In this work, Zr-M(M=Cu, Mn, Ce) type sulfur transfer agent was prepared by impregnation method. Under the condition similar to that in the regenerator of FCC units, the influence of different active metal components ...In this work, Zr-M(M=Cu, Mn, Ce) type sulfur transfer agent was prepared by impregnation method. Under the condition similar to that in the regenerator of FCC units, the influence of different active metal components and their contents on sulfur transfer agent were investigated. Moreover, the crystalline structure of sulfur transfer agent was characterized by X-ray diffraction(XRD) and Fourier transforms infrared spectroscopy(FT-IR). The result showed that the Zr-Mn sulfur transfer agent could effectively reduce the SO2 content in FCC regenerator flue gas, featuring high SO2 adsorption capacity. The sulfur transfer agent was inactivated in 40—60 min during the test. In the course of reduction reaction, after several reaction cycles, the formation of SO2 ceased and only H2 S was detected as the reduction product.展开更多
Catalytic cracking experiments of FCC cycle oil were carried out in a fixed fluidized bed reactor.Effects of reaction conditions,such as temperature,catalyst to oil ratio and weight hourly space velocity,were investig...Catalytic cracking experiments of FCC cycle oil were carried out in a fixed fluidized bed reactor.Effects of reaction conditions,such as temperature,catalyst to oil ratio and weight hourly space velocity,were investigated.Hydrocarbon composition of gasoline was analyzed by gas chromatograph.Experimental results showed that conversion of cycle oil was low on account of its poor crackability performance,and the effect of reaction conditions on gasoline yield was obvious.The paraffin content was very high in gasoline.Based on the experimental yields under different reaction conditions,a model for prediction of gasoline and diesel yields was established by radial basis function neural network(RBFNN).In the model,the product yield was viewed as function of reaction conditions.Particle swarm optimization(PSO)algorithm with global search capability was used to obtain optimal conditions for a highest yield of light oil.The results showed that the yield of gasoline and diesel predicted by RBF neural network agreed well with the experimental values.The optimized reaction conditions were obtained at a reaction temperature of around 520℃,a catalyst to oil ratio of 7.4 and a space velocity of 8 h-1.The predicted total yield of gasoline and diesel reached 42.2% under optimized conditions.展开更多
The integration of refinery and petrochemical units(IRPUs)has become an inevitable choice for the sustainable development of petrochemical industry.The utilization efficiency of petroleum resources could be improved o...The integration of refinery and petrochemical units(IRPUs)has become an inevitable choice for the sustainable development of petrochemical industry.The utilization efficiency of petroleum resources could be improved obviously through IRPUs.However,integrating economic and environmental impacts into the model of IRPUs is still a grand challenge.Herein,a model called TEA-GHG-OPWM(Techno-Economic Analysis and GreenHouse Gases Oriented Plant-Wide Model)has been established on Aspen HYSYSTM platform to calculate the energy consumption,the technoeconomic performance,and the GHG emissions for two different kinds of schemes,viz,:VRHCU(Vacuum Residue Hydrocracking Unit)and VRDS-RFCC(Vacuum Residue Desulfurization and Residue Fluid Catalytic Cracking).Furthermore,a novel processing pathway named VGOHDT-HTMP-DC(Vacuum Gas Oil Hydrotreating,Hydrogenation and TMP coupling process and Delayed Coking)has also been developed to find methods to improve the economic performance based on a ten-million-CNY output value(TMYOV)and a reduced GHG emissions.Our results demonstrate that VRHCRU could consume more energy and emit more GHG(877.11 t of CO2 eq·TMYOV^-1·h^-1)than VRDS-RFCC(817.03 t of CO2 eq·TMYOV^-1·h^-1)and VGOHDT-HTMP-DC(721.96 t of CO2 eq·TMYOV^-1·h^-1),while obtaining a higher mass yield of petrochemicals.The VGOHDT-HTMP-DC process exhibits the lowest feedstock consumption,hydrogen consumption,energy consumption,and GHG emissions,indicating that VGOHDT-HTMP-DC has both well economic and environmentally friendly performance.展开更多
