production of CPO. The acidic sites, however, facilitated hydrogenolysis of vanillyl alcohol to selectively produce (yield: 94.3%) in hydrogenation of vanillin. Characterization of hydrogenation of FA with in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) technique suggested the oxygen-containing functionalities in FA, instead of furan ring, could strongly adsorb on the NiS 10 /SiO 2 catalyst, enhancing rearrangement reaction to form CPO while suppressing hydrogenation of the furan ring.
研究领域:
催化化学
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生物质转化
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材料科学
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高影响因子
JOURNAL OF CATALYSIS
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2024
·
IF 6.5
Zepeng Zhao,Wenguang Zhou,Guozhang Chang,Lungang Chen,Chenguang Wang,Yuhe Liao,Jinxing Long,Longlong Ma,Yong Liu
In this study, the structure–activity relationships were investigated in converting biomass-derived furfural into cyclopentanone (CPO) or tetrahydrofuran alcohol (THFA) using a rinsing method to modulate the NiCoAl catalyst. Characterization of two catalysts, NiCoAl (without rinsing) and NiCoAl-R (with rinsing), reveals differences in morphology, composition, and acidity. Rinsing induced a transition from agglomerate to layered structure in NiCoAl-R, which exhibited higher acid strength and improved Lewis to Brønsted acid ratio. NiCoAl-R contained a high percentage of metal oxides, while NiCoAl had a high percentage of metallic species on its surface. These distinctions resulted in varied performance in FFA hydrogenolysis, with NiCoAl-R favoring CPO formation and NiCoAl facilitating THFA production. In situ DRIFTS experiments reveals differing furfural sorption states, and DFT calculations highlighted the higher activity of metal oxides in ring-opening reactions. This investigation elucidates the intricate relationship between catalyst properties and performance, offering insights for tailored catalyst design in biomass conversion.
研究领域:
催化化学
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生物质转化
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高影响因子
Catalysts
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2019
·Vol. 9
·期 11
·886
·
IF 3.444
Wei Wang,Shaoying Sun,Fengan Han,Guangyi Li,Xianzhao Shao,Ning Li
Diesel and jet fuel range cycloalkanes were obtained in ~84.8% overall carbon yield with cyclopentanone and furfural, which can be produced from hemicellulose. Firstly, 2,5-bis(furan-2-ylmethyl)-cyclopentanone was prepared by the aldol condensation/hydrogenation reaction of cyclopentanone and furfural under solid base and selective hydrogenation catalyst. Over the optimized catalyst (Pd/C-CaO), 98.5% carbon yield of 2,5-bis(furan-2-ylmethyl)-cyclopentanone was acquired at 423 K. Subsequently, the 2,5-bis(furan-2-ylmethyl)-cyclopentanone was further hydrodeoxygenated over the M/H-ZSM-5(Pd, Pt and Ru) catalyst. Overall, 86.1% carbon yield of diesel and jet fuel range cycloalkanes was gained over the Pd/H-ZSM-5 catalyst under solvent-free conditions. The cycloalkane mixture obtained in this work has a high density (0.82 g mL−1) and a low freezing point (241.7 K). Therefore, it can be mixed into diesel and jet fuel to increase their volumetric heat values or payloads.Keywords:high density fuel;cyclopentanone;furfural;aldol condensation;hydrodeoxygenation
研究领域:
能源化学
·
催化反应工程
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高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
·
IF 22.1
Wei Lin,Yuexing Zhang,Zixu Ma,Zhiwei Sun,Xiaolong Liu,Chunbao Charles Xu,Renfeng Nie
Selectivity controlling is a crucial and challenging issue for the hydrogenation of furfural (FAL) to cyclopentanone (CPO). Herein, Ni 3 Sn 2 -ReO x /TiO 2 is synthesized via successive impregnation and exhibits full conversion and 92.5 % CPO selectivity under 3.0 MPa H 2 at 140 °C, which are much higher than those of Ni/TiO 2 and Ni 3 Sn 2 /TiO 2 . Characterizations show that Ni 3 Sn 2 is the main active phase that remarkably restrains the over-hydrogenation of the furan ring, while ReO x plays an electrophile or Lewis acid site to activate C-OH of furfuryl alcohol and induces its rearrangement. DFT calculations verify that Sn doping weakens the furan ring adsorption on Ni 3 Sn 2 and shifts its adsorption configuration, which consequently inhibits side reactions and favors the metal-acid (Ni 3 Sn 2 -ReO x ) synergy. The catalyst is stable, recyclable and also active at even 0.5 MPa H 2 and 80 °C. This study provides an advanced strategy for the rational design of superior catalysts for tuning product selectivity, with practical potential for upgrading biomass-derived platform molecules.
研究领域:
催化化学
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生物质转化
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理论计算
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DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2024
·
IF 15.7
Xu Zhang,Wen-Jing Zhang,Yan-Cheng Hu,Zhi-Guang Zhang,Jing-Pei Cao
High-energy-density (HED) fuels (e.g. JP-10) are of great importance in safeguarding territorial air security, since they can increase the flight range and payload of military aircrafts. To reduce the reliance on limited petroleum source, the production of HED fuel with renewable biomass feedstocks is highly appealing. But currently, most of the synthetic biofuels, due to their intrinsic ring structure, are incapable of competing with JP-10 in terms of energy density and freezing point. By emulating the structural characteristic of JP-10, we herein design and prepare a special C 16 fused tetracyclic biofuel using renewable cyclopentanone and benzoquinone as feedstocks. Key to success depends on selective dehydration of vicinal diol (dimer of cyclopentanone) over Amberlyst-15 in [Hmim]Cl. The Amberlyst-15/[Hmim]Cl system effectively suppresses the dominant pinacol-type rearrangement pathway and also exhibits good reusability for the dehydration. The hydrogen-bonding interaction between vicinal diol and imidazolium ring, as well as electrostatic force between carbocation intermediate and chloride anion contribute to the high diene selectivity. The compact ring framework gives rise to a density of 0.966 g/mL, combustion heat of 43.1 MJ/L, freezing point of ‒67 °C, and kinematic viscosity of 12.4 cSt, which are comparable to the properties of JP-10. It is expected that this as-prepared HED biofuel may potentially serve as a renewable alternative to petroleum fuel JP-10.
研究领域:
能源化学
·
可再生资源
·
催化化学
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高影响因子
危险品化学品经营许可证（带存储）