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
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 s...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 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
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 investigated the recovery of rare earth elements(REEs)and aluminum(AI)from the waste slag discharged by FCC catalyst factory(FCC waste slag)via acid leaching and selective precipitation.Analysis methods suc...This paper investigated the recovery of rare earth elements(REEs)and aluminum(AI)from the waste slag discharged by FCC catalyst factory(FCC waste slag)via acid leaching and selective precipitation.Analysis methods such as ICP-AES,XRF and XRD were applied to obtain experiment data.The maximum leaching efficiency of REEs and Al was achieved at pH value of 1 and with liquid to solid ratio of 4:1,Under such conditions,91.01%,92.24%and 94.77%of La,Ce and Al were extracted at 20℃for 2 h from the FCC waste slag,respectively.The SiOcontent in the leaching residue was 88.3%,which can be used as an available silicon resource.The REEs can be precipitated in the form of REEs and sodium double sulfate(NaRE(SO)·xHO)by adding NaSOto the leaching solution,while Al remained in the solution.Afterwards,the pH value of the filtrate was adjusted to 4.5,and Al was precipitated as AI(OH).Finally,NaRE(SO)·xHO and Al(OH)were converted into RECland Al(SO4)solution,respectively,which were recycled to manufacture zeolite.This process recovered REEs and Al from the FCC waste slag and reduced the emissions of waste slag simultaneously,which has an important economic and environment significance.展开更多
The chemical composition, structure and thermal stability of the spent FCC equilibrium catalyst from an oil refinery were characterized by XRD, FT-IR, DTA-TG, BET, complete chemical analysis, SEM, and XRF. The spent F...The chemical composition, structure and thermal stability of the spent FCC equilibrium catalyst from an oil refinery were characterized by XRD, FT-IR, DTA-TG, BET, complete chemical analysis, SEM, and XRF. The spent FCC equilibrium catalyst, clay, barium carbonate, and talc were used as the main raw materials to prepare the alumina abrasion-resistant ceramic balls to be used in the powder grinding mill for manufacture of architecture tiles. The results showed that after proper formulation study, the spent FCC equilibrium catalyst could replace industrial alumina to prepare high performance grinding balls. Meanwhile, the various performance indices of the grinding ball could meet the quality standard for similar products, and additionally, the energy saving effect was achieved in the operation of the grinding section, resulting in a successful comprehensive utilization of solid wastes.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
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
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 wi...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
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
A handy gamma-ray transmission method for estimating the particle concentration distribution in a fluid catalytic cracking （FCC） riser is proposed. The method is based on an empirical correlation ε（r）= ε-（0.19...A handy gamma-ray transmission method for estimating the particle concentration distribution in a fluid catalytic cracking （FCC） riser is proposed. The method is based on an empirical correlation ε（r）= ε-（0.191＋φ25＋3φ11）, which has only one unknown parameter y, hence only one single-beam experimental result is enough to estimate the particle concentration distribution in the riser. In order to verify the feasibility of this method, the particle concentrations of three cross-sections of the laboratory riser were measured and the distribution profiles were compared with those reported in the literature. Furthermore, by comparing other gamma-ray function methods applied in the measurement of risers, this method has distinct advantages, such as the device is simple and has no moving parts, the measurement is rapid, and the safety is high because only one gamma-ray beam is used. Therefore, the method has promising applications in estimating particle concentrations or monitoring operation conditions of risers.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
