It is important to understand the effects of demineralization on the reactivity of coal pyrolysis for demineralization coal in OCCSS systems.The molecular dynamics of the pyrolysis of ZD-R and ZD-D was investigated us...It is important to understand the effects of demineralization on the reactivity of coal pyrolysis for demineralization coal in OCCSS systems.The molecular dynamics of the pyrolysis of ZD-R and ZD-D was investigated using the ReaxFF MD method.It is indicated that the pyrolysis reactivity of ZD-D is enhanced.Acid demineralization treatment helps to enhance the cross-linking reaction of light tar C5-14 molecules in the main pyrolysis stage,generating light tar fragments with higher molecular mass.In the polycondensation pyrolysis stage,the acid demineralization treatment promotes the polycondensation reaction at high temperatures.The generation of H2 in ZD-R pyrolysis is primarily attributed to the N-H bond breaking in pyrrole at low temperatures.At high temperatures,it is predominantly associated with the hydrogen abstraction reaction between carboxyl functional groups and the dehydrogenation reaction of hydrogen bond breaking in the aliphatic hydrocarbon structures.H2O is primarily attributed to the reaction of the hydroxyl group on the carboxyl group.CO_(2) is always related to the carboxyl group.CO is mainly related to the reduction reaction of carbonyl group,carboxyl group,and CO_(2).During the initial pyrolysis stage of ZD-D after acid demineralization treatment,the hydrogen abstraction reaction of the carboxyl functional group and the generation of CO molecules by the methoxy group are enhanced.The generation of H2 by the aliphatic structure is enhanced in the main pyrolysis stage.The ring-opening reaction of the phenoxy group to generate CO in the polycondensation pyrolysis stage is also facilitated.展开更多
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
The experiment explored the Fe_(2)O_(3) reduction process with H_(2)/CO mixed gas and confirmed a promoting effect from CO when its volume proportion in mixed gas is 20% at 850℃.The ReaxFF molecular dynamics(MD)simul...The experiment explored the Fe_(2)O_(3) reduction process with H_(2)/CO mixed gas and confirmed a promoting effect from CO when its volume proportion in mixed gas is 20% at 850℃.The ReaxFF molecular dynamics(MD)simulation method was used to observe the reduction process and provide an atomic-level explanation.The accuracy of the parameters used in the simulation was verified by the density functional theory(DFT)calculation.The simulation shows that the initial reduction rate of H_(2) is much faster than that of CO(from 800 to 950℃).As the reduction proceeds,cementite,obtained after CO participates in the reduction at 850℃,will appear on the iron surface.Due to the active properties of C atoms in cementite,they are easy to further react with the O atoms in Fe_(2)O_(3).The generation of internal CO may destroy the dense structure of the surface layer,thereby affecting the overall reduction swelling of Fe_(2)O_(3).However,excess CO is detrimental to the reaction rate,mainly because of the poor thermodynamic conditions of CO in the temperature range and the molecular diffusion capacity is not as good as that of H_(2).Furthermore,the surface structures obtained after H_(2) and CO reduction have been compared,and it was found that the structure obtained by CO reduction has a larger surface area,thus promoting the sub sequent reaction of H_(2).展开更多
海底充油电缆的安全稳定运行至关重要,但内部的十二烷基苯(DDB)绝缘油在热故障导致的局部高温下会快速热解和产气。基于反应分子动力学模拟(Reax FF-MD)和热重-红外光谱(TG-IR)实验,对十二烷基苯绝缘油的热解和产气过程进行探究。热解...海底充油电缆的安全稳定运行至关重要,但内部的十二烷基苯(DDB)绝缘油在热故障导致的局部高温下会快速热解和产气。基于反应分子动力学模拟(Reax FF-MD)和热重-红外光谱(TG-IR)实验,对十二烷基苯绝缘油的热解和产气过程进行探究。热解模拟结果表明:十二烷基苯分子初始裂解反应主要为C—C键的断裂产生长链大分子,后逐渐热解产生小烷基自由基和烯烃分子,DDB最终会热解为侧链为·C_(2)H_(5)、·CH_(3)和·C_(3)H_(7)基团的短链烷基苯分子。热解过程中主要特征气体为C_(2)H_(4)、H_(2)、CH_(4),与IR实验结果相同,特征气体生成的主要反应机理分别为:β位C—C键的断裂、加氢反应和脱氢反应;·H自由基攻击其他自由基上的H原子;甲基自由基(·CH_(3))与游离的氢(·H)自由基反应。动力学结果表明TG实验与Reax FF-MD的活化能分别为86.606 k J/mol以及99.867 k J/mol,相近的活化能进一步验证了仿真结果的合理性。研究结论为深入了解十二烷基苯绝缘油的裂解和产气机理提供了理论支持。展开更多
