Active sites of Fluid catalytic cracking (FCC) catalyst are poisoned during operation in the FCC reactor due to causes including feedstock contaminant metals deposition. This leads to activity, selectivity and increas...Active sites of Fluid catalytic cracking (FCC) catalyst are poisoned during operation in the FCC reactor due to causes including feedstock contaminant metals deposition. This leads to activity, selectivity and increasing coking problems, thereby raising concern to the refiner. This work investigated effect of nickel coexisting with vanadium in the FCC feedstock on the standard FCC catalyst during cracking process, in which destruction of active sites occurs as a result of the metals deposition. Laboratory simulated equilibrium catalysts (E-cats) were studied by XRD, FTIR spectroscopy, N-2 adsorption, solid state MAS-NMR, SEM and H-2-TPR. Results revealed that vanadium, above a certain concentration in the catalyst, under hydrothermal conditions, is highly detrimental to the catalyst's structure and activity. Conversely, nickel hardly affects the catalyst structure, but its co-presence in the catalyst reduces destructive effects of vanadium. The mechanism of nickel inhibition of vanadium poisoning of the catalyst is discussed. (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
This paper has provided an effective method to utilize the flter residue. A Y zeolite-containing composite and a fuid catalytic cracking （FCC） catalyst had been successfully prepared by an in-situ crystallization te...This paper has provided an effective method to utilize the flter residue. A Y zeolite-containing composite and a fuid catalytic cracking （FCC） catalyst had been successfully prepared by an in-situ crystallization technology using flter residue and kaolin as raw materials. The samples were characterized by XRD, FT-IR, SEM, and N2 adsorption-desorption techniques and evaluated in a bench FCC unit. In comparison to the reference samples synthesized from single kaolin, the silica/alumina molar ratio, the external surface area, and the total pore volume of the composite increased by 16.2%, 14.5%, and 16.2%, respectively. The catalyst possessed more meso- and macro-pores and more acid sites than the reference catalyst, and exhibited better coke selectivity. The prepared catalyst had the optimum isomerization and aromatization performance. The olefn content in the cracked gasoline obtained over this catalyst was reduced by 5.05 percentage points with the research octane number of gasoline increased by 0.5 units.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
Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadiu...Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadium with low Oxnum could affect the chemical conversion of large-size hydrocarbon molecules. However, the vanadium deposited on equilibrium catalyst bad high Oxnum because of the oxidation reaction taking place in the regenerator, so an activation method to reduce vanadium Oxnum named ＂selective activation＂ was introduced. It was proved by means of Electron Paramagnetic Resonance （EPR） and Temperature-Programmed Reduction （TPR） methods that the vanadium Oxnum was decreased, when the catalyst was activated. The molecular modeling studies are consistent well with the lab evaluation results. The light olefins selectivity of activated equilibrium catalysts was better than that achieved by the inactivated catalysts. Similar results were observed with the lab vanadium-contaminated catalyst. The light olefins selectivity of the catalyst was optimized when the vanadium Oxnum was close to 2 （VO）.展开更多
An advanced silica-dominated matrix technology platform and its application were introduced in this paper. Through novel proprietary processing,the advanced silica-dominated matrix was prepared from the unique silica ...An advanced silica-dominated matrix technology platform and its application were introduced in this paper. Through novel proprietary processing,the advanced silica-dominated matrix was prepared from the unique silica sol and pseudo-boehmite.The matrix pore size distribution and acidity can be tailored to provide optimal coke-selectivity and bottoms-cracking ability matched to feedstock characteristics.A novel FCC catalyst(RSC-2006) for reducing coke and slurry yields was developed based on the silica-dominated matrix technology platform.The results of commercial application of the said technology indicated that the RSC-2006 catalyst exhibited excellent performance on bottoms cracking,coke selectivity and high value products yields.展开更多
