Case Studies in Thermal Engineering
·
2023
·
IF 6.8
Haijun Cheng,Haoping Chen,Qilin Huang,Qiaoni Luo,Min Liang,Suyi Dai,Fang Lai,Li Ma,Weiguang Li,Xiongmin Liu
Although pinane has a wide range of uses, there are no reports on the safety of pinane oxidation. The thermal oxidation properties of pinane were investigated through MCPVT. The primary oxidation products of pinane were separated and structurally characterised, and its decomposition properties were assessed by MCPVT and DSC. The results showed that pinane had an initial oxygen uptake temperature of 123.5 °C and exploded when the temperature rose to 132.7 °C. Pinane autoxidised at 110 °C for 9 h formed a high level of peroxide (81.18 mmol/kg) with an activation energy of 138.77 kJ/mol. The oxidation of pinane occurs mainly at the tertiary carbon atom attached to the methyl group, and the main peroxide produced is pinane hydroperoxide (PHP). PHP has an exothermic onset temperature (T onset ), a heat of decomposition (Q DSC ) and an activation energy of decomposition of 114.6 °C, 1878.0 J/g and 109.4 kJ/mol respectively, which should classify it as a hazardous substance. PHP has a lower activation energy than pinane and is the determining factor for the safety of the pinane oxidation reaction. The products of thermal runaway of pinane are relatively complex and consist mainly of 1-(2, 2-dimethyl-3-ethylcyclobutyl) ethanone, nopinone, 2, 3-pinanediol and pinonic acid.
研究领域:
化学
·
安全科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2021
·
IF 6.609
Yakun Liu,Chengxiang Shi,Lun Pan,Xiangwen Zhang,Ji-Jun Zou
With the rapid development of aerospace industry, it is significantly necessary to develop advanced rocket fuels with high density, high specific impulse and good combustion performance. In this work, we report the synthesis of cyclopropanated pinanes through cyclopropanation of pinene. The reaction conditions including reaction time, solvent type, halohydrocarbon and molar ratio of zinc carbenoid to pinene were optimized. The basic physical properties of fuel, including density, kinematic viscosity, freezing point, calorific value, and combustion performance were tested, and the specific impulses of cyclopropanated pinanes were also calculated. Importantly, the cyclopropanated α- and β-pinane possess high density of 0.90 and 0.91 g/mL, specific impulse of 330.58 and 330.39 s, which results in higher volumetric specific impulse than reported rocket fuels. They also show good low-temperature performance and better ignition and combustion performance than JP-10. These excellent performances indicate that the cyclopropanated α- and β-pinane have great application prospect as high-energy rocket fuel.
研究领域:
燃料化学
·
航空航天工程
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yu-Xuan Fu,Shu-Yi Huang,Ming-Shuai Sun,Yan Zhou,Dan-Dan Cai,Wen-Shuai Zhu,Wei Hui,Duan-Jian Tao
Current industrial catalysts for α-pinene hydrogenation suffer from harsh reaction conditions and poor selectivity to cis -pinane, primarily due to their inability to effectively adsorb α-pinene in a specific favorable configuration on the catalyst surface. In this study, a high-specific-surface-area, rod-shaped CeO 2 -supported ultra-fine Ru nanoparticle (average particle size of 4 nm) catalyst was synthesized via hydrothermal method for the highly stereoselective hydrogenation of α-pinene to cis -pinane. The resulting Ru/CeO 2 -H catalyst achieved an α-pinene conversion of 99.3 % and an impressive cis -pinane selectivity of up to 99.6 % under exceptionally low temperature (30°C), 0.6 MPa H 2 and 0.5 h with high TOF (1236 h −1 ). Density functional theory (DFT) calculations indicated that α-pinene preferentially adsorbs onto the Ru surface via the backside of its intramolecular dimethyl bridge. This particular adsorption mode lowers the energy barriers for further hydrogenation to generate cis -pinane. The oriented dimethyl-up configuration of α-pinene and ultra-low activation energy (12.04 kJ/mol obtained from kinetic tests) enable the highly selective production of cis -pinane at ambient temperature. Furthermore, the strong interaction between the CeO 2 -H support and highly dispersed Ru, combined with the ambient-temperature reaction conditions, effectively prevents metal nanoparticle agglomeration and coking, imparting the catalyst with exceptional stability. Notably, the catalyst was reused at least 15 times without observing any significant deactivation, demonstrating its significant potential for practical applications.
