A novel porous binder was obtained from acid-treated kaolin. This new binder possessed abundant meso/macropores, good hydrothermal stability and heavy metal resistance. The prepared catalyst using new binder featured ...A novel porous binder was obtained from acid-treated kaolin. This new binder possessed abundant meso/macropores, good hydrothermal stability and heavy metal resistance. The prepared catalyst using new binder featured low attrition index and large pore volume. The catalysts were contaminated with Ni, V, and tested in a fixed-fluidized bed reactor unit. In comparison with the reference sample, the oil conversion achieved by the above-mentioned catalyst increased by 3.50 percentage points, and heavy oil yield decreased by 2.86 percentage points, while the total liquid yield and light oil yield increased by 2.82 percentage points and 0.79 percentage points, respectively. The perfect pore structure, good hydrothermal stability and heavy metal resistant performance of new binder were the possible causes leading to its outstanding performance.展开更多
Increasing gasoline production in FCC unit can improve the utilization efficiency of petroleum resources and gain economic benefit.This paper discusses the technical principles for increasing FCC gasoline yield from t...Increasing gasoline production in FCC unit can improve the utilization efficiency of petroleum resources and gain economic benefit.This paper discusses the technical principles for increasing FCC gasoline yield from the aspects of feedstock properties,operating conditions,LCO(light cycle oil)recycling,catalyst selection and reactor type,and illustrates the industrial application examples for maximizing gasoline production.The technical measures,such as optimizing the feedstock,properly increasing the catalyst activity and reaction temperature,recycling LCO or hydrotreated LCO,applying high gasoline yield catalyst,and adopting the two-zone riser reactor,are proposed to enhance the gasoline yield.展开更多
In this study,the deactivation mechanism caused by high accessibility of strong acid sites for the waste FCC catalyst was proposed and verified for the first time.Based on the proposed deactivation mechanism,magnesium...In this study,the deactivation mechanism caused by high accessibility of strong acid sites for the waste FCC catalyst was proposed and verified for the first time.Based on the proposed deactivation mechanism,magnesium modification through magnesium chloride impregnation was employed for the regeneration of waste FCC catalyst.The regenerated waste FCC catalyst was characterized,with its heavy oil catalytic cracking performance tested.The characterization results indicated that,in comparison with the unmodified waste FCC catalyst,the acid sites strength of the regenerated waste FCC catalyst was weakened,with no prominent alterations of the total acid sites quantity and textural properties.The heavy oil catalytic cracking results suggested that the catalytic cracking performance of the regenerated waste FCC catalyst was greatly improved due to the suitable surface acidity of the sample.In contrast with the unmodified waste FCC catalyst,the gasoline yield over the regenerated waste FCC catalyst significantly increased by 3.04 percentage points,meanwhile the yield of dry gas,LPG,coke and bottoms obviously decreased by 0.36,0.81,1.28 and 0.87 percentage points,respectively,making the regenerated waste FCC catalyst serve as a partial substitute for the fresh FCC catalyst.Finally,the acid property change mechanism was discussed.展开更多
In this paper, carbon nanotube supported Co-Mo catalysts for selective hydrodesulphurization (HDS) of fluid catalytic cracking (FCC) gasoline were studied, using di-isobutylene, cyclohexene, 1-octene and thiophene...In this paper, carbon nanotube supported Co-Mo catalysts for selective hydrodesulphurization (HDS) of fluid catalytic cracking (FCC) gasoline were studied, using di-isobutylene, cyclohexene, 1-octene and thiophene as model compounds to simulate FCC gasoline. The results show that the Co-Mo/CNT has very high HDS activity and HDS/hydrogenation selectivity comparing with the Co-Mo/γ-Al2O3 and Co-Mo/AC catalyst systems. The saturation ratio of cyclohexene was lower than 50%, and the saturation ratio of 1,3-di-isobutylene lower than 60% for the Co-Mo/CNT catalysts. Co/Mo atomic ratio was found to be one of the most important key factors in influencing the hydrogenation selectivity and HDS activity, and the most suitable Co/Mo atomic ratio was 0.4. Co/CNT and Mo/CNT mono-metallic catalysts showed lower HDS activity and selectivity than the Co-Mo/CNT bi-metallic catalysts.展开更多
The failure of a fluid catalysis and cracking unit (FCCU) in a Chinese refinery was investigated by using nondestructive detection methods, fracture surface examination, hardness measurement, chemical composition and...The failure of a fluid catalysis and cracking unit (FCCU) in a Chinese refinery was investigated by using nondestructive detection methods, fracture surface examination, hardness measurement, chemical composition and corrosion products analysis. The results showed that the failure was caused by the dew point nitrate stress corrosion cracking. For a long operation period, the wall temperature of the regenerator in the FCCU was below the fume dew point. As a result, an acid fume NOx-SOx-H2O medium present- ed on the surface, resulting in stress corrosion cracking of the component with high residual stress. In order to confirm the relative conclusion, simulated testing was conducted in laboratory, and the results showed similar cracking characteristics. Finally, some sug- gestions have been made to prevent the stress corrosion cracking of an FCCU from re-occurring in the future.展开更多
