The thermal behavior, nonisothermal decomposition reaction kinetics and specific heat capacity of nitrate glycerol ether cellulose（NGEC） were determined by thermogravimetric analysis（TGA）, differential scanning ca...The thermal behavior, nonisothermal decomposition reaction kinetics and specific heat capacity of nitrate glycerol ether cellulose（NGEC） were determined by thermogravimetric analysis（TGA）, differential scanning calori- metry（DSC） and microcalorimetry. The apparent activity energy（Ea）, reaction mechanism function, quadratic equa- tion of specific heat capacity（Cp） with temperature were obtained. The kinetic parameters of the decomposition reac- tion are Ea=170.2 kJ/mol and lg（A/s^-l）=16.3. The kinetic equation isf（α）=（4/3）（1-α）[-ln（1-α）]^1/4. The specific heat capacity equation is Cp=1.285-6.276×10^-3T＋1.581×10^-5T^2（283 K〈T〈353 K）. With these parameters, the thermal safety properties of NGEC were studied, such as the self-accelerating decomposition temperature（TSADT）, critical temperature of thermal explosion（Tb） and adiabatic time-to-explosion（tTlad）. The results of the thermal safety evalua- tion of NGEC are： TSADV=459.6 K, Tb=492.8 K, tTlad=0.8 S.展开更多
This research was focused on the valorisation of glycerol,exploring the feasibility of an efficient route for oxygenated additives production based on its etherification with bio-butanol.A home-made BEA zeolite sample...This research was focused on the valorisation of glycerol,exploring the feasibility of an efficient route for oxygenated additives production based on its etherification with bio-butanol.A home-made BEA zeolite sample with a tuneable acidity has been proposed as the catalytic system,being tested in a stirred reactor under different etherification conditions.Although a reaction temperature as high as 200℃resulted to be beneficial in terms of glycerol conversion(-90%),only by operating at milder conditions the product selectivity to glycerol-ethers can be better controlled,in order to obtain a bio-fuel complying with the requirements for mixing with fossil diesel or biodiesel,without any need of purification from large amount of by-products.A comprehensive identification of all the compounds formed during the reaction was performed by a GC-MS analysis,on the basis of the complex network of consecutive and parallel reaction paths leading not only to the desired ethers,but also to many side products not detected in similar acid-catalyzed reactions in liquid phase and not available in the most used mass-spectra libraries.展开更多
The 1-O-monoalkyl glycerol ethers （MAGEs） were initially viewed as the biomarkers for sulfate-reducing bacteria （SRB） me- diating anaerobic oxidation of methane in the marine environments. However, limited informa...The 1-O-monoalkyl glycerol ethers （MAGEs） were initially viewed as the biomarkers for sulfate-reducing bacteria （SRB） me- diating anaerobic oxidation of methane in the marine environments. However, limited information is known about their distri- bution in terrestrial and other aquatic settings including soils, fresh water lakes, and cave sediments, which may obscure our understanding of their biological sources. Here we found that MAGEs were ubiquitous but differed obviously in distributional pattern among those environments. The surface soils are dominated generally by iC15：0-MAGE, followed by nCI6：o-MAGE whereas the lake sediments show the opposite, resulting in significantly higher iC15：0/nC16：0 ratios in soils than in lake sedi- ments. The cave deposits are characterized by considerably higher proportions of branched MAGEs than the former two envi- ronments. The logarithm of iC15：0/aC15：0 ratio shows a significant negative correlation with soil pH, likely reflecting an adapta- tion of microbial cell membrane to change in the ambient proton concentration. The MAGE profiles in cultured bacteria cannot fully explain the MAGE distribution in all the samples analyzed. Therefore, MAGEs in soil, lake sediments, and cave deposits likely have additional biological source（s） other than SRB and cultured MAGE-producing bacteria. The difference in MAGE pattern among environments is likely to be attributed to change in microbial communities.展开更多
At modern cold seeps,the anaerobic oxidation of methane(AOM)is the dominant pathway for methane consumption in marine sediments.AOM,which is mediated by a consortium of methane oxidizing archaea and sulfate reducing b...At modern cold seeps,the anaerobic oxidation of methane(AOM)is the dominant pathway for methane consumption in marine sediments.AOM,which is mediated by a consortium of methane oxidizing archaea and sulfate reducing bacteria,is proposed to be responsible for authigenic carbonate formation.A methane-derived carbonate chimney was collected from the Shenhu area, northern South China Sea.The membrane lipids and their very low carbon isotopic compositions(?115‰to?104‰)in the Shenhu chimney suggest the presence of an AOM process.Three specific archaeal and bacterial biomarkers were detected,including Ar,DAGE 1f,and monocyclic MDGD.Their strongly depleted??13C values(?115‰to?104‰),which are lower than those of the normal marine lipids in sediments,reveal biogenic methane as their origin.The carbonate deposits exhibiting a chimney structure indicate that a vigorous methane-rich fluid expulsion may have occurred at the seafloor.We propose that the decomposition of gas hydrates at depth is the likely cause of seepage and cold seep carbonate formation in the Shenhu area.展开更多
基金Supported by the Foundation of National Key Laboratory of Science and Technology on Combustion and Explosion of China(No.9140C3503011004)
文摘The thermal behavior, nonisothermal decomposition reaction kinetics and specific heat capacity of nitrate glycerol ether cellulose（NGEC） were determined by thermogravimetric analysis（TGA）, differential scanning calori- metry（DSC） and microcalorimetry. The apparent activity energy（Ea）, reaction mechanism function, quadratic equa- tion of specific heat capacity（Cp） with temperature were obtained. The kinetic parameters of the decomposition reac- tion are Ea=170.2 kJ/mol and lg（A/s^-l）=16.3. The kinetic equation isf（α）=（4/3）（1-α）[-ln（1-α）]^1/4. The specific heat capacity equation is Cp=1.285-6.276×10^-3T＋1.581×10^-5T^2（283 K〈T〈353 K）. With these parameters, the thermal safety properties of NGEC were studied, such as the self-accelerating decomposition temperature（TSADT）, critical temperature of thermal explosion（Tb） and adiabatic time-to-explosion（tTlad）. The results of the thermal safety evalua- tion of NGEC are： TSADV=459.6 K, Tb=492.8 K, tTlad=0.8 S.