研究领域:
催化化学
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材料科学
·
理论化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2018
·
IF 4.439
Li Qu,Hailong Yu,Fengli Yu,Bing Yuan,Congxia Xie,Shitao Yu
A new and environmental friendly route has been developed to hydrogenate α-pinene to cis -pinane. The α-pinene was hydrogenated using ruthenium (Ru) nanoparticles that were stabilized by modified carboxymethyl cellulose in aqueous medium. The conversion of α-pinene reached 96.6% and the selectivity of cis -pinane was 98.4%. Ru nanoparticles could be recycled 18 times. Ru nanoparticles and micelles were characterized by transmission electron microscopy (TEM), confocal laser scanning microscopy (CLSM), dynamic light scattering (DLS), X-ray diffraction (XRD), and other detection techniques. Ru nanoparticles (3.2 nm) had a good stability and uniform distribution, the reaction was divided into micelles that appeared to act as “microreactors”, and the micelle size was increased in the absence of sodium carbonate. The good stability of the Ru nanoparticles could be attributed to electrostatic and steric stabilization.
研究领域:
化学工程
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2017
·Vol. 7
·期 81
·51452-51459
·
IF 3.108
Lihua Xie,Xiaoyan Wang,Fengli Yu,Bing Yuan,Congxia Xie,Shitao Yu
Amphiphilic mesoporous silica modified with trimethoxy (3,3,3-trifluoropropyl) silane (TFPS) and (3-aminopropyl) trimethoxysilane (APTS) was prepared by one-step synthesis. The structure and morphology of the mesoporous silica were characterized and confirmed by solid-state nuclear magnetic resonance, X-ray diffraction (XRD), N2 adsorption–desorption, Fourier transfer infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Meanwhile, the thermostability of the amphiphilic mesoporous silica was detected by thermogravimetric (TG) technique. Highly dispersed Ru nanoparticles supported on such amphiphilic mesoporous silica (marked as Ru/MF@MN) were synthesized by wet impregnation method with the assistance of ultrasonic. The catalyst was characterized by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). In water medium, Ru/MF@MN was used in α-pinene hydrogenation to prepare cis-pinane. Under the optimum reaction conditions (35 °C, 2 MPa H2, 1 h, m (H2O) : m (α-pinene) : m (Ru/MF@MN) = 200 : 60 : 1), 99.9% α-pinene conversion and 98.9% cis-pinane selectivity were obtained. When Ru/MF@MN was recycled six times, the conversion slightly decreased and the selectivity was nearly unchanged.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2019
·Vol. 9
·期 11
·5978-5986
·
IF 3.049
Shunyou Hu,Linlin Wang,Xiaopeng Chen,Xiaojie Wei,Zhangfa Tong,Lijiang Yin
The concept of a solid catalyst coated with a thin ionic liquid layer (SCILL) was applied to the stereoselective hydrogenation of α-pinene. Nickel, a non-noble metal, was supported on a discarded fluid catalytic cracking catalyst (DF3C) and then modified with different loadings of the ionic liquid 1-ethanol-3-methylimidazolium tetrafluoroborate ([C2OHmim][BF4]). The resulting catalysts showed a range of conversions and selectivities for the hydrogenation of α-pinene. The SCILL catalysts afforded cis-pinane with high selectivity and their activity depended on the ionic liquid loading. For an ionic liquid loading of 10 wt%, although the catalytic activity was suppressed, the selectivity and conversion could reach above 98% and 99%, respectively. In addition, the catalyst remained stable after 13 runs and the activity was almost unchanged with the conversion maintained at approximately 99%. Thus, the ionic liquid layer not only improved the selectivity for cis-pinane but also protected the active site of the catalyst and prolonged the service lifetime of the catalyst. The SCILL catalytic system provides an example of an ionic liquid catalytic system which eliminates organic solvents from the catalytic process.
