Application of New Heavy Metals Resistant Porous Binder Material Used in Fluid Catalytic Cracking Reaction

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.

Fluid Catalytic Cracking Technology for Maximum Gasoline Production

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.

Study of Carbon Nanotube Supported Co-Mo Selective Hydrodesulphurization Catalysts for Fluid Catalytic Cracking Gasoline

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.

Modeling and Optimization of a Fractionation,Absorption,and Stabilization System in an Industrial Fluid Catalytic Cracking Process

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.

Industrial Application and Fundamental Research Progress on Fluid Catalytic Cracking Technology of Downer Reactors

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.

Failure analysis of corrosion cracking and simulated testing for a fluid catalytic cracking unit

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.

Effect of baffles on performance of fluid catalytic cracking riser

Increasing demand of automobile fuel and a need to process heavier crude oil makes it imperative to find improvements to the design of existing fluid catalytic cracking （FCC） units. Several modifications to the design of the riser section of FCC units have been suggested in previous studies including： improved feed nozzle designs, multiple nozzle configurations, internal baffles, and novel two-stage-riser systems. In this study, we investigate the effects of baffles on the performance of FCC risers using computational fluid dynamics simulations. In this study, predictions from a basis model （without baffles） are compared with those from four different configurations including： （i） 5-cm baffles at 5-m spacing, （ii） 7.5-cm baffles at 5- m spacing, （iii） 10-cm baffles with 5-m spacing, （iv） lO-cm baffles at 2.5-m spacing, and （v） lO-cm baffles at 1-m spacing. The baffles force the catalyst away from wails toward the center of the riser, enhancing the radial dispersion of the catalyst and the heat transfer inside the riser. The use of longer baffles and smaller spacings further increases the dispersion, yielding more homogeneous radial profiles. The changes in the radial dispersion result in variations in the conversion, yields, and pressure drops. The baffles increase conversion of vacuum gas oil （VGO） and the yield of gasoline. However, the simulations showed that longer baffles and a larger number of baffles did not always give a higher yield or higher conversion. Among the simulated configurations, the 5-cm baffles at 5-m spacing gave the highest conversion of VGO, whereas the 10-cm baffles at 1 -m spacing resulted in the highest yield of the gasoline. Thus, rational optimization of baffle configurations is required to achieve optimal performance.

Numerical comparison of two modes of gas-solid riser operation： Fluid catalytic cracking vs CFB combustor

Two modes of gas-solid riser operation, i.e., fluid catalytic cracking （FCC） and circulating fluidized bed combustor （CFBC）, have been recognized in literature; particularly in the understanding of choking phenomena. This work compares these two modes of operation through computational fluid dynamics （CFD） simulation. In CFD simulations, the different operations are represented by fixing appropriate boundary conditions： solids flux or solids inventory. It is found that the FCC and CFBC modes generally have the same dependence of solids flux on the mean solids volume fraction or solids inventory. However, during the choking transition, the FCC mode of operation needs more time to reach a steady state; thus the FCC system may have insufficient time to respond to valve adjustments or flow state change, leading to the choking. The difference between FCC and CFBC systems is more pronounced for the systems with longer risers. A more detailed investigation of these two modes of riser operation may require a three-dimensional full loop simulation with dynamic valve adjustment.

CFD SIMULATION OF FLUID CATALYTIC CRACKING IN DOWNER REACTORS

A mathematical model has been developed for the simulation of gas-particle flow and fluid catalytic cracking in downer reactors. The model takes into account both cracking reaction and flow behavior through a four-lump reaction kinetics coupled with two-phase turbulent flow. The prediction results show that the relatively large change of gas velocity affects directly the axial distribution of solids velocity and void fraction, which significantly interact with the chemical reaction. Furthermore, model simulations are carried out to determine the effects of such parameters on product yields, as bed diameter, reaction temperature and the ratio of catalyst to oil, which are helpful for optimizing the yields of desired products. The model equations are coded and solved on CFX4.4.

Study on reformulation of fluid catalytic cracking gasoline and increasing production of light olefins

The effects of reaction temperature,mass ratio of catalystto oil,space velocity,andmass ratio of water to oil on the product distribution,the yields of light olefins(light olefins including ethylene,propylene and butylene)and the composition of the fluid catalytic cracking(FCC)gasoline upgraded over the self-made catalyst GL in a confined fluidized bed reactor were investigated.The experimental results showed that FCC gasoline was obviously reformulated under appropriate reaction con-ditions.The olefins(olefins with C atom number above 4)content of FCC gasoline was markedly reduced,and the aromaticscontent andoctanenumber were increased.The upgraded gasoline met the new standard of gasoline,and meanwhile,higher yields of light olefins were obtained.Furthermore,higher reaction temperature,higher mass ratio of catalyst to oil,higher mass ratio of water to oil,and lower space velocity were found to be beneficial to FCC gasoline reformulation and light olefins production.

Studies on the preliminary cracking: The reasons why matrix catalytic function is indispensable for the catalytic cracking of feed with large molecular size

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.

Mechanistic Insights into the Catalytic Cracking of Cyclohexane

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.

Effects of Temperature and Catalyst to Oil Weight Ratio on the Catalytic Conversion of Heavy Oil to Propylene Using ZSM-5 and USY Catalysts

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.

Effects of the properties of FCCS on the removing of catalyst particles from FCCS under a DC electrostatic field

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℃.

