To accurately investigate the evolution characteristics and generation mechanism of retained oil,the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag,Bohai Bay...To accurately investigate the evolution characteristics and generation mechanism of retained oil,the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag,Bohai Bay Basin.This analysis involves Rock-Eval pyrolysis,pyrolysis simulation experiments,Gas Chromatograph Mass Spectrometer(GC-MS),and reactive molecular dynamics simulations(ReaxFF).The results revealed the retained oil primarily consisted of n-alkanes with carbon numbers ranging from C14 to C36.The generation of retained oil occurred through three stages.A slow growth stage of production rate was observed before reaching the peak of oil production in Stage Ⅰ.Stage Ⅱ involved a rapid increase in oil retention,with C12-C17 and C24-C32 serving as the primary components,increasing continuously during the pyrolysis process.The generation process involved the cleavage of weak bonds,including bridging bonds(hydroxyl,oxy,peroxy,imino,amino,and nitro),ether bonds,and acid amides in the first stage(Ro=0.50%-0.75%).The carbon chains in aromatic ring structures with heteroatomic functional groups breaks in the second stage(R_(o)=0.75%-1.20%).In the third stage(R_(o)=1.20%-2.50%),the ring structures underwent ring-opening reactions to synthesize iso-short-chain olefins and radicals,while further breakdown of aliphatic chains occurred.By coupling pyrolysis simu-lation experiments and molecular simulation technology,the evolution characteristics and bond breaking mechanism of retained oil in three stages were revealed,providing a reference for the for-mation and evolution mechanism of retained oil.展开更多
Using high pressure and geological condition simulation vessels, we conducted hydrous pyrolysis experiments of kerogen, solid bitumen and liquid hydrocarbons in southern China in order to study the processes of gas ge...Using high pressure and geological condition simulation vessels, we conducted hydrous pyrolysis experiments of kerogen, solid bitumen and liquid hydrocarbons in southern China in order to study the processes of gas generation and derive geo- chemical indicators of gas genesis under approximate pressure and temperature. The results indicate that gas generation productivity of different marine material decreased in the ganic matter （solid bitumen and heavy oil）, and kerogen. order of crude oil （light oil and condensate）, dispersed soluble or- Under identical temperature-pressure regimes, pyrolysates derived from kerogen and dispersed soluble organic matter display drastically different geochemical characteristics. For example, the δ13Cc02-δ13C1 values of gaseous products from dispersed soluble organic matter are greater than 20%o, whereas those from kerogen are less than 20%~. The 813C1 values of pyrolysates from different marine hydrocarbon sources generally increase with pyrolysis temperature, but are always lower than those of the source precursors. The δ13C values of ethane and propane in the pyrolysates also increase with increasing pyrolysis temperature, eventually approaching that of their sources, at peak hydro- carbon generation. At high-over mature stages, the δ13C values of ethane and propane are often greater than those of their sources but close to those of coal gases, and thus become ineffective as gas genetic indicators. Ln（CffC3） can clearly distin- guish kerogen degradation gas from oil cracking gas and Ln（CJC2）-（δ13C1-δ13C2） can be an effective indicator for distinguishing oil cracking gas from dispersed soluble organic matter cracking gas.展开更多
基金financially supported by the National Natural Science Foundation of China (Grant No. 42072150)
文摘To accurately investigate the evolution characteristics and generation mechanism of retained oil,the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag,Bohai Bay Basin.This analysis involves Rock-Eval pyrolysis,pyrolysis simulation experiments,Gas Chromatograph Mass Spectrometer(GC-MS),and reactive molecular dynamics simulations(ReaxFF).The results revealed the retained oil primarily consisted of n-alkanes with carbon numbers ranging from C14 to C36.The generation of retained oil occurred through three stages.A slow growth stage of production rate was observed before reaching the peak of oil production in Stage Ⅰ.Stage Ⅱ involved a rapid increase in oil retention,with C12-C17 and C24-C32 serving as the primary components,increasing continuously during the pyrolysis process.The generation process involved the cleavage of weak bonds,including bridging bonds(hydroxyl,oxy,peroxy,imino,amino,and nitro),ether bonds,and acid amides in the first stage(Ro=0.50%-0.75%).The carbon chains in aromatic ring structures with heteroatomic functional groups breaks in the second stage(R_(o)=0.75%-1.20%).In the third stage(R_(o)=1.20%-2.50%),the ring structures underwent ring-opening reactions to synthesize iso-short-chain olefins and radicals,while further breakdown of aliphatic chains occurred.By coupling pyrolysis simu-lation experiments and molecular simulation technology,the evolution characteristics and bond breaking mechanism of retained oil in three stages were revealed,providing a reference for the for-mation and evolution mechanism of retained oil.
基金supported by Petroleum & Chemical United Fund Project(Grant No. 40739902)
文摘Using high pressure and geological condition simulation vessels, we conducted hydrous pyrolysis experiments of kerogen, solid bitumen and liquid hydrocarbons in southern China in order to study the processes of gas generation and derive geo- chemical indicators of gas genesis under approximate pressure and temperature. The results indicate that gas generation productivity of different marine material decreased in the ganic matter （solid bitumen and heavy oil）, and kerogen. order of crude oil （light oil and condensate）, dispersed soluble or- Under identical temperature-pressure regimes, pyrolysates derived from kerogen and dispersed soluble organic matter display drastically different geochemical characteristics. For example, the δ13Cc02-δ13C1 values of gaseous products from dispersed soluble organic matter are greater than 20%o, whereas those from kerogen are less than 20%~. The 813C1 values of pyrolysates from different marine hydrocarbon sources generally increase with pyrolysis temperature, but are always lower than those of the source precursors. The δ13C values of ethane and propane in the pyrolysates also increase with increasing pyrolysis temperature, eventually approaching that of their sources, at peak hydro- carbon generation. At high-over mature stages, the δ13C values of ethane and propane are often greater than those of their sources but close to those of coal gases, and thus become ineffective as gas genetic indicators. Ln（CffC3） can clearly distin- guish kerogen degradation gas from oil cracking gas and Ln（CJC2）-（δ13C1-δ13C2） can be an effective indicator for distinguishing oil cracking gas from dispersed soluble organic matter cracking gas.