研究领域:
化学工程
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催化科学
✓ 已验证
DOI
PubMed
高影响因子
ChemCatChem
·
2019
·Vol. 11
·期 5
·1518-1525
·
IF 4.495
Fengli Yu,Lihua Xie,Fangzhu Wu,Bing Yuan,Congxia Xie,Shitao Yu,Xien Liu,Lei Wang,Dan Wang
Graphical Take core ! Highly dispersed and stable Ru nanoparticle catalysts loaded on boron-doped amphiphilic, core-shell, mesoporous molecular sieves are successfully prepared and used to catalyze the hydrogenation of α-pinene to cis -pinane with an excellent catalytic activity, high selectivity, and good recyclability, in mild experimental conditions given that every nanocomposite is equivalent to a microreactor. Highly dispersed and stable catalysts comprising Ru nanoparticles supported on boron-doped amphiphilic core-shell mesoporous molecular sieves (MMS−C@MMS−NH 2 /B/Ru) with alkyl-modified hydrophobic silica core and NH 2 -functionalized hydrophilic silica shell are successfully prepared for use in hydrogenation of α-pinene for the first time. Dodecyl-modified MMS−C 12 @MMS−NH 2 /B/Ru exhibits the best catalytic activity under mild hydrogenation conditions. The abundant −NH 2 functional groups on the molecular sieve surface and their amphipathy allow the sieves to facilitate attachment of more Ru nanoparticles, and to simplify their dispersion in the water-organic reaction medium. Moreover, B-doped molecular sieves may adjust their acidity to meet the needs of α-pinene hydrogenation. Under mild reaction conditions (25 °C, 1 MPa H 2 , and 1 h), α-pinene can be completely converted with 99 % selectivity to cis -pinane, because every nanocomposite is equivalent to a microreactor. The catalytic activity does not change much over 5 cycles, indicating that Ru nanoparticles are stably loaded on the molecular sieves.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 109
·89552-89558
·
IF 3.84
Shengli Hou,Congxia Xie,Hua Zhong,Shitao Yu
Ruthenium (Ru) nanoparticles were prepared using polyoxyethylene–polyoxypropylene–polyoxyethylene triblock copolymer (P123) micelles in water as a stabilizing agent. The P123–Ru micellar catalyst was first used in the hydrogenation of α-pinene to pinane, and the selectivity for cis-pinane reached 98.9%. This result is attributed to the formation of vesicles. The isolated catalyst phase could be used seven times with no treatment, and its catalytic activity and selectivity were almost unchanged. The preparation process of the catalyst and hydrogenation reaction of α-pinene was under mild and environmentally friendly conditions. This research offers an effective method for the hydrogenation of α-pinene and provides a reference for other hydrophobic natural products in hydrogenation reactions.
研究领域:
化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 46
·期 3
·1399-1408
·
IF 3.591
Wanbing Li,Haibo Zhang,Zhaolan Zhai,Xujuan Huang,Shibin Shang,Zhanqian Song
Novel ‘bola’ rosin-based photo-responsive amphiphilic polymers PMPn (n = 17, 34, or 69) were synthesized using poly(ethylene glycol) (PEG) as a double hydrophilic head and N-azobenzenemaleimidepimaric acid (AZOMPA) as a hydrophobic tail. The relatively fixed position of the rigid group of rosin can reduce the entanglement of PEG chains and enhance the influence of the cis-isomerization of azobenzene on the volume and polarity of the entire polymer. Consequently, all polymers with different chain lengths show an extremely high photoresponsive efficiency and various morphological changes. For the PMP17 and PMP34 assemblies, collapse of the sphere micelles takes place upon UV irradiation and this process is reversible; by contrast, the PMP69 assemblies transformed from worm micelles to large spherical micelles, cloud-like micelles, large composite micelles and irregular spherical micelles. Subsequently, encapsulation of the hydrophobic fluorescent probe Nile red and as well as its release from the loaded probes triggered by UV irradiation were evaluated. The UV irradiation experiments demonstrated the photoresponsive behavior of the “bola” amphiphilic polymers PMPn containing the rigid rosin-based azobenzene group, giving an elegant strategy for design of stimuli-responsive materials.