Fluid catalytic cracking(FCC)technologies of downer reactors,which have reached the demonstration or commercial scale,are systematically discussed,i.e.,millisecond catalytic cracking,fluidization lab of Tsinghua Unive...Fluid catalytic cracking(FCC)technologies of downer reactors,which have reached the demonstration or commercial scale,are systematically discussed,i.e.,millisecond catalytic cracking,fluidization lab of Tsinghua University,and high-severity FCC.Moreover,aiming to promote industrial application,the fundamental studies are comprehensively described,particularly focusing on high-density downer reactors,clusters,and up-scaling.Furthermore,from the perspective of industrial application,some research directions toward further developments are suggested.展开更多
Fluid catalytic cracking(FCC)is a vitally important refinery process.The fractionation,absorption,and stabilization system in the FCC process is a significant way to obtain key products,and its parameters will directl...Fluid catalytic cracking(FCC)is a vitally important refinery process.The fractionation,absorption,and stabilization system in the FCC process is a significant way to obtain key products,and its parameters will directly affect the quality of the products.In this work,using industrial data from an actual FCC process,a model of the FCC fractionation,absorption,and stabilization system was developed using process simulation software.The sequence quadratic program algorithm was then used to identify the parameters of each tower,increasing the accuracy of the simulation results.Next,using this improved model,a sensitivity analysis was performed to examine the effects of different operating conditions.The pattern-search method was then used to optimize the operating parameters of the system.The results showed that the optimized model has good prediction accuracy,and using the model,it was found that changing the operation parameters could result in a 1.84%improvement in economic benefits.As such,the developed model was demonstrated to be usefully applicable to the optimization of the process operation of an FCC fractionation,absorption,and stabilization system.展开更多
A new generic reaction in the form of PC_i→PC_m+[i,m]→PC_m+λi,m coke+surplusage has been proposed for describing the catalytic cracking behavior of petroleum narrow cuts or pseudo-components(PCs),where the rate con...A new generic reaction in the form of PC_i→PC_m+[i,m]→PC_m+λi,m coke+surplusage has been proposed for describing the catalytic cracking behavior of petroleum narrow cuts or pseudo-components(PCs),where the rate constant formula is derived from the transition state theory and the coking amount is correlated to the properties of the intermediate substance [i,m].In composing the cracking reaction network for feedstock and product oils,only the product PC m of the proposed generic reaction is used,which together with a criterion for excluding exothermic reactions,distinctly reduces the number of reactions in the network.With the proposed cracking reaction scheme coupled with special pseudo-components,a predictive one-dimensional steady state model for fluid catalytic cracking risers is formulated in the sense that for a given riser and given catalyst,the model parameters are independent of stock oils,product schemes and other operational conditions.The great correlating and predicting capability of the resulted model is tested with production data in different scenarios of four commercial risers.展开更多
The matrix catalytic function when cracking the feed oil with large molecular size was systematically studied using three different catalyst configurations, including staged bed, partly mixed bed and completely mixed ...The matrix catalytic function when cracking the feed oil with large molecular size was systematically studied using three different catalyst configurations, including staged bed, partly mixed bed and completely mixed bed. Results showed that molecules in the feed oil with large molecular size indeed preferred to be first precracked on the matrix surface and then entered into the zeolite pores during the practical reaction process. Furthermore, the matrix catalytic function exhibited a great matrix-precracking ability to large feed molecules, which considerably increased the catalyst activity and the light oil selectivity. Besides the much better accessibility, the matrix-precracking ability was also from the similar capability to crack large feed hydrocarbons into the moderate fragments with that of the zeolite component. More interestingly, the interactions between the matrix catalytic function and the zeolite catalytic function made the catalyst not only exhibit much more catalytic advantages of the zeolite component, but also retain the matrix-precracking ability. As a result, the interactions enhanced the catalyst activity and improved the product distribution at the same time. The matrix catalytic function is indispensable for the catalytic cracking of feed with large molecular size, although the matrix component itself presented an inferior catalytic performance than the zeolite component did. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units,their cacking mechanism and microscopic reaction netw...Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units,their cacking mechanism and microscopic reaction networks,such as activation modes,ring-opening paths,and the production of aromatics,remain debated.In this context,we reported experimental and computational work aimed at elucidating the reaction network of naphthenes in fluid catalytic cracking using cyclohexane as the model naphthene.First,the main reactions for the formation of highly selective and value-added products such as light olefins and aromatics were discussed.Then,the proportions of cyclohexane activation via(i)the non-classical carbonium mechanism and(ii)the classical carbenium mechanism were analyzed by data fitting methods,which revealed that around 32.6%of cyclohexane was initiated by path(i),and the remaining naphthene was activated by path(ii).Moreover,our DFT results showed that the ring opening of cyclohexane through pathway(i)was more difficult than that through path(ii),and ring opening followed by the ring contraction of cyclohexane carbenium ions was the most energetically favorable route among the different ring-opening ways.展开更多
