A series of poly(9,9-dihexylfluorene)s (PDHFs) have been synthesized via microwave-assisted Suzuki and Yamamoto coupling reactions. Compared with the conventional oil-bath heating (48 h, Mw 20100 g/mol by Suzuki react...A series of poly(9,9-dihexylfluorene)s (PDHFs) have been synthesized via microwave-assisted Suzuki and Yamamoto coupling reactions. Compared with the conventional oil-bath heating (48 h, Mw 20100 g/mol by Suzuki reaction and Mw 24000 g/mol by Yamamoto reaction), microwave-assisted polymerization can yield PDHFs with higher molecular weights (Mw 37200 g/mol by Suzuki reaction and Mw 43400 g/mol by Yamamoto reaction) in shorter time (14 and 60 min). However, sometimes formation of insoluble gels was observed together with PDHF in Suzuki coupling reaction. PDHF and insoluble gels were analyzed by XPS, elemental analysis, FTIR, TGA and DSC. Experimental results demonstrated that H2O might take part in the Suzuki coupling reaction under microwave condition, which could make the cross-linking reaction occur and form gels.展开更多
Compaction and silicon cementation are the dominant processes reducing porosity and permeability in quartzose sandstones during diagenesis. Despite the wealth of information about quartz cementation, there are still u...Compaction and silicon cementation are the dominant processes reducing porosity and permeability in quartzose sandstones during diagenesis. Despite the wealth of information about quartz cementation, there are still unanswered questions related to mechanisms of growth of quartz cement and the diagenesis processes. In this study we present an electron backscatter diffraction （EBSD） analysis, combined with optics and cathodoluminescence （CL） information, for the quartz sandstones from the Upper Triassic Xujiahe Formation of Sichuan Basin, in order to reveal the microstructural and crystallographic features of the silica cementation and detrital grain during the compaction. The EBSD is a crucial technique to provide essential crystallographic data on the quartz grain and its cement. Quartz cement is shown to be syntaxial to its host quartz grain. EBSD data-based orientation maps show dauphin6 twinning and low angle boundary to be common in the host grains and quartz cement of the samples. The dauphin6 twins occurred in grain-grain contacts and in cement-crystal boundaries, and commonly crossed grain cement boundaries. These features indicate that there may be two types of dauphin6 twins, one inherited twins from the source area and the other developed by compaction-induced grain boundary deformation. These investigations suggest that strong mechanical compaction may occur after and/or during quartz cement growth in the later diagenesis of the Xujiahe sandstones. EBSD has a capability of revealing microstructural information and regarding mechanisms of diagenesis crystal growth in quartzose sandstones.展开更多
Tight reservoirs are widely distributed, especially in coal measure strata. Identification of the densification mechanism of the tight sandstone reservoirs is critical in effectively exploring and exploiting tight gas...Tight reservoirs are widely distributed, especially in coal measure strata. Identification of the densification mechanism of the tight sandstone reservoirs is critical in effectively exploring and exploiting tight gasoil resources. In this study, the gas for mation from type III organic matter in coal was kinetically modeled for the whole diagenetic stage, from the shallow buried biogas generation stage to the deep buried thermal gas generation stage. The results demonstrated that during hydrocarbon formation, quantities of nonhydrocarbon gases, such as CO2, were generated. The proportion of CO2 is about 50%70% of that of the C15, which far exceeds the CO2 content （05%） in the natural gas in the sedimentary basins. Geological case study analysis showed that a considerable part of the ＂lost＂ gaseous CO2 was converted into carbonate cement under favorable envi ronments. Under the ideal conditions, the volume of the carbonate cement transformed from total CO2 generated by 1 m3 coal （Junggar Basin Jurassic, TOC 67%） can amount to 0.32 m3. Obviously, this process plays a very important role in the for mation of tight sandstone reservoirs in the coal measures. Our results also show that the kinetic generation processes of Ci5 and CO2 are asynchronous. There are two main stages of CO2 generation, one at the weak diagenetic stage and the other at the overmature stage, which are different from largescale multistage hydrocarbon gas generation. Therefore, we can understand the mechanism of tight gas charging by determining the filling time for a tight gas reservoir and the key period of CO2 genera tion. Further analysis and correlation studies of a specific region are of great significance for determining the mechanism and modeling gas charging in tight reservoirs. It should be noted that the formation of tight sandstone reservoirs is the combined result of complex organicinorganic and waterrockhydrocarbon interactions. The details of spatial and temporal distributions of the carbonate cement derived from the organic C02, which combines with metal ions （Ca/Mg/Fe） in the formation water, should be further investigated.展开更多
基金supported by the National Natural Science Foundation of China (21174050, 20834006)
文摘A series of poly(9,9-dihexylfluorene)s (PDHFs) have been synthesized via microwave-assisted Suzuki and Yamamoto coupling reactions. Compared with the conventional oil-bath heating (48 h, Mw 20100 g/mol by Suzuki reaction and Mw 24000 g/mol by Yamamoto reaction), microwave-assisted polymerization can yield PDHFs with higher molecular weights (Mw 37200 g/mol by Suzuki reaction and Mw 43400 g/mol by Yamamoto reaction) in shorter time (14 and 60 min). However, sometimes formation of insoluble gels was observed together with PDHF in Suzuki coupling reaction. PDHF and insoluble gels were analyzed by XPS, elemental analysis, FTIR, TGA and DSC. Experimental results demonstrated that H2O might take part in the Suzuki coupling reaction under microwave condition, which could make the cross-linking reaction occur and form gels.
