Co-reporter:Hong Yin;Caiping Sheng;Shenfeng Yuan;Haoran Li ;Jun Mei
Chemical Engineering & Technology 2014 Volume 37( Issue 10) pp:1797-1804
Publication Date(Web):
DOI:10.1002/ceat.201300726
Abstract
The mass transfer reaction kinetics of β-isophorone (β-IP) oxidation reaction by air was investigated in a lab-scale agitator bubbling reactor. This reaction can be regarded as instantaneous and there exists a critical concentration of β-IP. When the catalyst concentration is kept unchanged, the reaction rate is only controlled by the gas film and the reaction kinetics is of zero order with respect to β-IP when the β-IP concentration lies over the critical concentration. The reaction rate is controlled by the dual film and the kinetics is of first order with respect to β-IP when its concentration is below the critical concentration. Under the gas film-controlling condition, the effect of temperature, agitator speed, and aeration on the reaction rate is evaluated. A correlation equation of gas phase volumetric mass transfer coefficients combining superficial gas velocity and agitator speed is defined.
Co-reporter:DAN QIU;SHUANG-XI SHAO;BO ZHAO;YUE-CHAN WU;LI-FANG SHI;JIA-CHAO ZHOU;ZHI-RONG CHEN
Journal of Food Biochemistry 2012 Volume 36( Issue 2) pp:198-206
Publication Date(Web):
DOI:10.1111/j.1745-4514.2010.00526.x
ABSTRACT
The isomerization and decay of β-carotene in thermal oils were monitored using high-performance liquid chromatography and UV–vis spectroscopy (UV). For the first time, the effects of temperature, dissolved oxygen, oil type and antioxidants on the stability of β-carotene were systematically investigated by first-order kinetics. Isomerization of all-trans- to cis-isomer was a dominating reaction in the initial period (about 3 h for 140–180C). Lower temperature and oil with more unsaturated fatty acids gave positive effects on the β-carotene stability, whereas the dissolved oxygen slowed the decay rate at several conditions (150–180C of soybean oil, 140–180C of peanut oil and 140–150C of ODO). The antioxidants significantly protected β-carotene only when the temperature was lower than 150C, and they almost did not affect the β-carotene stability when the dissolved oxygen was removed.
PRACTICAL APPLICATIONS
As thermal treatment of β-carotene in oils become popular during food processing, and the stability of β-carotene is most related to its potential health benefits and nutritive value, the study on isomerization and decay kinetics of β-carotene in thermal oils is particularly important. We found that when β-carotene in oil was heated at 140–180C, isomerization was a dominating reaction in the initial period (about 2–4 h). The following decay of β-carotene of most conditions followed first-order kinetics. When β-carotene was dissolved in thermal oils, low temperature and oil with more unsaturated fatty acids gave positive effects on the β-carotene stability. Moreover, β-carotene always became more sensitive to temperature when dissolved oxygen is removed and antioxidants are added. Those positive impacts were effective only below 150C.
Co-reporter:Yeqiang Chen;Shenfeng Yuan;Hong Yin
Reaction Kinetics, Mechanisms and Catalysis 2011 Volume 102( Issue 1) pp:183-194
Publication Date(Web):2011 February
DOI:10.1007/s11144-010-0250-7
The kinetics of the reversible dimerization reaction of cyclohexanone in the presence of γ-alumina catalyst was investigated over the temperature range of 383.15–403.15 K at atmospheric pressure. The mechanism of the dimerization reaction of cyclohexanone catalyzed by γ-alumina is proposed. The Langmuir–Hinshelwood (LH) adsorption mechanism was used to study the reaction and a kinetic model was set up. The rate determining step of the reaction was found to be the reaction between two activated cyclohexanone molecules on the surface of the catalyst. Kinetic parameters such as activation energy and preexponential factor were calculated. The conversions calculated by model agreed with the experimental ones.
Co-reporter:Dan Qiu, Zhi-Rong Chen, Hao-Ran Li
Food Chemistry 2009 Volume 112(Issue 2) pp:344-349
Publication Date(Web):15 January 2009
DOI:10.1016/j.foodchem.2008.05.071
The effect of heating on isomerisation and stability of solid β-carotene was investigated, and the products generated by heating were analysed by a number of analytical techniques, including high-performance liquid chromatography (HPLC), UV/VIS-spectroscopy (UV) and gel permeation chromatography (GPC). For the first time, isomerisation of cis- to all-trans-isomer was demonstrated in partly melted solid β-carotene when β-carotene was heated at 90 and 140 °C. Only a few high molecular weight components were detected by GPC when β-carotene was heated in a nitrogen environment. In contrast, more high molecular weight polymers, as well as low molecular fragments, were produced when β-carotene was heated and exposed to air, suggesting that polymerisation was one of the dominant side-reactions of β-carotene change, in addition to degradation.
Co-reporter:Dan Qiu, Zhi-Rong Chen, Hao-Ran Li
Journal of Molecular Structure: THEOCHEM 2008 Volume 865(1–3) pp:44-48
Publication Date(Web):30 September 2008
DOI:10.1016/j.theochem.2008.06.015
The density functional theory method B3LYP is employed to study the thermal isomerization of β-carotene. The results present the following sequence of stability of neutral isomers: all-trans > 9-cis > 13-cis > 9,13-di-cis = 9,13′-di-cis > 15-cis > 9,15-di-cis > 13,15-di-cis > 7-cis > 11-cis. PCM calculations show that all isomers are influenced by the stabilizing effect of melting. The mechanism of thermal isomerization suggests that the isomerization of β-carotene occurs primarily via the radical cation while triplet-excited β-carotene is also a possible intermediate of isomerization, especially under mild conditions.
Co-reporter:Kejing Liu, Cheng Liang, Qiyi Ma, Renfeng Du, Yongtao Wang, Jianyong Mao, Zhirong Chen, Haoran Li
Molecular Catalysis (March 2017) Volume 428() pp:24-32
Publication Date(Web):1 March 2017
DOI:10.1016/j.molcata.2016.11.037
•It was found that 4-methyl guaiacol was oxidized to vinillin catalyzed by CoCl2 but to oligomers by CuCl2.•Co(II) was predominant when Cu(II) and Co(II) catalysts were cooperative in extensive alkali.•The structures of Co/Cu-NaOH complexes and the complementary mechanisms were investigated.•It was speculated that the extraordinary activity of CoCl2/NaOH system resulted from Co(IV) = O.In excess alkali, 4-methylguaiacol was successfully oxidized to vanillin by Co-salt/NaOH catalytic system with conversion of 100% and selectivity of 90%; however, with conversion of 87% and selectivity of 9% when the catalytic system was replaced by Cu-salt/NaOH. To explore the different catalytic effects, the detailed structural characterizations of the catalysts were carried out by EPR, DLS, and UV–vis technologies. The results suggest that both Co(II)/NaOH and Cu(II)/NaOH systems are heterogeneous and the Co(IV) = O might be an essential factor for the high selectivity in Co(II)-catalysis.Download full-size image