研究领域:
材料科学
·
高分子化学
·
光化学
✓ 已验证
DOI
高影响因子
RSC Advances
·
2016
·Vol. 6
·期 84
·81310-81317
·
IF 3.289
Yue Liu,Lu Li,Shiwei Liu,Congxia Xie,Shitao Yu
(3-Aminopropyl)-triethoxysilane (APTS) and (3-mercaptopropyl)-trimethoxysilane (MPTS) grafted SiO2-coated iron oxide (Fe3O4@SiO2) magnetic supports were prepared. Various noble metal nanoparticles such as Ru, Pt, Rh and Pd were directly grown on the surfaces of the magnetic supports with ultrasmall and nearly monodisperse sizes, especially the APTS grafted Fe3O4@SiO2 (Fe3O4@SiO2/APTS) nanospheres. The Fe3O4@SiO2/APTS/Ru catalyst demonstrated a high catalytic activity towards the hydrogenation of α-pinene to form cis-pinane. The conversion of α-pinene was 99.1% and the selectivity for cis-pinane reached 97.6% at 120 °C after 4 h. The Fe3O4@SiO2/APTS/Ru catalyst was easily separated from the reaction mixture when applying an external magnetic field, and the separated Fe3O4@SiO2/APTS/Ru had good reusability. After being reused eight times, the α-pinene conversion and the cis-pinane selectivity also can reach 97.8% and 96.9%, respectively.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Defu Yin,Zewei Hu,Mingya Liu,Jingyun Zhang,Hanli Zheng,Yunxi Hou,Shitao Yu,Lu Li,Shiwei Liu,Yue Liu
The highly stereoselective hydrogenation of α-pinene was very important and challenging in the utilization of natural products at mild conditions. Here, we reported a core–shell catalyst coated with Ir metal particles by mesoporous silica shell, and revealing the dependence of reducing agents during the preparation process. The prepared nano catalyst exhibited excellent performance in the hydrogenation of chiral substance α-pinene, especially under very mild conditions (40 °C, 1 MPa H 2 and 2 h), with a yield of cis -pinane reaching ∼99 %. The characterization methods revealed that the excellent performance was attributed to the strong hydrogenolysis ability of Ir particles. DFT results further indicated that α-pinene can stably adsorb on the edge sites of Ir metal in a cis structure, thereby achieving highly stereoselective hydrogenation. This work utilized heterogeneous catalysis to achieve performance close to that of homogeneous catalysts. The stable core shell structure greatly prolonged the lifespan of the catalyst and overcame the drawbacks of homogeneous catalysts. This work provided more reference cases for chiral hydrogenation.
研究领域:
催化
·
材料科学
·
化学工程
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
Russian Journal of Physical Chemistry A
·
2019
·Vol. 93
·期 9
·1754-1761
·
IF 0.581
Yin Hu,Chen Wei,Ba Mingwei,Xie Xin,Song Weiguo
Abstract Ru/TiO 2 nanocomposite was prepared via loading the active ruthenium species on anatase TiO 2 by a simple hydrothermal approach combined with a sol–gel method. The optimal catalyst with 5.0% of Ru species showed excellent catalytic performance in the solvent-free selective hydrogenation of α-pinene with the conversion of α-pinene and selectivity to cis -pinane of 100.0 and 97.1%, respectively. It has been verified that the superior performance depends on the large amounts of acidic sites induced by HF acid and the SMSI effect between the reducible TiO 2 support and Ru species on its surface. The partial loss of its activity after five hydrogenation cycles should be due to the agglomeration of the catalyst particles and the carbon deposition on the surface. The possible hydrogenation mechanism was also discussed. This work provides an effective approach to develop a highly efficient and recyclable catalyst for the solvent-free selective hydrogenation of α-pinene.
研究领域:
催化
·
化学工程
·
材料科学
·
有机化学
✓ 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）