Abstract Asphaltene, from co-processing of coal and petroleum residues is one of the most precious and complex molecular mixtures existing, with tremendous economic relevance. Asphaltene was separated by Soxhlet extra...Abstract Asphaltene, from co-processing of coal and petroleum residues is one of the most precious and complex molecular mixtures existing, with tremendous economic relevance. Asphaltene was separated by Soxhlet extraction with methylbenzene and then divided into three parts by distillation. Gas chromatography （GC） and high-performance liquid chromatography （HPLC） were coupled with quadrupole time-of-flight mass spectrometry （Q-TOF MS） to separate and characterize organic nitrogen species in the distillates of asphaltene at molecular level. Molecular mass of compounds was mainly distributed from 150 to 600 ~t. Number of rings plus double bonds （rdb） and synchronous fluorescence spectra indicated that most of the organonitrogen compounds （NPAC） contained heterocyclic aromatic rings, including pyridines, anilines, quinolins, pyrroles, carbazoles and indoles plus various alkyl groups. Constant-wavelength synchronous fluo- rescence spectrometry （CWSFS） indicated NPAC with 2-3 rings were the main structures of organonitrogen compounds and the corresponding structural information was proposed. Some organic nitrogen isomers were separated and identified by atmospheric pressure chemical ionization （APCI） GC-Q-TOF MS and electrospray ionization （ESI） HPLC-Q-TOF MS. The methodology applied here contained chromatographic injection of the diluted sample using conventional columns sets and Data Analysis 4.2 software. Identifying molecular structures provides a foundation to understand all aspects of coal- derived asphaltene, enabling a first-principles approach to optimize resource utilization.展开更多
The changes in properties and structural parameters of four vacuum residue samples before and after ultrasonic treatment were analyzed. Ultrasonic treatment could increase the carbon residue value, decrease the averag...The changes in properties and structural parameters of four vacuum residue samples before and after ultrasonic treatment were analyzed. Ultrasonic treatment could increase the carbon residue value, decrease the average molecular weight and viscosity, which can barely inlfuence the density of vacuum residue. Meanwhile the constitution of residue can be varied including the decrease in the content of saturates, aromatics and asphaltenes, while the increase in the content of resins can lead to an increase in the total content of asphaltenes and resins. Among the four kinds of residue samples, there is a common trend that the more the content of asphaltenes in feedstock is, the more the increase in the content of resins, the more signiifcant decrease in the aromatic content and the less decrease in the saturates content after ultrasonic treatment of residue would be. Changes in the structure and content of asphaltenes caused by ultrasonic treatment have a signiifcant impact on the changes in residue properties. Ultrasonic treatment has changed the structural parameters of residue such as decrease in the total carbon number of average molecule （CTotal）, the total number of rings （RT）, the aromatic carbon number （CA）,the aromatic rings number （RA） and the naphthenic rings number （RN） , and increase of characterization factor （KH）. The study has indicated that ultrasonic treatment of vacuum residue can change the average structure of residue, and the changes in the content and structure of asphaltenes are the main cause leading to property changes. The results of residue hydrotreat-ing revealed that coke yield decreased, whereas the gas and light oil yield and conversion increased after ultrasonic treat-ment of vacuum residue.展开更多
基金Acknowledgements The authors gratefully acknowledge the financial support of this work by the National Natural Science Foundation of China （No. U1510122）. The authors declare that the experiments comply with the current laws of China.
文摘Abstract Asphaltene, from co-processing of coal and petroleum residues is one of the most precious and complex molecular mixtures existing, with tremendous economic relevance. Asphaltene was separated by Soxhlet extraction with methylbenzene and then divided into three parts by distillation. Gas chromatography （GC） and high-performance liquid chromatography （HPLC） were coupled with quadrupole time-of-flight mass spectrometry （Q-TOF MS） to separate and characterize organic nitrogen species in the distillates of asphaltene at molecular level. Molecular mass of compounds was mainly distributed from 150 to 600 ~t. Number of rings plus double bonds （rdb） and synchronous fluorescence spectra indicated that most of the organonitrogen compounds （NPAC） contained heterocyclic aromatic rings, including pyridines, anilines, quinolins, pyrroles, carbazoles and indoles plus various alkyl groups. Constant-wavelength synchronous fluo- rescence spectrometry （CWSFS） indicated NPAC with 2-3 rings were the main structures of organonitrogen compounds and the corresponding structural information was proposed. Some organic nitrogen isomers were separated and identified by atmospheric pressure chemical ionization （APCI） GC-Q-TOF MS and electrospray ionization （ESI） HPLC-Q-TOF MS. The methodology applied here contained chromatographic injection of the diluted sample using conventional columns sets and Data Analysis 4.2 software. Identifying molecular structures provides a foundation to understand all aspects of coal- derived asphaltene, enabling a first-principles approach to optimize resource utilization.
基金support provided by the Fundamental Research Funds for the Central Universities(Grant No.11CX05008A)the PetroChina Innovation Foundation(Grant No.2011D-5006-0405)the UPC Innovation Project of Postgraduate(Grant No.CX201304)
文摘The changes in properties and structural parameters of four vacuum residue samples before and after ultrasonic treatment were analyzed. Ultrasonic treatment could increase the carbon residue value, decrease the average molecular weight and viscosity, which can barely inlfuence the density of vacuum residue. Meanwhile the constitution of residue can be varied including the decrease in the content of saturates, aromatics and asphaltenes, while the increase in the content of resins can lead to an increase in the total content of asphaltenes and resins. Among the four kinds of residue samples, there is a common trend that the more the content of asphaltenes in feedstock is, the more the increase in the content of resins, the more signiifcant decrease in the aromatic content and the less decrease in the saturates content after ultrasonic treatment of residue would be. Changes in the structure and content of asphaltenes caused by ultrasonic treatment have a signiifcant impact on the changes in residue properties. Ultrasonic treatment has changed the structural parameters of residue such as decrease in the total carbon number of average molecule （CTotal）, the total number of rings （RT）, the aromatic carbon number （CA）,the aromatic rings number （RA） and the naphthenic rings number （RN） , and increase of characterization factor （KH）. The study has indicated that ultrasonic treatment of vacuum residue can change the average structure of residue, and the changes in the content and structure of asphaltenes are the main cause leading to property changes. The results of residue hydrotreat-ing revealed that coke yield decreased, whereas the gas and light oil yield and conversion increased after ultrasonic treat-ment of vacuum residue.