The strontium modified waste FCC catalyst was prepared by magnetic stirring method and characterized by Xray diffractometry(XRD),UV-Vis diffuse reflectance spectrometry(DRS),X-ray photoelectron spectroscopy(XPS)and sc...The strontium modified waste FCC catalyst was prepared by magnetic stirring method and characterized by Xray diffractometry(XRD),UV-Vis diffuse reflectance spectrometry(DRS),X-ray photoelectron spectroscopy(XPS)and scanning electron microscopy(SEM).Meanwhile,its photocatalytic denitrogenation performance was evaluated in terms of its ability to degrade the N-containing simulation oil under visible light.A mixture of strontium nitrate solution(with a concentration of 0.5 mol/L)and waste FCC catalyst was calcined at 400℃for 5 h prior to taking part in the photocatalytic denitrogenation reaction.The test results showed that the photocatalytic degradation rate of pyridine contained in simulation oil in the presence of the strontium modified FCC catalyst could reach 92.0% under visible light irradiation for 2.5 h.展开更多
On January 7, 2015 the project ＂Study on the technology formanufacture of high-spheroidicity FCC catalysts ＂undertakenby the SINOPEC Research Institute of Petroleum Processing（RIPP） has passed the technical apprai...On January 7, 2015 the project ＂Study on the technology formanufacture of high-spheroidicity FCC catalysts ＂undertakenby the SINOPEC Research Institute of Petroleum Processing（RIPP） has passed the technical appraisal organized by theScience and Technology Division of the Sinopec Corp.展开更多
The addition of distillation residues to the FCC feedstock leads to increased vanadiumloading on catalyst and the problems in catalyst deactivation.The deactivation process is related tothe destructive attack on the z...The addition of distillation residues to the FCC feedstock leads to increased vanadiumloading on catalyst and the problems in catalyst deactivation.The deactivation process is related tothe destructive attack on the zeolite crystallite by V<sub>2</sub>O<sub>5</sub>.Formation of low melting pointV<sub>2</sub>O<sub>5</sub>-USY-Na<sub>2</sub>O phases accelerates the diffusion of vanadium through the catalyst.A proposedmechanism,based on accelerated dealumination,is shown in the paper.Comparative vanadiumtrapping performances have been tested for FCC catalysts and the crystalline ABO<sub>3</sub> as an effectivevanadium trap is demonstrated in laboratory tests.展开更多
Novel composite material with a wide pore distribution was synthesized by an in situ technique using spent FCC catalyst as raw material. The characterization results indicated that the composite material contained 56....Novel composite material with a wide pore distribution was synthesized by an in situ technique using spent FCC catalyst as raw material. The characterization results indicated that the composite material contained 56.7% of zeolite Y and exhibited a much larger specific surface area and pore volume as well as strong hydrothermal stability. Fluid catalytic cracking(FCC) catalyst was prepared based on the composite material. The results indicated that the as-prepared catalyst possessed a unique pore structure that was advantageous to the diffusion-controlled reactions. In addition, the attrition resistance, activity and hydrothermal stability of the studied catalyst were superior to those of the reference catalyst. The catalyst also exhibited excellent nickel and vanadium passivation performance, strong bottoms upgrading selectivity, and better gasoline and coke selectivity. In comparison to the reference catalyst, the yields of the gasoline and light oil increased by 1.61 and 1.31 percentage points, respectively, and the coke yield decreased by 0.22 percentage points, and the olefin content in the produced gasoline reduced by 2.51 percentage points, with the research octane number increased by 0.7 unit.展开更多
The effect of temperature on the fluid-bed stability of three FCC catalysts has been analyzed through considerations on fluid-bed elasticity. Experimental findings on the effect of temperature on the elasticity modulu...The effect of temperature on the fluid-bed stability of three FCC catalysts has been analyzed through considerations on fluid-bed elasticity. Experimental findings on the effect of temperature on the elasticity modulus at minimum bubbling conditions, （E）mb, were analyzed using the hydrodynamic fluid-bed stability model developed by Foscolo and Gibilaro （1984） and adopting the interparticle-forces-based stability criterion developed by Mutsers and Rietema （1977）. For both models, the parameters which control changes in （E）mb with temperature are discussed, in order to establish the origin of the fluid-bed elasticity and analyze the ability of these models to discriminate between the relative importance of the hydrodynamic and interoarticle forces on the stability of the fluidized catalysts.展开更多