Nitrogen oxides （NOx） emission during the regeneration ofcoked fluid catalytic cracking （FCC） catalysts is an en- vironmental issue. In order to identify the correlations between nitrogen species in coke and diffe...Nitrogen oxides （NOx） emission during the regeneration ofcoked fluid catalytic cracking （FCC） catalysts is an en- vironmental issue. In order to identify the correlations between nitrogen species in coke and different nitrogen- containing products in tail gas, three coked catalysts with multilayer structural coke molecules were prepared in a fixed bed with model compounds （o-xylene and quinoline） at first. A series of characterization methods were used to analyze coke, including elemental analysis, FT-IR, XPS, and TG-MS. XPS characterization indicates all coked catalysts present two types of nitrogen species and the type with a higher binding energy is related with the inner part nitrogen atoms interacting with acid sites. Due to the stronger adsorption ability on acid sites for basic nitrogen compounds, the multilayer structural coke has unbalanced distribution of carbon and ni- trogen atoms between the inner part and the outer edge, which strongly affects gas product formation. At the early stage of regeneration, oxidation starts from the outer edge and the product NO can be reduced to N2 in high CO concentration. At the later stage, the inner part rich in nitrogen begins to be exposed to 02. At this period, the formation of CO decreases due to lack of carbon atoms, which is not beneficial to the reduction of NO. There- fore, nitrogen species in the inner part of multilayer structural coke contributes more to NOx formation. Based on the multilayer structure model of coke molecule and its oxidation behavior, a possible strategy to control NOx emission was discussed merely from concept.展开更多
The need for more active and hydrothermally stable fluid catalytic cracking（FCC）catalysts to combat the effect of metal contaminants has led to an increase in demand for rare earth oxides.Rare earth oxides enhance c...The need for more active and hydrothermally stable fluid catalytic cracking（FCC）catalysts to combat the effect of metal contaminants has led to an increase in demand for rare earth oxides.Rare earth oxides enhance catalyst activity and prevent the loss of acid sites during the FCC unit operation,especially when heavy residue with high metal content is used as feed.In this paper,a review was carried out to show the effects of rare earth elements on the structure,activity,and stability of FCC catalysts.Also,the use of rare earth elements as vanadium traps was analyzed in conjunction with the mechanism of catalyst deactivation by vanadium.The objective was to elucidate the interaction of vanadium species with the zeolite component of the FCC catalysts and the role of rare earth elements in countering the deleterious effects of vanadium on the FCC catalysts.展开更多
The commercial application of a novel RFCC catalyst HSC used in an 1.4 Mt/a RFCC unit at a refinery A was introduced. The application results show that in comparison with the base catalyst, the yield of dry gas and sl...The commercial application of a novel RFCC catalyst HSC used in an 1.4 Mt/a RFCC unit at a refinery A was introduced. The application results show that in comparison with the base catalyst, the yield of dry gas and slurry was reduced, while the total liquid yield, gasoline yield and LPG yield increased by 1.34, 5.05 and 1.43 percentage points,respectively. The properties of the products showed no significant change while the anti-abrasion strength of the catalyst was relatively high. Based on the mid-term calibration test, the summary calibration test and the daily statistics of long term industrial application practice, the HSC catalyst features a strong conversion ability of heavy oil, a high gasoline yield, a satisfactory product distribution and a good selectivity.展开更多
A series of MCM 41 molecular sieves have been prepared on an industrial scale, and the effect of preparation factors such as aging temperature, pH values on the structure and pore distribution of the MCM 41 product ...A series of MCM 41 molecular sieves have been prepared on an industrial scale, and the effect of preparation factors such as aging temperature, pH values on the structure and pore distribution of the MCM 41 product have been studied by using X ray diffraction(XRD), thermogravimetric(TG) and electron microscopy(TEM). It is shown that the pH values have a significant effect on the crystallinity of the synthesized product. Under proper conditions, the MCM 41 prepared on an industrial scale has the same performance as the samples prepared on an Lab scale. The prepared MCM 41 was used as a modifier of zeolite Y for fluid catalytic cracking(FCC) of residual oil. It is shown that the addition of the MCM 41 in the zeolite Y catalyst increases the pore size, and surface area of the catalysts, which helps to increase the yield of gasoline and diesel and decrease the production of gaseous product and carbon deposition in the catalyst. The better performance of the MCM 41 modified zeolite Y catalyst is believed to be due to its adjustment on the acidity and increase of the pore size.展开更多