文摘This research was focused on the valorisation of glycerol,exploring the feasibility of an efficient route for oxygenated additives production based on its etherification with bio-butanol.A home-made BEA zeolite sample with a tuneable acidity has been proposed as the catalytic system,being tested in a stirred reactor under different etherification conditions.Although a reaction temperature as high as 200℃resulted to be beneficial in terms of glycerol conversion(-90%),only by operating at milder conditions the product selectivity to glycerol-ethers can be better controlled,in order to obtain a bio-fuel complying with the requirements for mixing with fossil diesel or biodiesel,without any need of purification from large amount of by-products.A comprehensive identification of all the compounds formed during the reaction was performed by a GC-MS analysis,on the basis of the complex network of consecutive and parallel reaction paths leading not only to the desired ethers,but also to many side products not detected in similar acid-catalyzed reactions in liquid phase and not available in the most used mass-spectra libraries.
基金supported by the National Basic Research Program of China(Grant No.2011CB808800)the National Natural Science Foundation of China(Grant No.41330103)the"111"Project(Grant No.B08030)
文摘The 1-O-monoalkyl glycerol ethers （MAGEs） were initially viewed as the biomarkers for sulfate-reducing bacteria （SRB） me- diating anaerobic oxidation of methane in the marine environments. However, limited information is known about their distri- bution in terrestrial and other aquatic settings including soils, fresh water lakes, and cave sediments, which may obscure our understanding of their biological sources. Here we found that MAGEs were ubiquitous but differed obviously in distributional pattern among those environments. The surface soils are dominated generally by iC15：0-MAGE, followed by nCI6：o-MAGE whereas the lake sediments show the opposite, resulting in significantly higher iC15：0/nC16：0 ratios in soils than in lake sedi- ments. The cave deposits are characterized by considerably higher proportions of branched MAGEs than the former two envi- ronments. The logarithm of iC15：0/aC15：0 ratio shows a significant negative correlation with soil pH, likely reflecting an adapta- tion of microbial cell membrane to change in the ambient proton concentration. The MAGE profiles in cultured bacteria cannot fully explain the MAGE distribution in all the samples analyzed. Therefore, MAGEs in soil, lake sediments, and cave deposits likely have additional biological source（s） other than SRB and cultured MAGE-producing bacteria. The difference in MAGE pattern among environments is likely to be attributed to change in microbial communities.
基金supported by the National Natural Science Foundation of China (40773029, 40903002 and 40772073)the National Basic Research Program of China (2009- CB219506)
文摘At modern cold seeps,the anaerobic oxidation of methane(AOM)is the dominant pathway for methane consumption in marine sediments.AOM,which is mediated by a consortium of methane oxidizing archaea and sulfate reducing bacteria,is proposed to be responsible for authigenic carbonate formation.A methane-derived carbonate chimney was collected from the Shenhu area, northern South China Sea.The membrane lipids and their very low carbon isotopic compositions(?115‰to?104‰)in the Shenhu chimney suggest the presence of an AOM process.Three specific archaeal and bacterial biomarkers were detected,including Ar,DAGE 1f,and monocyclic MDGD.Their strongly depleted??13C values(?115‰to?104‰),which are lower than those of the normal marine lipids in sediments,reveal biogenic methane as their origin.The carbonate deposits exhibiting a chimney structure indicate that a vigorous methane-rich fluid expulsion may have occurred at the seafloor.We propose that the decomposition of gas hydrates at depth is the likely cause of seepage and cold seep carbonate formation in the Shenhu area.