Effects of metal oxide in ZSM-5 zeolite on its catalytic performance in fluid catalytic cracking reaction were studied via characterization by XRD and FT-IR spectroscopy using pyridine and collidine as molecular probe...Effects of metal oxide in ZSM-5 zeolite on its catalytic performance in fluid catalytic cracking reaction were studied via characterization by XRD and FT-IR spectroscopy using pyridine and collidine as molecular probes,and the modified ZSM-5 zeolite was evaluated in a micro reactor using standard light diesel fraction as the feedstock.Test results indicate that the metal species introduced into the ZSM-5 zeolite had led to the formation of Lewis acid centers.When the modified ZSM-5 zeolite with the metal species on its surface was used as the catalyst in FCC reaction,both the propylene yield and the propylene concentration in the liquefied petroleum gas increased,but in the meantime,more hydrogen and coke were formed at high conversion rate under the joint action of nonselective cracking of Lewis acid centers and dehydrogenation at metal centers on its outside surface.展开更多
The demand for propylene has been growing recently. The concentration of olefins in the gasoline is strictly limited by the related environmental regulations. The olefins contained in the gasoline used as the feed cou...The demand for propylene has been growing recently. The concentration of olefins in the gasoline is strictly limited by the related environmental regulations. The olefins contained in the gasoline used as the feed could be cracked into light olefins to slash the olefin concentration in the gasoline to yield more propylene at the same time. The monolithic catalyst washcoated on the modified ZSM-5 zeolite was used in the experiments. The effect of the temperature, the Si/Al ratio in ZSM-5 and the addition of the rare earth elements on the selectivities and the yields of the light olefins were studied. The high yields of propylene and butene could be obtained under the experimental conditions of a higher temperature and Si/Al ratio with the addition of rare earth elements.展开更多
It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC (fluid catalytic cracking). The effects of temperature and C/O ratio (catalyst to o...It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC (fluid catalytic cracking). The effects of temperature and C/O ratio (catalyst to oil weight ratio) on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil (VGO) was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas (LPG), repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC (hydrogen transfer coefficient) and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.展开更多
Catalytic cracking is the main method to lighten heavy crude oil,this process can produce high quality oil products such as gasoline and diesel,but also produces a large amount of fluid catalytic cracking slurry(FCCS)...Catalytic cracking is the main method to lighten heavy crude oil,this process can produce high quality oil products such as gasoline and diesel,but also produces a large amount of fluid catalytic cracking slurry(FCCS).The catalyst particles in FCCS seriously restrict the secondary processing of FCCS and need to be removed,and the properties of Fccs is an important factor that affects the removal efficiency of the catalyst particles.Based on the"effective contact point"model proposed by the research group,this study further proposed the"electrostatic separation efficiency calculation"model.In this model,since Fccs has a uniform distribution of catalyst particles,the ratio of the number of catalyst particles can be expressed as the ratio of area to achieve the calculation of separation efficiency.Then the catalyst removal efficiency under different viscosity was analyzed,thus verifying the feasibility of this model.The effects of temperature and mass ratio of four components on the viscosity of FccS were investigated respectively,then the effects of temperature and four components'mass ratio on the electrostatic sep-aration can be directly converted into the effect of viscosity on the electrostatic separation efficiency.All the results show the electrostatic separation efficiency decreases with increasing viscosity,and the best separationtemperatureis120℃.展开更多
基金the Department of Science and Technology Management of PetroChina for providing financial support
文摘A novel porous binder was obtained from acid-treated kaolin. This new binder possessed abundant meso/macropores, good hydrothermal stability and heavy metal resistance. The prepared catalyst using new binder featured low attrition index and large pore volume. The catalysts were contaminated with Ni, V, and tested in a fixed-fluidized bed reactor unit. In comparison with the reference sample, the oil conversion achieved by the above-mentioned catalyst increased by 3.50 percentage points, and heavy oil yield decreased by 2.86 percentage points, while the total liquid yield and light oil yield increased by 2.82 percentage points and 0.79 percentage points, respectively. The perfect pore structure, good hydrothermal stability and heavy metal resistant performance of new binder were the possible causes leading to its outstanding performance.