Fluid catalytic cracking(FCC)is still a key process in the modern refining industry,in which nickel contamination of the FCC catalyst can significantly increase the dry gas and coke yields and thus seriously affect th...Fluid catalytic cracking(FCC)is still a key process in the modern refining industry,in which nickel contamination of the FCC catalyst can significantly increase the dry gas and coke yields and thus seriously affect the stability of the FCC unit.Therefore,in this work,B_(2)O_(3)-modified SBA-15 molecular sieves(B_(2)O_(3)/SBA-15)with different B_(2)O_(3) contents were prepared,characterized,and further used as matrix component in the preparation of Ni-tolerant FCC catalyst.The characterization results indicated that the B_(2)O_(3)/SBA-15 samples possessed excellent Ni passivation ability and kept the characteristic structure of the parent SBA-15 such as highly ordered mesopores,large surface area,and high pore volume,which enabled the B_(2)O_(3)/SBA-15 sample to greatly improve the Ni tolerance of the prepared FCC catalyst.The heavy oil catalytic cracking tests indicated that,under the same Ni contamination conditions,the dry gas,coke,and heavy oil yields of the FCC catalyst containing B_(2)O_(3)/SBA-15 decreased by 0.92%,1.65%,and 1.26%,respectively,compared with those of conventional FCC catalyst,while the total liquid yield increased by 3.83%.展开更多
The evaluation testing of propylene promoter LCC-A was carried out in a bench scale fixed fluidized bed reactor and a pilot scale riser. The commercial application experiments on this promoter were conducted in the #3...The evaluation testing of propylene promoter LCC-A was carried out in a bench scale fixed fluidized bed reactor and a pilot scale riser. The commercial application experiments on this promoter were conducted in the #3 RFCCU at Dalian Petrochemical Co. and #1 integrated refining unit at Shanghai Petro- chemical Co. The test results have shown that after adding 5%—6% of the promoter LCC-A to the main FCC catalyst the propylene yield and selectivity were raised obviously. The octane rating of FCC gasoline was increased by more than one unit; which could alleviate the negative impact of octane number decline resulted from reduction of olefin content in FCC naphtha along with an increased propylene yield to meet the urgent market demand for propylene. The test results achieved at Shanghai Petrochemical Company have revealed that when the addition of the LCC-A promoter reached 5% of the catalyst inventory, its performance could be on a par with that of the overseas promoter OlefinsMax.展开更多
The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the...The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon （C1-C4） as the minor product while little heavy oil was produced. The chemical compositions of the product were： aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were： n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point （〈 -10 ℃）, while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount （- 30 wt%） of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.展开更多
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.
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.
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Project supported by the Rare-earth Adjustment Upgrade Projects of Ministry of Industry and Information Technology of ChinaBeijing Nova Program(Z161100004916108)
文摘This paper investigated the recovery of rare earth elements(REEs)and aluminum(AI)from the waste slag discharged by FCC catalyst factory(FCC waste slag)via acid leaching and selective precipitation.Analysis methods such as ICP-AES,XRF and XRD were applied to obtain experiment data.The maximum leaching efficiency of REEs and Al was achieved at pH value of 1 and with liquid to solid ratio of 4:1,Under such conditions,91.01%,92.24%and 94.77%of La,Ce and Al were extracted at 20℃for 2 h from the FCC waste slag,respectively.The SiOcontent in the leaching residue was 88.3%,which can be used as an available silicon resource.The REEs can be precipitated in the form of REEs and sodium double sulfate(NaRE(SO)·xHO)by adding NaSOto the leaching solution,while Al remained in the solution.Afterwards,the pH value of the filtrate was adjusted to 4.5,and Al was precipitated as AI(OH).Finally,NaRE(SO)·xHO and Al(OH)were converted into RECland Al(SO4)solution,respectively,which were recycled to manufacture zeolite.This process recovered REEs and Al from the FCC waste slag and reduced the emissions of waste slag simultaneously,which has an important economic and environment significance.
基金the funding provided by the Fujian Provincial Education Department Project(JA09054)the Project administered by the Fujian Normal University(XG-004)+4 种基金the Fujian Provincial Eco- nomic and Trade Commission Project(HE0536)the Open Project of the MOE's Key Laboratory for Medical and Photoelectrical Science and Technology(JYG0821)the Open Project of Hubei Province,the State Nationalities Committee,and the MOE Joint Key Laboratory for Catalytic Material Science(CHCL08008)the Fujian Provincial Testing Fund Project for the Key Laboratory of Highmolecular Materials(FJKL-POLY2010-17)the Training for Excellence Youth Skeleton Teacher of Fujian Normal University(No.2008100228).
