Two alkyl phenols,namely,2,5-dimethoxy-3-undecylphenol（1） and 5-methoxy-3-undecylphenol（2）,were isolated together with two known benzoquinones,5-O-methylembelin（3） and 2-dehydroxy-5-O-methylembelin（4） from the...Two alkyl phenols,namely,2,5-dimethoxy-3-undecylphenol（1） and 5-methoxy-3-undecylphenol（2）,were isolated together with two known benzoquinones,5-O-methylembelin（3） and 2-dehydroxy-5-O-methylembelin（4） from the wood of Averrhoa carambola.Their structures were elucidated on the basis of spectroscopic methods（1D and 2D NMR）.展开更多
The presence of Alkyl Phenols(APs) in aquatic systems is considered as one of the environmental concerns in recent decades which are generally used as surfactants. APs are endocrine disruptors and estrogen-mimicking,c...The presence of Alkyl Phenols(APs) in aquatic systems is considered as one of the environmental concerns in recent decades which are generally used as surfactants. APs are endocrine disruptors and estrogen-mimicking,causing harmful effects such as feminization and carcinogenesis on aquatic environment and human health.The most commercially important APs are 4-Nonyl Phenol(4-NP) and 4-tert-OctylP henol(4-t-OP). Moving bed biofilm reactor(MBBR), which combined attached and suspended growth advantages, is an advanced biological treatment process for municipal and industrial wastewaters that has drawn considerable attention from many researchers to remove toxic pollutants from wastewater. The aim of this research was to evaluate Bacterial activities and kinetic coefficients in the presence of APs. This study was carried out using laboratory-scale MBBR fed with synthetic wastewater containing 4-NP and 4-t-OP. The reactor was operated at different loads of chemical oxygen demand(COD) and APs and different hydraulic retention time(HRT). The respirometric technique was applied to investigate the effect of APs on heterotrophic and autotrophic activity and kinetic coefficients in biomass obtained from MBBR. Respirometric technique demonstrates a reliable tool in order to assess the biofilm kinetic coefficients and biomass viability to insert in the mathematical models. The calculated kinetic parameters were in the range of conventional and extended aeration activated sludge processes. The results demonstrate that APs have significant inhibitory effects on activity and growth rate of heterotrophic and autotrophic bacteria, heterotrophs have been less affected by the presence of 4-NP and 4-t-OP, and these compounds had greater inhibitory effects on autotrophic bacteria.展开更多
A negligible depletion-solid phase microextraction (nd-SPME) method is developed to measure free concentrations of two alkyl phenols (4-t-octylphenol, nonylphenol) and bisphenol A in activated sludge, with which aerob...A negligible depletion-solid phase microextraction (nd-SPME) method is developed to measure free concentrations of two alkyl phenols (4-t-octylphenol, nonylphenol) and bisphenol A in activated sludge, with which aerobic biodegradation kinetics of three pollutants was determined. For the degradation of octylphenol, nonylphenol and bisphenol A, the apparent rate constant based on total concentration is 0.02, 0.01 and 0.03 h-1, respectively; with the half life being 34.9, 54.3 and 22.3 h correspondingly. Meanwhile, real rate constants based on free concentration are 0.74, 0.60 and 1.03 h-1, respectively; with the half life being 0.9, 1.2 and 0.7 h accordingly. Differences between two constants revealed that desorption of targeted pollutants from activated sludge should be the rate-limiting step. Compared to the rapid biodegradation of alkyl phenols and bisphenol A in free state, the desorption of pollutants from the sludge is relatively slow, which made the apparent biodegradation rate constants much lower.展开更多
The alkylation of phenol with methanol was studied and a high selectivity for O-alkylation was attained over alkali-metal cation-exchanged X zeolites. The transformation of primary products of the title reaction was a...The alkylation of phenol with methanol was studied and a high selectivity for O-alkylation was attained over alkali-metal cation-exchanged X zeolites. The transformation of primary products of the title reaction was also studied over CsX zeolite. On the basis of experimental results, a reaction scheme on CsX zeolite was suggested.展开更多
Gas chromatographic measurements of the relative retention times of alkyl-substituted arenes and phenols on capillary columns at temperatures of 125 – 140°C have shown that logarithms of retention times increase...Gas chromatographic measurements of the relative retention times of alkyl-substituted arenes and phenols on capillary columns at temperatures of 125 – 140°C have shown that logarithms of retention times increase bilinearly with the number of carbon atoms in the molecule. It was found that in a high density stationary phase, the longer alkyl side chains of compounds in question are subject to cyclization as a result of the resistance force of this phase affecting molecules during their thermal and diffusion motion. Consequently, common conventional aromatic-aliphatic molecules become new molecules with quasi-alicyclic rings. In comparison with the conventionally conceived molecules, the resulting aromatic–quasi-alicyclic molecules are characterized by rather different, possibly even completely different non-covalent interactions between the molecules, which then affect the retention characteristics. Moreover, cyclization facilitates the mixing of n-alkyl arenes and n-alkyl phenols with high-molecular stationary phases, because the thermodynamic condition for mixing is better fulfilled.展开更多