基金supported by National Natural Science Foundation of China(Grant Nos. 40802050,40872149)China Postdoctoral Science Foundation (Grant No. 20070420065)
文摘Compaction and silicon cementation are the dominant processes reducing porosity and permeability in quartzose sandstones during diagenesis. Despite the wealth of information about quartz cementation, there are still unanswered questions related to mechanisms of growth of quartz cement and the diagenesis processes. In this study we present an electron backscatter diffraction （EBSD） analysis, combined with optics and cathodoluminescence （CL） information, for the quartz sandstones from the Upper Triassic Xujiahe Formation of Sichuan Basin, in order to reveal the microstructural and crystallographic features of the silica cementation and detrital grain during the compaction. The EBSD is a crucial technique to provide essential crystallographic data on the quartz grain and its cement. Quartz cement is shown to be syntaxial to its host quartz grain. EBSD data-based orientation maps show dauphin6 twinning and low angle boundary to be common in the host grains and quartz cement of the samples. The dauphin6 twins occurred in grain-grain contacts and in cement-crystal boundaries, and commonly crossed grain cement boundaries. These features indicate that there may be two types of dauphin6 twins, one inherited twins from the source area and the other developed by compaction-induced grain boundary deformation. These investigations suggest that strong mechanical compaction may occur after and/or during quartz cement growth in the later diagenesis of the Xujiahe sandstones. EBSD has a capability of revealing microstructural information and regarding mechanisms of diagenesis crystal growth in quartzose sandstones.
基金supported by National Natural Science Foundation of China (Grant No. 40873031)China Petroleum Foundation (Grant Nos. 2012Y-011, 2011B-0601)National Oil and Gas Special Foundation (Grant No. 2011ZX05007-001)
文摘Tight reservoirs are widely distributed, especially in coal measure strata. Identification of the densification mechanism of the tight sandstone reservoirs is critical in effectively exploring and exploiting tight gasoil resources. In this study, the gas for mation from type III organic matter in coal was kinetically modeled for the whole diagenetic stage, from the shallow buried biogas generation stage to the deep buried thermal gas generation stage. The results demonstrated that during hydrocarbon formation, quantities of nonhydrocarbon gases, such as CO2, were generated. The proportion of CO2 is about 50%70% of that of the C15, which far exceeds the CO2 content （05%） in the natural gas in the sedimentary basins. Geological case study analysis showed that a considerable part of the ＂lost＂ gaseous CO2 was converted into carbonate cement under favorable envi ronments. Under the ideal conditions, the volume of the carbonate cement transformed from total CO2 generated by 1 m3 coal （Junggar Basin Jurassic, TOC 67%） can amount to 0.32 m3. Obviously, this process plays a very important role in the for mation of tight sandstone reservoirs in the coal measures. Our results also show that the kinetic generation processes of Ci5 and CO2 are asynchronous. There are two main stages of CO2 generation, one at the weak diagenetic stage and the other at the overmature stage, which are different from largescale multistage hydrocarbon gas generation. Therefore, we can understand the mechanism of tight gas charging by determining the filling time for a tight gas reservoir and the key period of CO2 genera tion. Further analysis and correlation studies of a specific region are of great significance for determining the mechanism and modeling gas charging in tight reservoirs. It should be noted that the formation of tight sandstone reservoirs is the combined result of complex organicinorganic and waterrockhydrocarbon interactions. The details of spatial and temporal distributions of the carbonate cement derived from the organic C02, which combines with metal ions （Ca/Mg/Fe） in the formation water, should be further investigated.