文摘It is important to understand the effects of demineralization on the reactivity of coal pyrolysis for demineralization coal in OCCSS systems.The molecular dynamics of the pyrolysis of ZD-R and ZD-D was investigated using the ReaxFF MD method.It is indicated that the pyrolysis reactivity of ZD-D is enhanced.Acid demineralization treatment helps to enhance the cross-linking reaction of light tar C5-14 molecules in the main pyrolysis stage,generating light tar fragments with higher molecular mass.In the polycondensation pyrolysis stage,the acid demineralization treatment promotes the polycondensation reaction at high temperatures.The generation of H2 in ZD-R pyrolysis is primarily attributed to the N-H bond breaking in pyrrole at low temperatures.At high temperatures,it is predominantly associated with the hydrogen abstraction reaction between carboxyl functional groups and the dehydrogenation reaction of hydrogen bond breaking in the aliphatic hydrocarbon structures.H2O is primarily attributed to the reaction of the hydroxyl group on the carboxyl group.CO_(2) is always related to the carboxyl group.CO is mainly related to the reduction reaction of carbonyl group,carboxyl group,and CO_(2).During the initial pyrolysis stage of ZD-D after acid demineralization treatment,the hydrogen abstraction reaction of the carboxyl functional group and the generation of CO molecules by the methoxy group are enhanced.The generation of H2 by the aliphatic structure is enhanced in the main pyrolysis stage.The ring-opening reaction of the phenoxy group to generate CO in the polycondensation pyrolysis stage is also facilitated.
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financial support from the National Natural Science Foundation of China(Nos.52204335 and 52374319)the National Nature Science Foundation of China(No.52174291)the Central Universities Foundation of China(No.06500170)。
文摘The experiment explored the Fe_(2)O_(3) reduction process with H_(2)/CO mixed gas and confirmed a promoting effect from CO when its volume proportion in mixed gas is 20% at 850℃.The ReaxFF molecular dynamics(MD)simulation method was used to observe the reduction process and provide an atomic-level explanation.The accuracy of the parameters used in the simulation was verified by the density functional theory(DFT)calculation.The simulation shows that the initial reduction rate of H_(2) is much faster than that of CO(from 800 to 950℃).As the reduction proceeds,cementite,obtained after CO participates in the reduction at 850℃,will appear on the iron surface.Due to the active properties of C atoms in cementite,they are easy to further react with the O atoms in Fe_(2)O_(3).The generation of internal CO may destroy the dense structure of the surface layer,thereby affecting the overall reduction swelling of Fe_(2)O_(3).However,excess CO is detrimental to the reaction rate,mainly because of the poor thermodynamic conditions of CO in the temperature range and the molecular diffusion capacity is not as good as that of H_(2).Furthermore,the surface structures obtained after H_(2) and CO reduction have been compared,and it was found that the structure obtained by CO reduction has a larger surface area,thus promoting the sub sequent reaction of H_(2).
文摘海底充油电缆的安全稳定运行至关重要,但内部的十二烷基苯(DDB)绝缘油在热故障导致的局部高温下会快速热解和产气。基于反应分子动力学模拟(Reax FF-MD)和热重-红外光谱(TG-IR)实验,对十二烷基苯绝缘油的热解和产气过程进行探究。热解模拟结果表明:十二烷基苯分子初始裂解反应主要为C—C键的断裂产生长链大分子,后逐渐热解产生小烷基自由基和烯烃分子,DDB最终会热解为侧链为·C_(2)H_(5)、·CH_(3)和·C_(3)H_(7)基团的短链烷基苯分子。热解过程中主要特征气体为C_(2)H_(4)、H_(2)、CH_(4),与IR实验结果相同,特征气体生成的主要反应机理分别为:β位C—C键的断裂、加氢反应和脱氢反应;·H自由基攻击其他自由基上的H原子;甲基自由基(·CH_(3))与游离的氢(·H)自由基反应。动力学结果表明TG实验与Reax FF-MD的活化能分别为86.606 k J/mol以及99.867 k J/mol,相近的活化能进一步验证了仿真结果的合理性。研究结论为深入了解十二烷基苯绝缘油的裂解和产气机理提供了理论支持。