Hydrothermally stable mesoporous aluminosilicates as superior FCC catalyst:From laboratory to refinery

Well-ordered aluminosilicates(MAs)were prepared by in-situ assembly of pre-crystallized units of zeolite Y precursors at a commercial scale,and applied in an industrial fluid catalytic cracking unit for the first time.Compared with incumbent equilibrium catalyst,the surface area of trial equilibrium catalysts(30%inventory ratio)increased from 110 m^(2)g^(-1)to 120m^(2)g^(-1).Moreover,a significant increase of the mesoporous surfaceareaof trial equlibrium catalysts(30%inventoryrati)from 33 m g/to 40magi(22%increase).Furthermore,the equilibrium catalyst that contain 80%LPC-65 yields significantly lower heavy oil(0.23%)and higher total liquids(0.53%)compared with LDO-70.The industrial results demonstrated excellent hydrothermal stability and superior catalytic cracking properties,showing the promising futurein the industrial units.

Post-riser Regeneration Technology in FCC Unit

In our present work, a post-riser regeneration technology （PRRT） for fluid catalytic cracking （FCC） units was developed to deal with increasingly heavier feedstock and hereby the larger amount of coke deposited on the catalyst particles during reaction. This technology can make full use of the advantages of riser regenerator, such as high cokeburning efficiency and low residual carbon, and at the same time overcome its disadvantages, such as difficulty in starting combustion. The average particles concentration on the cross section of the system was studied on a large scale cold model experimental set-up. Also a necessary software was developed by combining the hydrodynamics research results in our work with the coke-burning kinetics model and the heat and mass transfer model developed by previous researchers. The simulation results showed that the PRRT could increase regeneration capability by 16.28%-26.24% over the conventional turbulent fluidized bed regenerator under the similar operation conditions, and that the residual carbon could be kept below 0.1 wt %.

FCC Study of Canadian Heavy Gas Oils—Comparisons of Product Yields and Qualities between Reactors

Several series of cracking tests in a comprehensive study were conducted on separate occasions involving all or parts of ten Canadian vacuum gas oils (VGOs) and two catalysts with bottoms-cracking or octane-barrel capability. VGOs were cracked in fixed- and/or fluid-bed microactivity test (MAT) units, in an Advanced Cracking Evaluation (ACE) unit, and in a modified ARCO riser reactor. Individual yields of gas, liquid, and coke from the MATs at 55, 65, 70, and 81 wt% conversion levels were compared with their respective pilot plant data. Good linear correlations could be established between MAT and riser yields except for liquefied petroleum gas (LPG) and light cycle oil (LCO). At a given conversion, correlations existed among the fixed- and fluid-bed MAT units and the ACE for each product yield. Liquid products from the fixed or fluid-bed MAT were analyzed for hydrocarbon types, sulfur, nitrogen and density, most of which showed good agreement with those obtained from the riser study. When cracking Canadian oil-sands-derived VGOs, the bottoms-cracking catalyst containing a large-pore active matrix was found to be more suitable than the octane-barrel catalyst with smaller pores to produce higher yields of valuable distillates, but with less superior qualities (in terms of sulfur and nitrogen contents). The advantages of hydrotreating some poor feeds to improve product yields and qualities were demonstrated and discussed.

Injection of gas-liquid jets into gas-solid fluidized beds:A review

Injection of gas-liquid sprays into gas-solid fluidized beds finds application in many industries.Effective mixing and distribution of liquid feed and solid bed material is paramount to ensure an efficient and profitable process.Despite its long-term use,the mechanism of liquid injection into gas-solid fluidized beds continues to raise questions and is only partially understood.This paper provides a thorough and up-to-date review of experimental and numerical investigations of gas-liquid sprays into gas-solid fluidized beds conducted over the past decades.Based on the surveyed literature,a phenomenological description of the prevalent mechanisms of gas-liquid injection under different operating conditions is presented.This review identifies suitable computational fluid dynamic models for simulating the mechanisms involved in gas-liquid-solid interactions along with recommendations for future numer-ical and experimental work.

Experimental analysis of volatile liquid injection into a fluidized bed

Experiments were conducted on a lab-scale fluidized bed to study the distribution of liquid ethanol injected into fluidized catalyst particles. Electrical capacitance measurements were used to study the liquid distribution inside the bed, and a new method was developed to determine the liquid content inside fluidized beds of fluid catalytic cracking particles. The results shed light on the complex liquid injection region and reveal the strong effect of superficial gas velocity on liquid distribution inside the fluidized bed, which is also affected by the imbibition of liquid inside particle pores. Particle internal porosity was found to play a major role when the changing mass of liquid in the bed was monitored. The results also showed that the duration of liquid injection affected liquid-solid contact inside the bed and that liouid-solid mixin~ was not homogeneous durin~ the limited liouid injection time.

Fluidization science,its development and future

By revisiting the three stage theory for the progress of science proposed by Taketani in 1942, the footmarks of fluidization research are examined. The bubbling and fast fluidization issues were emphasized so that the future offluidization research can be discussed among scientists and engineers in a wider perspective. The first cycle of fluidization research was started in the early 1940s by an initial stage of phenomenology. The second stage of structural studies was kicked off in the early 1950s with the introduction of the two phase theory. The third stage of essential studies occurred in the early 1960s in the form of bubble hydrodynamics. The second cycle, which confirmed the aforementioned three stages closed at the turn of the century, established a general understanding of suspension structures including agglomerating fluidization, bubbling, turbulent and fast fluidizations and pneumatic transport; also established powerful measurement and numerical simulation tools.After a general remark on science, technology and society issues the interactions between fluidization technology and science are revisited. Our future directions are discussed including the tasks in the third cycle, particularly in its phenomenology stage where strong motivation and intention are always necessary, in relation also to the green reforming of the present technology. A generalized definition of ＇fluidization＇ is proposed to extend fluidization principle into much wider scientific fields, which would be effective also for wider collaborations.