文摘The chemical composition, structure and thermal stability of the spent FCC equilibrium catalyst from an oil refinery were characterized by XRD, FT-IR, DTA-TG, BET, complete chemical analysis, SEM, and XRF. The spent FCC equilibrium catalyst, clay, barium carbonate, and talc were used as the main raw materials to prepare the alumina abrasion-resistant ceramic balls to be used in the powder grinding mill for manufacture of architecture tiles. The results showed that after proper formulation study, the spent FCC equilibrium catalyst could replace industrial alumina to prepare high performance grinding balls. Meanwhile, the various performance indices of the grinding ball could meet the quality standard for similar products, and additionally, the energy saving effect was achieved in the operation of the grinding section, resulting in a successful comprehensive utilization of solid wastes.
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.
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).
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.
基金the financial support of the China National High Technology Research and DevelopmentProgram(863 Program)(Grant no.2011AA060802)the National Natural Science Foundation of China(Grant no.21176250)
文摘A handy gamma-ray transmission method for estimating the particle concentration distribution in a fluid catalytic cracking （FCC） riser is proposed. The method is based on an empirical correlation ε（r）= ε-（0.191＋φ25＋3φ11）, which has only one unknown parameter y, hence only one single-beam experimental result is enough to estimate the particle concentration distribution in the riser. In order to verify the feasibility of this method, the particle concentrations of three cross-sections of the laboratory riser were measured and the distribution profiles were compared with those reported in the literature. Furthermore, by comparing other gamma-ray function methods applied in the measurement of risers, this method has distinct advantages, such as the device is simple and has no moving parts, the measurement is rapid, and the safety is high because only one gamma-ray beam is used. Therefore, the method has promising applications in estimating particle concentrations or monitoring operation conditions of risers.
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.
基金Supported by the National Natural Science Foundation of China(21476263)the National Natural Science Foundation for Young Scholars(21206198)
文摘Nitrogen oxides （NOx） emission during the regeneration ofcoked fluid catalytic cracking （FCC） catalysts is an en- vironmental issue. In order to identify the correlations between nitrogen species in coke and different nitrogen- containing products in tail gas, three coked catalysts with multilayer structural coke molecules were prepared in a fixed bed with model compounds （o-xylene and quinoline） at first. A series of characterization methods were used to analyze coke, including elemental analysis, FT-IR, XPS, and TG-MS. XPS characterization indicates all coked catalysts present two types of nitrogen species and the type with a higher binding energy is related with the inner part nitrogen atoms interacting with acid sites. Due to the stronger adsorption ability on acid sites for basic nitrogen compounds, the multilayer structural coke has unbalanced distribution of carbon and ni- trogen atoms between the inner part and the outer edge, which strongly affects gas product formation. At the early stage of regeneration, oxidation starts from the outer edge and the product NO can be reduced to N2 in high CO concentration. At the later stage, the inner part rich in nitrogen begins to be exposed to 02. At this period, the formation of CO decreases due to lack of carbon atoms, which is not beneficial to the reduction of NO. There- fore, nitrogen species in the inner part of multilayer structural coke contributes more to NOx formation. Based on the multilayer structure model of coke molecule and its oxidation behavior, a possible strategy to control NOx emission was discussed merely from concept.
基金Program supported by Chemicals R&D Division,Saudi Aramco
文摘The need for more active and hydrothermally stable fluid catalytic cracking（FCC）catalysts to combat the effect of metal contaminants has led to an increase in demand for rare earth oxides.Rare earth oxides enhance catalyst activity and prevent the loss of acid sites during the FCC unit operation,especially when heavy residue with high metal content is used as feed.In this paper,a review was carried out to show the effects of rare earth elements on the structure,activity,and stability of FCC catalysts.Also,the use of rare earth elements as vanadium traps was analyzed in conjunction with the mechanism of catalyst deactivation by vanadium.The objective was to elucidate the interaction of vanadium species with the zeolite component of the FCC catalysts and the role of rare earth elements in countering the deleterious effects of vanadium on the FCC catalysts.