This study analyzed the pyrolysis mechanism,developed a pyrolysis kinetic model,and determined the corresponding thermodynamic parameters for the removal of calcium from used lubricating oil using sulfurized calcium a...This study analyzed the pyrolysis mechanism,developed a pyrolysis kinetic model,and determined the corresponding thermodynamic parameters for the removal of calcium from used lubricating oil using sulfurized calcium alkyl phenolate(T-115B)as a model compound.The pyrolysis process and products were evaluated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.Visual inspection indicated that the removal of calcium from T-115B depended primarily on the destruction of micelles caused by the pyrolysis of compounds at high temperatures.The pyrolysis characteristics of T-115B at different heating rates were investigated by thermogravimetry and differential thermal analysis,which revealed two distinct pyrolysis phases.Thus,the pyrolysis mechanism can be described by a twostep model.The activation energy and thermodynamic parameters(ΔH,ΔG,andΔS)were determined by applying the Kissinger-Akahira-Sunose,Flynn-Wall-Ozawa,Friedman,and Starink methods;the average activation energies for T-115B pyrolysis obtained using these methods were 115.80,119.84,124.96,and 116.14 kJ/mol,respectively.Further,both stages of the pyrolysis reaction followed Fn mechanisms with n=1.39 in the first stage and n=0.86 in the second stage.This study provides reliable and effective pyrolysis models along with kinetic and thermodynamic parameters to facilitate the largescale industrial application of used lubricating oil.展开更多
Para-tert-butyl phenol (p-TBP) and 2,4-di-tert-butyl phenol (2,4-DTBP) are widely used for the preparation of antioxidants. Zeolite catalysts showed good performance for the synthesis of p-TBP and 2,4-DTBP. In this wo...Para-tert-butyl phenol (p-TBP) and 2,4-di-tert-butyl phenol (2,4-DTBP) are widely used for the preparation of antioxidants. Zeolite catalysts showed good performance for the synthesis of p-TBP and 2,4-DTBP. In this work, zeolite H-mordenite (HM) catalyst was prepared and the alkylation of phenol with tert-butyl alcohol over zeolite HM catalyst was investigated at different reaction conditions. It is found that increasing temperature enhances the selectivity to p-TBP and the optimum reaction temperature for phenol conversion is 438 K. Increasing flow rate decreases phenol conversion apparently while the selectivity to p-TBP has a little increase. The suitable tert-butyl alcohol/phenol molar ratio is 2. Lower alcohol/phenol molar ratios are beneficial to p-TBP while higher ones are helpful for producing 2,4-DTBP.展开更多
基金support from the Commission on Higher Education(CHE-RES-RG)
文摘Two alkyl phenols,namely,2,5-dimethoxy-3-undecylphenol（1） and 5-methoxy-3-undecylphenol（2）,were isolated together with two known benzoquinones,5-O-methylembelin（3） and 2-dehydroxy-5-O-methylembelin（4） from the wood of Averrhoa carambola.Their structures were elucidated on the basis of spectroscopic methods（1D and 2D NMR）.
基金the result of PhD thesis approved in the Isfahan University of Medical Sciences(IUMS)Vice Chancellery of Research of IUMS for the financial support,Research Project,#394773
文摘The presence of Alkyl Phenols(APs) in aquatic systems is considered as one of the environmental concerns in recent decades which are generally used as surfactants. APs are endocrine disruptors and estrogen-mimicking,causing harmful effects such as feminization and carcinogenesis on aquatic environment and human health.The most commercially important APs are 4-Nonyl Phenol(4-NP) and 4-tert-OctylP henol(4-t-OP). Moving bed biofilm reactor(MBBR), which combined attached and suspended growth advantages, is an advanced biological treatment process for municipal and industrial wastewaters that has drawn considerable attention from many researchers to remove toxic pollutants from wastewater. The aim of this research was to evaluate Bacterial activities and kinetic coefficients in the presence of APs. This study was carried out using laboratory-scale MBBR fed with synthetic wastewater containing 4-NP and 4-t-OP. The reactor was operated at different loads of chemical oxygen demand(COD) and APs and different hydraulic retention time(HRT). The respirometric technique was applied to investigate the effect of APs on heterotrophic and autotrophic activity and kinetic coefficients in biomass obtained from MBBR. Respirometric technique demonstrates a reliable tool in order to assess the biofilm kinetic coefficients and biomass viability to insert in the mathematical models. The calculated kinetic parameters were in the range of conventional and extended aeration activated sludge processes. The results demonstrate that APs have significant inhibitory effects on activity and growth rate of heterotrophic and autotrophic bacteria, heterotrophs have been less affected by the presence of 4-NP and 4-t-OP, and these compounds had greater inhibitory effects on autotrophic bacteria.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 50625823 and 50538090)
文摘A negligible depletion-solid phase microextraction (nd-SPME) method is developed to measure free concentrations of two alkyl phenols (4-t-octylphenol, nonylphenol) and bisphenol A in activated sludge, with which aerobic biodegradation kinetics of three pollutants was determined. For the degradation of octylphenol, nonylphenol and bisphenol A, the apparent rate constant based on total concentration is 0.02, 0.01 and 0.03 h-1, respectively; with the half life being 34.9, 54.3 and 22.3 h correspondingly. Meanwhile, real rate constants based on free concentration are 0.74, 0.60 and 1.03 h-1, respectively; with the half life being 0.9, 1.2 and 0.7 h accordingly. Differences between two constants revealed that desorption of targeted pollutants from activated sludge should be the rate-limiting step. Compared to the rapid biodegradation of alkyl phenols and bisphenol A in free state, the desorption of pollutants from the sludge is relatively slow, which made the apparent biodegradation rate constants much lower.