The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of...The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of asphaltene molecules were estimated by combining 1 H nuclear magnetic resonance and X-ray diffraction analyses,and were also ob-tained from vapor pressure osmometry and elemental analysis.Heteroatoms,such as S,N,and O atoms,were considered in the construction of average molecular structure of heavy oils.Two important structural parameters were proposed,including the number of alkyl chain substituents to aromatic rings and the number of total rings with heteroatoms.Ultimately,the av-erage molecular structures of polycyclic aromatics,heavy resins and asphaltene molecules were constructed.The number of α-,β-,γ-,and aromatic hydrogen atoms of the constructed average molecular structures fits well with the number of hydro-gen atoms derived from the experimental spectral data.展开更多
Adsorption of FCC dry gas components, hydrogen(H_2), nitrogen(N_2), methane(CH_4), ethane(C_2H_6) and ethylene(C_2H_4) in zeolite Y was studied by performing the Grant Canonical Monte Carlo(GCMC) simulations at 298K a...Adsorption of FCC dry gas components, hydrogen(H_2), nitrogen(N_2), methane(CH_4), ethane(C_2H_6) and ethylene(C_2H_4) in zeolite Y was studied by performing the Grant Canonical Monte Carlo(GCMC) simulations at 298K and 823K and under a pressure range up to 10 MPa. Simulation results were analyzed using the Langmuir model, which presented fitting of dry gas components adsorption to be suggested as the monolayer adsorption. C_2H_4 presented most single adsorption amount, which reached 7.63 mol/kg at 298K under a pressure of 200kPa. Thermodynamic parameters of the Gibbs free energy change, enthalpy change and entropy change were analyzed based on adsorption equilibrium constant obtained from the GCMC simulations. The results suggested that it was more favorable for C_2H_4 to be adsorbed in zeolite Y. Adsorption molecules were in ordered arrangement in the zeolite, and C_2H_4 exhibited a more orderly arrangement than other components. Additionally, a competition in the adsorption of a mixture of dry gas components was found, and supercages were the priority adsorption space. The competition was favorable to CH_4 and C_2H_6, and the competitive power was affected by temperature.展开更多
The distribution and form of iron and calcium compounds were studied using hydrogenation feedstock and hydrogenation products with different space velocities as the research object.The content of metallic elements,suc...The distribution and form of iron and calcium compounds were studied using hydrogenation feedstock and hydrogenation products with different space velocities as the research object.The content of metallic elements,such as calcium and iron in hydrogenation feedstock,and extract samples were determined via flame atomic absorption spectrometry.The water-soluble iron and calcium species in oil samples were determined by an IC2010 high-throughput ion chromatograph.Nearly 60%-80%of the iron or calcium compounds were mainly concentrated in resins and asphaltenes.Iron and calcium compounds mainly exist in the form of oil-soluble metal species in hydrogenation feedstock and hydrogenation products.Under certain conditions of reaction temperature,pressure,and volume ratio of hydrogen to oil,when the reaction space velocity was 0.6 h^(−1),about 30%of the iron or calcium compounds were converted from oil-soluble to water-soluble species after hydrogenation.When the reaction space velocity was decreased from 1.70 to 0.60 h^(−1),the proportion of iron compounds converted from oil-soluble to water-soluble increased from 8.4%to 28%.Moreover,the proportion of calcium compounds converted from oil-soluble to water-soluble increased from 10%to 37%.This denotes that with decreasing reaction space velocity,the ratio of oil-soluble to water-soluble species increases.Water-soluble iron and calcium compounds are present in the form of inorganic salts,such as chlorate and sulfate.This study helps in understanding the removal mechanism of iron and calcium compounds and optimizing the operating conditions of residue hydrogenation.展开更多