基金financially supported by the Joint Funds of the National Natural Science Foundation of ChinaChina National Petroleum Corporation(U1362202)+4 种基金National Natural Science Foundation of China(21206195)the Fundamental Research Funds for the Central Universities(14CX02050A,14CX02123A)Shandong Provincial Natural Science Foundation(ZR2012BM014)the project sponsored by Scientific Research Foundation for Returned Overseas Chinese Scholarthe support from Chinese Government under the Chinese scholarship scheme for international students
文摘Active sites of Fluid catalytic cracking (FCC) catalyst are poisoned during operation in the FCC reactor due to causes including feedstock contaminant metals deposition. This leads to activity, selectivity and increasing coking problems, thereby raising concern to the refiner. This work investigated effect of nickel coexisting with vanadium in the FCC feedstock on the standard FCC catalyst during cracking process, in which destruction of active sites occurs as a result of the metals deposition. Laboratory simulated equilibrium catalysts (E-cats) were studied by XRD, FTIR spectroscopy, N-2 adsorption, solid state MAS-NMR, SEM and H-2-TPR. Results revealed that vanadium, above a certain concentration in the catalyst, under hydrothermal conditions, is highly detrimental to the catalyst's structure and activity. Conversely, nickel hardly affects the catalyst structure, but its co-presence in the catalyst reduces destructive effects of vanadium. The mechanism of nickel inhibition of vanadium poisoning of the catalyst is discussed. (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financially supported by the National Natural Science Foundation of China (No.21371055)the Hunan Provincial Colleges and Universities Innovation Platform Open Fund Project (No.15K049)
文摘This paper has provided an effective method to utilize the flter residue. A Y zeolite-containing composite and a fuid catalytic cracking （FCC） catalyst had been successfully prepared by an in-situ crystallization technology using flter residue and kaolin as raw materials. The samples were characterized by XRD, FT-IR, SEM, and N2 adsorption-desorption techniques and evaluated in a bench FCC unit. In comparison to the reference samples synthesized from single kaolin, the silica/alumina molar ratio, the external surface area, and the total pore volume of the composite increased by 16.2%, 14.5%, and 16.2%, respectively. The catalyst possessed more meso- and macro-pores and more acid sites than the reference catalyst, and exhibited better coke selectivity. The prepared catalyst had the optimum isomerization and aromatization performance. The olefn content in the cracked gasoline obtained over this catalyst was reduced by 5.05 percentage points with the research octane number of gasoline increased by 0.5 units.
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.
文摘Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadium with low Oxnum could affect the chemical conversion of large-size hydrocarbon molecules. However, the vanadium deposited on equilibrium catalyst bad high Oxnum because of the oxidation reaction taking place in the regenerator, so an activation method to reduce vanadium Oxnum named ＂selective activation＂ was introduced. It was proved by means of Electron Paramagnetic Resonance （EPR） and Temperature-Programmed Reduction （TPR） methods that the vanadium Oxnum was decreased, when the catalyst was activated. The molecular modeling studies are consistent well with the lab evaluation results. The light olefins selectivity of activated equilibrium catalysts was better than that achieved by the inactivated catalysts. Similar results were observed with the lab vanadium-contaminated catalyst. The light olefins selectivity of the catalyst was optimized when the vanadium Oxnum was close to 2 （VO）.
文摘An advanced silica-dominated matrix technology platform and its application were introduced in this paper. Through novel proprietary processing,the advanced silica-dominated matrix was prepared from the unique silica sol and pseudo-boehmite.The matrix pore size distribution and acidity can be tailored to provide optimal coke-selectivity and bottoms-cracking ability matched to feedstock characteristics.A novel FCC catalyst(RSC-2006) for reducing coke and slurry yields was developed based on the silica-dominated matrix technology platform.The results of commercial application of the said technology indicated that the RSC-2006 catalyst exhibited excellent performance on bottoms cracking,coke selectivity and high value products yields.