文摘Increasing gasoline production in FCC unit can improve the utilization efficiency of petroleum resources and gain economic benefit.This paper discusses the technical principles for increasing FCC gasoline yield from the aspects of feedstock properties,operating conditions,LCO(light cycle oil)recycling,catalyst selection and reactor type,and illustrates the industrial application examples for maximizing gasoline production.The technical measures,such as optimizing the feedstock,properly increasing the catalyst activity and reaction temperature,recycling LCO or hydrotreated LCO,applying high gasoline yield catalyst,and adopting the two-zone riser reactor,are proposed to enhance the gasoline yield.
基金supported by the Exploratory Research Program of Petrochemical Research Institute (16-yk-01-03),PetroChina
文摘In this study,the deactivation mechanism caused by high accessibility of strong acid sites for the waste FCC catalyst was proposed and verified for the first time.Based on the proposed deactivation mechanism,magnesium modification through magnesium chloride impregnation was employed for the regeneration of waste FCC catalyst.The regenerated waste FCC catalyst was characterized,with its heavy oil catalytic cracking performance tested.The characterization results indicated that,in comparison with the unmodified waste FCC catalyst,the acid sites strength of the regenerated waste FCC catalyst was weakened,with no prominent alterations of the total acid sites quantity and textural properties.The heavy oil catalytic cracking results suggested that the catalytic cracking performance of the regenerated waste FCC catalyst was greatly improved due to the suitable surface acidity of the sample.In contrast with the unmodified waste FCC catalyst,the gasoline yield over the regenerated waste FCC catalyst significantly increased by 3.04 percentage points,meanwhile the yield of dry gas,LPG,coke and bottoms obviously decreased by 0.36,0.81,1.28 and 0.87 percentage points,respectively,making the regenerated waste FCC catalyst serve as a partial substitute for the fresh FCC catalyst.Finally,the acid property change mechanism was discussed.
基金Supported by Foundation of Innovation for Middle-Aged and Youth, CNPC (Foundation No.W990411)
文摘In this paper, carbon nanotube supported Co-Mo catalysts for selective hydrodesulphurization (HDS) of fluid catalytic cracking (FCC) gasoline were studied, using di-isobutylene, cyclohexene, 1-octene and thiophene as model compounds to simulate FCC gasoline. The results show that the Co-Mo/CNT has very high HDS activity and HDS/hydrogenation selectivity comparing with the Co-Mo/γ-Al2O3 and Co-Mo/AC catalyst systems. The saturation ratio of cyclohexene was lower than 50%, and the saturation ratio of 1,3-di-isobutylene lower than 60% for the Co-Mo/CNT catalysts. Co/Mo atomic ratio was found to be one of the most important key factors in influencing the hydrogenation selectivity and HDS activity, and the most suitable Co/Mo atomic ratio was 0.4. Co/CNT and Mo/CNT mono-metallic catalysts showed lower HDS activity and selectivity than the Co-Mo/CNT bi-metallic catalysts.
基金This work was financially supported by the Major State Basic Research Development Program of China (973 ProgramNo.19990970) and Petrochemical Company of China.