The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which c...The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which could delay th aggregation and coke formation from asphaltenes on the catalyst, and make heavy components transformed into light oi The residue conversion in the presence of this additive increased by 1.94%, and the yield of light oil increased by 1.53%when the reaction time was 90 min. The surface properties of the catalyst in the presence of this additive were better tha that of the blank test within a very short time(30 min) and deteriorated rapidly after a longer reaction time due to highe conversion and coke deposition. Compared with the blank test, the case using the said additive had shown that the structur of hydrotreated asphaltene units was smaller and the condensation degrees were higher. The test results indicated that th additive could improve the hydrotreating reactivity of residue via permeation and depolymerization, the heavier componen could be transformed into light oil more easily, and the light oil yield and residue conversion were higher for the case usin the said additive in residue hydrotreating process.展开更多
ZSM-5 zeolite samples with a SiO2/Al2O3 ratio of 40 were synthesized by a hydrothermal method,and treated by 0.3 M tetrapropyl ammonium hydroxide(TPAOH)and 0.3 M sodium hydroxide(NaOH)solution separately to create hol...ZSM-5 zeolite samples with a SiO2/Al2O3 ratio of 40 were synthesized by a hydrothermal method,and treated by 0.3 M tetrapropyl ammonium hydroxide(TPAOH)and 0.3 M sodium hydroxide(NaOH)solution separately to create hollow structures.The synthesized ZSM-5 zeolite and treated ZSM-5 zeolite samples were evaluated for aromatization of 1-hexene in a continuous flow reactor.The prepared ZSM-5 zeolite samples were characterized by XRD,SEM,TEM,NMR,XPS,and other analyses.The results showed that the alkali treatment formed mesopores and hollow structures in the ZSM-5 crystals without destroying the topological structure.The acid amount of ZSM-5 zeolite was also increased after alkali treatment.Compared with the ZSM-5 zeolite treated by TPAOH,the ZSM-5 zeolite treated by NaOH had more mesopores and a higher total acid amount but a lower strong acid amount,resulting in higher aromatics yields and catalytic stability for 1-hexene aromatization.The characterization of spent ZSM-5 zeolites suggested that the spent treated ZSM-5 zeolites contained less coke,leading to a smaller reduction of micropore surface area and volume than in the spent parent ZSM-5,which contributed to the stability enhancement.展开更多
基金supported by the research fund of the National Natural Science Foundation of China (21306162)the National Basic Research Program "973" Project of China (2010CB226903)Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (AE201309)
文摘In this work, Zr-M(M=Cu, Mn, Ce) type sulfur transfer agent was prepared by impregnation method. Under the condition similar to that in the regenerator of FCC units, the influence of different active metal components and their contents on sulfur transfer agent were investigated. Moreover, the crystalline structure of sulfur transfer agent was characterized by X-ray diffraction(XRD) and Fourier transforms infrared spectroscopy(FT-IR). The result showed that the Zr-Mn sulfur transfer agent could effectively reduce the SO2 content in FCC regenerator flue gas, featuring high SO2 adsorption capacity. The sulfur transfer agent was inactivated in 40—60 min during the test. In the course of reduction reaction, after several reaction cycles, the formation of SO2 ceased and only H2 S was detected as the reduction product.
基金support of the Chinese National Program for Fundamental Research and Development(973 program)(2012CB215006)
文摘Catalytic cracking experiments of FCC cycle oil were carried out in a fixed fluidized bed reactor.Effects of reaction conditions,such as temperature,catalyst to oil ratio and weight hourly space velocity,were investigated.Hydrocarbon composition of gasoline was analyzed by gas chromatograph.Experimental results showed that conversion of cycle oil was low on account of its poor crackability performance,and the effect of reaction conditions on gasoline yield was obvious.The paraffin content was very high in gasoline.Based on the experimental yields under different reaction conditions,a model for prediction of gasoline and diesel yields was established by radial basis function neural network(RBFNN).In the model,the product yield was viewed as function of reaction conditions.Particle swarm optimization(PSO)algorithm with global search capability was used to obtain optimal conditions for a highest yield of light oil.The results showed that the yield of gasoline and diesel predicted by RBF neural network agreed well with the experimental values.The optimized reaction conditions were obtained at a reaction temperature of around 520℃,a catalyst to oil ratio of 7.4 and a space velocity of 8 h-1.The predicted total yield of gasoline and diesel reached 42.2% under optimized conditions.
