This article is based on the experimental data on reaction of FCC naphtha in the presence of acid catalysts. The data published in the literature were reprocessed and compared with experimental data and the relationsh...This article is based on the experimental data on reaction of FCC naphtha in the presence of acid catalysts. The data published in the literature were reprocessed and compared with experimental data and the relationship of hydrogen and methane contained in the dry gas with the conversion rate was identified.The similarity between the route for cracking of olefin enriched FCC gasoline and the route for reaction of individual hydrocarbons was deduced, while the route for formation of ethylene in dry gas was also proposed to identify the relationship between the reaction path for formation of ethylene and the conversion rate.展开更多
In order to investigate the impact of U-ore on organic matter maturation and isotopic fractionation,we designed hydrous pyrolysis experiments on Type-II kerogen samples,supposing that the water and water–mineral inte...In order to investigate the impact of U-ore on organic matter maturation and isotopic fractionation,we designed hydrous pyrolysis experiments on Type-II kerogen samples,supposing that the water and water–mineral interaction play a role.U-ore was set as the variable for comparison.Meanwhile,anhydrous pyrolysis under the same conditions was carried out as the control experiments.The determination of liquid products indicates that the presence of water and minerals obviously enhanced the yields of C（15＋） and the amounts of hydrocarbon and nonhydrocarbon gases.Such results may be attributed to waterorganic matter reaction in the high-temperature system,which can provide additional hydrogen and oxygen for the generation of gas and liquid products from organic matter.It is found that δD values of hydrocarbon gases generated in both hydrous pyrolysis experiments are much lower than those in anhydrous pyrolysis.What is more,δD values are lower in the hydrous pyrolysis with uranium ore.Therefore,we can infer that water-derived hydrogen played a significant role during the kerogen thermal evolution and the hydrocarbon generation in our experiments.Isotopic exchange was facilitated by the reversible equilibration between reaction intermediaries with hydrogen under hydrothermal conditions with uranium ore.Carbon isotopic fractionations of hydrocarbon gases were somehow affected by the presence of water and the uranium ore.The increased level of i-C4/n-C4ratios for gas products in hydrous pyrolysis implied the carbocation mechanism for water-kerogen reactions.展开更多
The hydrous thermo-simulation experiments on oil shale sample from Liushuhe basin have been performed using autoclave.The mechanism and kinetics of oil shale pyrolysis were investigated.The formation mechanism of pyro...The hydrous thermo-simulation experiments on oil shale sample from Liushuhe basin have been performed using autoclave.The mechanism and kinetics of oil shale pyrolysis were investigated.The formation mechanism of pyrolysates including retorting gas,oil and bitumen,were evaluated in the presence of saturated and unsaturated water,respectively.The results show that the physicochemical properties of water have greatly changed in high temperature and pressure.At the same time,water has three kinds of effect on the oil shale pyrolysis,including the protection of free radical,catalytic action and swelling.The pyrolysis temperature was carried out about 70C earlier,and the generated processing of hydrocarbon would be easier under the aqueous.The consecutive first order reaction model involving bitumen as an intermediate product was used in the data analysis in order to determine the pyrolysis kinetic parameters.It was found that the apparent activation energy of kerogen pyrolysis was lower than bitumen pyrolysis.展开更多
Halophilic attacks on C-X bonds (X=Br,Cl) by a base can easily initiate mtermolecular bromme-chlonne exchange reactions either among bromine-or chlorine-containing perhaloalkane molecules of different compounds of amo...Halophilic attacks on C-X bonds (X=Br,Cl) by a base can easily initiate mtermolecular bromme-chlonne exchange reactions either among bromine-or chlorine-containing perhaloalkane molecules of different compounds of among molecules of the same compound It provides a new and convenient method to synthesize perhaloal-kanes Apparently,it pertains to an amomc mechanism,i e.the reaction is initiated by halophilic attack on C-X bonds by the base,and an intermediate carbanion is formed.Distributions of the products depend on the equilibria involving all carbanion intermediates and perhaloalkane product molecules.展开更多
文摘This article is based on the experimental data on reaction of FCC naphtha in the presence of acid catalysts. The data published in the literature were reprocessed and compared with experimental data and the relationship of hydrogen and methane contained in the dry gas with the conversion rate was identified.The similarity between the route for cracking of olefin enriched FCC gasoline and the route for reaction of individual hydrocarbons was deduced, while the route for formation of ethylene in dry gas was also proposed to identify the relationship between the reaction path for formation of ethylene and the conversion rate.
文摘In order to investigate the impact of U-ore on organic matter maturation and isotopic fractionation,we designed hydrous pyrolysis experiments on Type-II kerogen samples,supposing that the water and water–mineral interaction play a role.U-ore was set as the variable for comparison.Meanwhile,anhydrous pyrolysis under the same conditions was carried out as the control experiments.The determination of liquid products indicates that the presence of water and minerals obviously enhanced the yields of C（15＋） and the amounts of hydrocarbon and nonhydrocarbon gases.Such results may be attributed to waterorganic matter reaction in the high-temperature system,which can provide additional hydrogen and oxygen for the generation of gas and liquid products from organic matter.It is found that δD values of hydrocarbon gases generated in both hydrous pyrolysis experiments are much lower than those in anhydrous pyrolysis.What is more,δD values are lower in the hydrous pyrolysis with uranium ore.Therefore,we can infer that water-derived hydrogen played a significant role during the kerogen thermal evolution and the hydrocarbon generation in our experiments.Isotopic exchange was facilitated by the reversible equilibration between reaction intermediaries with hydrogen under hydrothermal conditions with uranium ore.Carbon isotopic fractionations of hydrocarbon gases were somehow affected by the presence of water and the uranium ore.The increased level of i-C4/n-C4ratios for gas products in hydrous pyrolysis implied the carbocation mechanism for water-kerogen reactions.
基金We thank the following foundation for the financial support:the National Basic Research Program of China(973 programs,No.2014CB744302)Taishan Scholar Constructive Engineering Foun-dation of Shandong province,China(No.ts20120518).
文摘The hydrous thermo-simulation experiments on oil shale sample from Liushuhe basin have been performed using autoclave.The mechanism and kinetics of oil shale pyrolysis were investigated.The formation mechanism of pyrolysates including retorting gas,oil and bitumen,were evaluated in the presence of saturated and unsaturated water,respectively.The results show that the physicochemical properties of water have greatly changed in high temperature and pressure.At the same time,water has three kinds of effect on the oil shale pyrolysis,including the protection of free radical,catalytic action and swelling.The pyrolysis temperature was carried out about 70C earlier,and the generated processing of hydrocarbon would be easier under the aqueous.The consecutive first order reaction model involving bitumen as an intermediate product was used in the data analysis in order to determine the pyrolysis kinetic parameters.It was found that the apparent activation energy of kerogen pyrolysis was lower than bitumen pyrolysis.
基金Project supported by the National Natural Science Foundation of China
文摘Halophilic attacks on C-X bonds (X=Br,Cl) by a base can easily initiate mtermolecular bromme-chlonne exchange reactions either among bromine-or chlorine-containing perhaloalkane molecules of different compounds of among molecules of the same compound It provides a new and convenient method to synthesize perhaloal-kanes Apparently,it pertains to an amomc mechanism,i e.the reaction is initiated by halophilic attack on C-X bonds by the base,and an intermediate carbanion is formed.Distributions of the products depend on the equilibria involving all carbanion intermediates and perhaloalkane product molecules.