文摘The failure of a fluid catalysis and cracking unit (FCCU) in a Chinese refinery was investigated by using nondestructive detection methods, fracture surface examination, hardness measurement, chemical composition and corrosion products analysis. The results showed that the failure was caused by the dew point nitrate stress corrosion cracking. For a long operation period, the wall temperature of the regenerator in the FCCU was below the fume dew point. As a result, an acid fume NOx-SOx-H2O medium present- ed on the surface, resulting in stress corrosion cracking of the component with high residual stress. In order to confirm the relative conclusion, simulated testing was conducted in laboratory, and the results showed similar cracking characteristics. Finally, some sug- gestions have been made to prevent the stress corrosion cracking of an FCCU from re-occurring in the future.
基金the funding of the project by SINOPEC (No. 120009)
文摘Fluid catalytic cracking(FCC)technologies of downer reactors,which have reached the demonstration or commercial scale,are systematically discussed,i.e.,millisecond catalytic cracking,fluidization lab of Tsinghua University,and high-severity FCC.Moreover,aiming to promote industrial application,the fundamental studies are comprehensively described,particularly focusing on high-density downer reactors,clusters,and up-scaling.Furthermore,from the perspective of industrial application,some research directions toward further developments are suggested.
基金supported by the National Key Research&Development Program-Intergovernmental International Science and Technology Innovation Cooperation Project (Grant No.2021YFE0112800)National Natural Science Foundation of China (Grant Nos.61973124+2 种基金61873093)the SINOPEC Research Program (Grant No.119030-2)Shanghai AI Lab
文摘Fluid catalytic cracking(FCC)is a vitally important refinery process.The fractionation,absorption,and stabilization system in the FCC process is a significant way to obtain key products,and its parameters will directly affect the quality of the products.In this work,using industrial data from an actual FCC process,a model of the FCC fractionation,absorption,and stabilization system was developed using process simulation software.The sequence quadratic program algorithm was then used to identify the parameters of each tower,increasing the accuracy of the simulation results.Next,using this improved model,a sensitivity analysis was performed to examine the effects of different operating conditions.The pattern-search method was then used to optimize the operating parameters of the system.The results showed that the optimized model has good prediction accuracy,and using the model,it was found that changing the operation parameters could result in a 1.84%improvement in economic benefits.As such,the developed model was demonstrated to be usefully applicable to the optimization of the process operation of an FCC fractionation,absorption,and stabilization system.
基金Supported by the National Natural Science Foundation of China(21676012)the Fundamental Research Funds for the Central Universities(Project YS1404)the National High Technology Research and Development Program of China(2007AA04Z191)
文摘A new generic reaction in the form of PC_i→PC_m+[i,m]→PC_m+λi,m coke+surplusage has been proposed for describing the catalytic cracking behavior of petroleum narrow cuts or pseudo-components(PCs),where the rate constant formula is derived from the transition state theory and the coking amount is correlated to the properties of the intermediate substance [i,m].In composing the cracking reaction network for feedstock and product oils,only the product PC m of the proposed generic reaction is used,which together with a criterion for excluding exothermic reactions,distinctly reduces the number of reactions in the network.With the proposed cracking reaction scheme coupled with special pseudo-components,a predictive one-dimensional steady state model for fluid catalytic cracking risers is formulated in the sense that for a given riser and given catalyst,the model parameters are independent of stock oils,product schemes and other operational conditions.The great correlating and predicting capability of the resulted model is tested with production data in different scenarios of four commercial risers.
基金supported by the National Natural Science Foundation of China(U146220521476263+3 种基金21406270)the Fundamental Research Funds for the Central Universities(15CX06036A)the China University of Petroleum for Postgraduate Technology Innovation Project(YCX2015028)the Qingdao People’s Livelihood Project(13-1-3-126-nsh)
文摘The matrix catalytic function when cracking the feed oil with large molecular size was systematically studied using three different catalyst configurations, including staged bed, partly mixed bed and completely mixed bed. Results showed that molecules in the feed oil with large molecular size indeed preferred to be first precracked on the matrix surface and then entered into the zeolite pores during the practical reaction process. Furthermore, the matrix catalytic function exhibited a great matrix-precracking ability to large feed molecules, which considerably increased the catalyst activity and the light oil selectivity. Besides the much better accessibility, the matrix-precracking ability was also from the similar capability to crack large feed hydrocarbons into the moderate fragments with that of the zeolite component. More interestingly, the interactions between the matrix catalytic function and the zeolite catalytic function made the catalyst not only exhibit much more catalytic advantages of the zeolite component, but also retain the matrix-precracking ability. As a result, the interactions enhanced the catalyst activity and improved the product distribution at the same time. The matrix catalytic function is indispensable for the catalytic cracking of feed with large molecular size, although the matrix component itself presented an inferior catalytic performance than the zeolite component did. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
基金This work was performed with the financial support of Sinopec Research Institute of Petroleum Processing(RIPP,Proj.R17022).