基金The research was supported by the National Natural Science Foundation of China(21978325 and 21776312)the Fundamental Research Funds for the Central Universities(20CX06073A,20CX06095A,and 20CX06096A).
文摘The integration of refinery and petrochemical units(IRPUs)has become an inevitable choice for the sustainable development of petrochemical industry.The utilization efficiency of petroleum resources could be improved obviously through IRPUs.However,integrating economic and environmental impacts into the model of IRPUs is still a grand challenge.Herein,a model called TEA-GHG-OPWM(Techno-Economic Analysis and GreenHouse Gases Oriented Plant-Wide Model)has been established on Aspen HYSYSTM platform to calculate the energy consumption,the technoeconomic performance,and the GHG emissions for two different kinds of schemes,viz,:VRHCU(Vacuum Residue Hydrocracking Unit)and VRDS-RFCC(Vacuum Residue Desulfurization and Residue Fluid Catalytic Cracking).Furthermore,a novel processing pathway named VGOHDT-HTMP-DC(Vacuum Gas Oil Hydrotreating,Hydrogenation and TMP coupling process and Delayed Coking)has also been developed to find methods to improve the economic performance based on a ten-million-CNY output value(TMYOV)and a reduced GHG emissions.Our results demonstrate that VRHCRU could consume more energy and emit more GHG(877.11 t of CO2 eq·TMYOV^-1·h^-1)than VRDS-RFCC(817.03 t of CO2 eq·TMYOV^-1·h^-1)and VGOHDT-HTMP-DC(721.96 t of CO2 eq·TMYOV^-1·h^-1),while obtaining a higher mass yield of petrochemicals.The VGOHDT-HTMP-DC process exhibits the lowest feedstock consumption,hydrogen consumption,energy consumption,and GHG emissions,indicating that VGOHDT-HTMP-DC has both well economic and environmentally friendly performance.
基金the funding of the National Basic Research Program of China (Grant No.2006CB202505)
文摘The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of asphaltene molecules were estimated by combining 1 H nuclear magnetic resonance and X-ray diffraction analyses,and were also ob-tained from vapor pressure osmometry and elemental analysis.Heteroatoms,such as S,N,and O atoms,were considered in the construction of average molecular structure of heavy oils.Two important structural parameters were proposed,including the number of alkyl chain substituents to aromatic rings and the number of total rings with heteroatoms.Ultimately,the av-erage molecular structures of polycyclic aromatics,heavy resins and asphaltene molecules were constructed.The number of α-,β-,γ-,and aromatic hydrogen atoms of the constructed average molecular structures fits well with the number of hydro-gen atoms derived from the experimental spectral data.
基金financial support from the National Natural Science Foundation of China (No. 41302101 and No. 21476263)
文摘Adsorption of FCC dry gas components, hydrogen(H_2), nitrogen(N_2), methane(CH_4), ethane(C_2H_6) and ethylene(C_2H_4) in zeolite Y was studied by performing the Grant Canonical Monte Carlo(GCMC) simulations at 298K and 823K and under a pressure range up to 10 MPa. Simulation results were analyzed using the Langmuir model, which presented fitting of dry gas components adsorption to be suggested as the monolayer adsorption. C_2H_4 presented most single adsorption amount, which reached 7.63 mol/kg at 298K under a pressure of 200kPa. Thermodynamic parameters of the Gibbs free energy change, enthalpy change and entropy change were analyzed based on adsorption equilibrium constant obtained from the GCMC simulations. The results suggested that it was more favorable for C_2H_4 to be adsorbed in zeolite Y. Adsorption molecules were in ordered arrangement in the zeolite, and C_2H_4 exhibited a more orderly arrangement than other components. Additionally, a competition in the adsorption of a mixture of dry gas components was found, and supercages were the priority adsorption space. The competition was favorable to CH_4 and C_2H_6, and the competitive power was affected by temperature.