文摘The alkylation of phenol with methanol was studied and a high selectivity for O-alkylation was attained over alkali-metal cation-exchanged X zeolites. The transformation of primary products of the title reaction was also studied over CsX zeolite. On the basis of experimental results, a reaction scheme on CsX zeolite was suggested.
文摘Gas chromatographic measurements of the relative retention times of alkyl-substituted arenes and phenols on capillary columns at temperatures of 125 – 140°C have shown that logarithms of retention times increase bilinearly with the number of carbon atoms in the molecule. It was found that in a high density stationary phase, the longer alkyl side chains of compounds in question are subject to cyclization as a result of the resistance force of this phase affecting molecules during their thermal and diffusion motion. Consequently, common conventional aromatic-aliphatic molecules become new molecules with quasi-alicyclic rings. In comparison with the conventionally conceived molecules, the resulting aromatic–quasi-alicyclic molecules are characterized by rather different, possibly even completely different non-covalent interactions between the molecules, which then affect the retention characteristics. Moreover, cyclization facilitates the mixing of n-alkyl arenes and n-alkyl phenols with high-molecular stationary phases, because the thermodynamic condition for mixing is better fulfilled.
基金We are grateful for the support of the Science and Technology Innovation 2025 Major project of Ningbo[2018B10038]the Chair Professorship Program of Shandong University of Technology[117002]the Natural Science Foundation of Shandong Province[ZR2020MB130].
文摘This study analyzed the pyrolysis mechanism,developed a pyrolysis kinetic model,and determined the corresponding thermodynamic parameters for the removal of calcium from used lubricating oil using sulfurized calcium alkyl phenolate(T-115B)as a model compound.The pyrolysis process and products were evaluated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.Visual inspection indicated that the removal of calcium from T-115B depended primarily on the destruction of micelles caused by the pyrolysis of compounds at high temperatures.The pyrolysis characteristics of T-115B at different heating rates were investigated by thermogravimetry and differential thermal analysis,which revealed two distinct pyrolysis phases.Thus,the pyrolysis mechanism can be described by a twostep model.The activation energy and thermodynamic parameters(ΔH,ΔG,andΔS)were determined by applying the Kissinger-Akahira-Sunose,Flynn-Wall-Ozawa,Friedman,and Starink methods;the average activation energies for T-115B pyrolysis obtained using these methods were 115.80,119.84,124.96,and 116.14 kJ/mol,respectively.Further,both stages of the pyrolysis reaction followed Fn mechanisms with n=1.39 in the first stage and n=0.86 in the second stage.This study provides reliable and effective pyrolysis models along with kinetic and thermodynamic parameters to facilitate the largescale industrial application of used lubricating oil.
文摘Para-tert-butyl phenol (p-TBP) and 2,4-di-tert-butyl phenol (2,4-DTBP) are widely used for the preparation of antioxidants. Zeolite catalysts showed good performance for the synthesis of p-TBP and 2,4-DTBP. In this work, zeolite H-mordenite (HM) catalyst was prepared and the alkylation of phenol with tert-butyl alcohol over zeolite HM catalyst was investigated at different reaction conditions. It is found that increasing temperature enhances the selectivity to p-TBP and the optimum reaction temperature for phenol conversion is 438 K. Increasing flow rate decreases phenol conversion apparently while the selectivity to p-TBP has a little increase. The suitable tert-butyl alcohol/phenol molar ratio is 2. Lower alcohol/phenol molar ratios are beneficial to p-TBP while higher ones are helpful for producing 2,4-DTBP.