文摘The commercial application of a novel RFCC catalyst HSC used in an 1.4 Mt/a RFCC unit at a refinery A was introduced. The application results show that in comparison with the base catalyst, the yield of dry gas and slurry was reduced, while the total liquid yield, gasoline yield and LPG yield increased by 1.34, 5.05 and 1.43 percentage points,respectively. The properties of the products showed no significant change while the anti-abrasion strength of the catalyst was relatively high. Based on the mid-term calibration test, the summary calibration test and the daily statistics of long term industrial application practice, the HSC catalyst features a strong conversion ability of heavy oil, a high gasoline yield, a satisfactory product distribution and a good selectivity.
文摘A series of MCM 41 molecular sieves have been prepared on an industrial scale, and the effect of preparation factors such as aging temperature, pH values on the structure and pore distribution of the MCM 41 product have been studied by using X ray diffraction(XRD), thermogravimetric(TG) and electron microscopy(TEM). It is shown that the pH values have a significant effect on the crystallinity of the synthesized product. Under proper conditions, the MCM 41 prepared on an industrial scale has the same performance as the samples prepared on an Lab scale. The prepared MCM 41 was used as a modifier of zeolite Y for fluid catalytic cracking(FCC) of residual oil. It is shown that the addition of the MCM 41 in the zeolite Y catalyst increases the pore size, and surface area of the catalysts, which helps to increase the yield of gasoline and diesel and decrease the production of gaseous product and carbon deposition in the catalyst. The better performance of the MCM 41 modified zeolite Y catalyst is believed to be due to its adjustment on the acidity and increase of the pore size.
基金National Natural Science Foundation of China(grant number:21902008)Doctor Research Program of Shandong University of Technology(No.4041/420117).
文摘Fluid catalytic cracking(FCC)is still a key process in the modern refining industry,in which nickel contamination of the FCC catalyst can significantly increase the dry gas and coke yields and thus seriously affect the stability of the FCC unit.Therefore,in this work,B_(2)O_(3)-modified SBA-15 molecular sieves(B_(2)O_(3)/SBA-15)with different B_(2)O_(3) contents were prepared,characterized,and further used as matrix component in the preparation of Ni-tolerant FCC catalyst.The characterization results indicated that the B_(2)O_(3)/SBA-15 samples possessed excellent Ni passivation ability and kept the characteristic structure of the parent SBA-15 such as highly ordered mesopores,large surface area,and high pore volume,which enabled the B_(2)O_(3)/SBA-15 sample to greatly improve the Ni tolerance of the prepared FCC catalyst.The heavy oil catalytic cracking tests indicated that,under the same Ni contamination conditions,the dry gas,coke,and heavy oil yields of the FCC catalyst containing B_(2)O_(3)/SBA-15 decreased by 0.92%,1.65%,and 1.26%,respectively,compared with those of conventional FCC catalyst,while the total liquid yield increased by 3.83%.
文摘The evaluation testing of propylene promoter LCC-A was carried out in a bench scale fixed fluidized bed reactor and a pilot scale riser. The commercial application experiments on this promoter were conducted in the #3 RFCCU at Dalian Petrochemical Co. and #1 integrated refining unit at Shanghai Petro- chemical Co. The test results have shown that after adding 5%—6% of the promoter LCC-A to the main FCC catalyst the propylene yield and selectivity were raised obviously. The octane rating of FCC gasoline was increased by more than one unit; which could alleviate the negative impact of octane number decline resulted from reduction of olefin content in FCC naphtha along with an increased propylene yield to meet the urgent market demand for propylene. The test results achieved at Shanghai Petrochemical Company have revealed that when the addition of the LCC-A promoter reached 5% of the catalyst inventory, its performance could be on a par with that of the overseas promoter OlefinsMax.
文摘The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon （C1-C4） as the minor product while little heavy oil was produced. The chemical compositions of the product were： aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were： n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point （〈 -10 ℃）, while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount （- 30 wt%） of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.