文摘Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units,their cacking mechanism and microscopic reaction networks,such as activation modes,ring-opening paths,and the production of aromatics,remain debated.In this context,we reported experimental and computational work aimed at elucidating the reaction network of naphthenes in fluid catalytic cracking using cyclohexane as the model naphthene.First,the main reactions for the formation of highly selective and value-added products such as light olefins and aromatics were discussed.Then,the proportions of cyclohexane activation via(i)the non-classical carbonium mechanism and(ii)the classical carbenium mechanism were analyzed by data fitting methods,which revealed that around 32.6%of cyclohexane was initiated by path(i),and the remaining naphthene was activated by path(ii).Moreover,our DFT results showed that the ring opening of cyclohexane through pathway(i)was more difficult than that through path(ii),and ring opening followed by the ring contraction of cyclohexane carbenium ions was the most energetically favorable route among the different ring-opening ways.
文摘Effects of metal oxide in ZSM-5 zeolite on its catalytic performance in fluid catalytic cracking reaction were studied via characterization by XRD and FT-IR spectroscopy using pyridine and collidine as molecular probes,and the modified ZSM-5 zeolite was evaluated in a micro reactor using standard light diesel fraction as the feedstock.Test results indicate that the metal species introduced into the ZSM-5 zeolite had led to the formation of Lewis acid centers.When the modified ZSM-5 zeolite with the metal species on its surface was used as the catalyst in FCC reaction,both the propylene yield and the propylene concentration in the liquefied petroleum gas increased,but in the meantime,more hydrogen and coke were formed at high conversion rate under the joint action of nonselective cracking of Lewis acid centers and dehydrogenation at metal centers on its outside surface.
文摘The demand for propylene has been growing recently. The concentration of olefins in the gasoline is strictly limited by the related environmental regulations. The olefins contained in the gasoline used as the feed could be cracked into light olefins to slash the olefin concentration in the gasoline to yield more propylene at the same time. The monolithic catalyst washcoated on the modified ZSM-5 zeolite was used in the experiments. The effect of the temperature, the Si/Al ratio in ZSM-5 and the addition of the rare earth elements on the selectivities and the yields of the light olefins were studied. The high yields of propylene and butene could be obtained under the experimental conditions of a higher temperature and Si/Al ratio with the addition of rare earth elements.
文摘It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC (fluid catalytic cracking). The effects of temperature and C/O ratio (catalyst to oil weight ratio) on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil (VGO) was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas (LPG), repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC (hydrogen transfer coefficient) and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.
基金supported by the[Natural Science Foundation Project of Shandong Province#1]under Grant[ZR2019MEE033][Fundamental Research Funds for the central Universities#2]under Grant[19CX02035A].
文摘Catalytic cracking is the main method to lighten heavy crude oil,this process can produce high quality oil products such as gasoline and diesel,but also produces a large amount of fluid catalytic cracking slurry(FCCS).The catalyst particles in FCCS seriously restrict the secondary processing of FCCS and need to be removed,and the properties of Fccs is an important factor that affects the removal efficiency of the catalyst particles.Based on the"effective contact point"model proposed by the research group,this study further proposed the"electrostatic separation efficiency calculation"model.In this model,since Fccs has a uniform distribution of catalyst particles,the ratio of the number of catalyst particles can be expressed as the ratio of area to achieve the calculation of separation efficiency.Then the catalyst removal efficiency under different viscosity was analyzed,thus verifying the feasibility of this model.The effects of temperature and mass ratio of four components on the viscosity of FccS were investigated respectively,then the effects of temperature and four components'mass ratio on the electrostatic sep-aration can be directly converted into the effect of viscosity on the electrostatic separation efficiency.All the results show the electrostatic separation efficiency decreases with increasing viscosity,and the best separationtemperatureis120℃.