基金supported by the National Natural Science Foundation of China (No. 21576292)the independent innovation research project of China University of Petroleum (East China) (No. 22CX0300A)
文摘The distribution and form of iron and calcium compounds were studied using hydrogenation feedstock and hydrogenation products with different space velocities as the research object.The content of metallic elements,such as calcium and iron in hydrogenation feedstock,and extract samples were determined via flame atomic absorption spectrometry.The water-soluble iron and calcium species in oil samples were determined by an IC2010 high-throughput ion chromatograph.Nearly 60%-80%of the iron or calcium compounds were mainly concentrated in resins and asphaltenes.Iron and calcium compounds mainly exist in the form of oil-soluble metal species in hydrogenation feedstock and hydrogenation products.Under certain conditions of reaction temperature,pressure,and volume ratio of hydrogen to oil,when the reaction space velocity was 0.6 h^(−1),about 30%of the iron or calcium compounds were converted from oil-soluble to water-soluble species after hydrogenation.When the reaction space velocity was decreased from 1.70 to 0.60 h^(−1),the proportion of iron compounds converted from oil-soluble to water-soluble increased from 8.4%to 28%.Moreover,the proportion of calcium compounds converted from oil-soluble to water-soluble increased from 10%to 37%.This denotes that with decreasing reaction space velocity,the ratio of oil-soluble to water-soluble species increases.Water-soluble iron and calcium compounds are present in the form of inorganic salts,such as chlorate and sulfate.This study helps in understanding the removal mechanism of iron and calcium compounds and optimizing the operating conditions of residue hydrogenation.
基金the financial support provided by the National Natural Science Foundation of China (Grant No. 21376266)the Petro China Innovation Foundation (Grant No. 2011D-5006-0405)the Fundamental Research Funds for the Central Universities (Grant No. 27R1104049A)
文摘The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which could delay th aggregation and coke formation from asphaltenes on the catalyst, and make heavy components transformed into light oi The residue conversion in the presence of this additive increased by 1.94%, and the yield of light oil increased by 1.53%when the reaction time was 90 min. The surface properties of the catalyst in the presence of this additive were better tha that of the blank test within a very short time(30 min) and deteriorated rapidly after a longer reaction time due to highe conversion and coke deposition. Compared with the blank test, the case using the said additive had shown that the structur of hydrotreated asphaltene units was smaller and the condensation degrees were higher. The test results indicated that th additive could improve the hydrotreating reactivity of residue via permeation and depolymerization, the heavier componen could be transformed into light oil more easily, and the light oil yield and residue conversion were higher for the case usin the said additive in residue hydrotreating process.
基金We are grateful for financial support of the National Natural Science Foundation of China(21776312)the Fundamental Research Funds for the Central Universities(18CX02130A).
文摘ZSM-5 zeolite samples with a SiO2/Al2O3 ratio of 40 were synthesized by a hydrothermal method,and treated by 0.3 M tetrapropyl ammonium hydroxide(TPAOH)and 0.3 M sodium hydroxide(NaOH)solution separately to create hollow structures.The synthesized ZSM-5 zeolite and treated ZSM-5 zeolite samples were evaluated for aromatization of 1-hexene in a continuous flow reactor.The prepared ZSM-5 zeolite samples were characterized by XRD,SEM,TEM,NMR,XPS,and other analyses.The results showed that the alkali treatment formed mesopores and hollow structures in the ZSM-5 crystals without destroying the topological structure.The acid amount of ZSM-5 zeolite was also increased after alkali treatment.Compared with the ZSM-5 zeolite treated by TPAOH,the ZSM-5 zeolite treated by NaOH had more mesopores and a higher total acid amount but a lower strong acid amount,resulting in higher aromatics yields and catalytic stability for 1-hexene aromatization.The characterization of spent ZSM-5 zeolites suggested that the spent treated ZSM-5 zeolites contained less coke,leading to a smaller reduction of micropore surface area and volume than in the spent parent ZSM-5,which contributed to the stability enhancement.