基金financially supported by the Science and Technology Project of Fujian Province(No.CE0015)the Ningde Normal University Project on Serving the Western Coast to the TW Strait(No.2010H103)the National-level College Students’ Innovative Entrepreneurial Training Plan Project of Fujian Normal University(Nos.201210394005 and 201310394015)
文摘The strontium modified waste FCC catalyst was prepared by magnetic stirring method and characterized by Xray diffractometry(XRD),UV-Vis diffuse reflectance spectrometry(DRS),X-ray photoelectron spectroscopy(XPS)and scanning electron microscopy(SEM).Meanwhile,its photocatalytic denitrogenation performance was evaluated in terms of its ability to degrade the N-containing simulation oil under visible light.A mixture of strontium nitrate solution(with a concentration of 0.5 mol/L)and waste FCC catalyst was calcined at 400℃for 5 h prior to taking part in the photocatalytic denitrogenation reaction.The test results showed that the photocatalytic degradation rate of pyridine contained in simulation oil in the presence of the strontium modified FCC catalyst could reach 92.0% under visible light irradiation for 2.5 h.
文摘On January 7, 2015 the project ＂Study on the technology formanufacture of high-spheroidicity FCC catalysts ＂undertakenby the SINOPEC Research Institute of Petroleum Processing（RIPP） has passed the technical appraisal organized by theScience and Technology Division of the Sinopec Corp.
文摘The addition of distillation residues to the FCC feedstock leads to increased vanadiumloading on catalyst and the problems in catalyst deactivation.The deactivation process is related tothe destructive attack on the zeolite crystallite by V<sub>2</sub>O<sub>5</sub>.Formation of low melting pointV<sub>2</sub>O<sub>5</sub>-USY-Na<sub>2</sub>O phases accelerates the diffusion of vanadium through the catalyst.A proposedmechanism,based on accelerated dealumination,is shown in the paper.Comparative vanadiumtrapping performances have been tested for FCC catalysts and the crystalline ABO<sub>3</sub> as an effectivevanadium trap is demonstrated in laboratory tests.
基金provided by the National Natural Science Foundation of China(No.21371055)the Hunan provincial Natural Science Foundation of China(No.11JJ2008)the Hunan provincial Colleges and Universities Innovation Platform Open Fund Project(No.15K049)
文摘Novel composite material with a wide pore distribution was synthesized by an in situ technique using spent FCC catalyst as raw material. The characterization results indicated that the composite material contained 56.7% of zeolite Y and exhibited a much larger specific surface area and pore volume as well as strong hydrothermal stability. Fluid catalytic cracking(FCC) catalyst was prepared based on the composite material. The results indicated that the as-prepared catalyst possessed a unique pore structure that was advantageous to the diffusion-controlled reactions. In addition, the attrition resistance, activity and hydrothermal stability of the studied catalyst were superior to those of the reference catalyst. The catalyst also exhibited excellent nickel and vanadium passivation performance, strong bottoms upgrading selectivity, and better gasoline and coke selectivity. In comparison to the reference catalyst, the yields of the gasoline and light oil increased by 1.61 and 1.31 percentage points, respectively, and the coke yield decreased by 0.22 percentage points, and the olefin content in the produced gasoline reduced by 2.51 percentage points, with the research octane number increased by 0.7 unit.
文摘The effect of temperature on the fluid-bed stability of three FCC catalysts has been analyzed through considerations on fluid-bed elasticity. Experimental findings on the effect of temperature on the elasticity modulus at minimum bubbling conditions, （E）mb, were analyzed using the hydrodynamic fluid-bed stability model developed by Foscolo and Gibilaro （1984） and adopting the interparticle-forces-based stability criterion developed by Mutsers and Rietema （1977）. For both models, the parameters which control changes in （E）mb with temperature are discussed, in order to establish the origin of the fluid-bed elasticity and analyze the ability of these models to discriminate between the relative importance of the hydrodynamic and interoarticle forces on the stability of the fluidized catalysts.
