Hydrodynamics of the Stripper Section of Fluid Cokers

The hydrodynamics of fluid bed cokers were studied by analyzing pressure fluctuations and particle motion in a half‐column cold model, geometrically and dynamically similar (with key dimensionless groups matched) to the stripper section of two commercial fluid cokers. Superficial gas velocity and solids circulation strongly affected the hydrodynamics. The pressure drop over the top section of the stripper decreased at high solids circulation fluxes and high gas velocities due to flooding. Flooding occurred prematurely when fouling was simulated. Steam redistribution did not improve stripper performance for the conditions investigated. However, steep sheds on the top row, aeration behind the solids exit and standpipe aeration all improved solids circulation, leading to reduced fouling in two commercial fluid cokers.     

催化裂化油浆综合利用浅析

介绍了催化裂化油浆的性质和组成特点,油浆中脱除催化剂颗粒的常用分离技术与现状,对催化裂化油浆作为道路沥青改性剂、丙烷脱沥青强化剂、渣油强化蒸馏添加剂、橡胶软化剂和填充油、芳烃增塑剂、碳素纤维材料、针状焦、炭黑和导热油等进行综合利用及其研究进展进行了综述。     

Effect of Feedstocks on High‐Severity Fluid Catalytic Cracking

A novel fluid catalytic cracking (FCC) process, that utilizes a downer reactor, has been developed to enhance the yield of light olefins under high‐severity reaction conditions. The effect of heavier feedstock on this high‐severity fluid catalytic cracking (HS‐FCC) process has been investigated using a small‐scale HS‐FCC pilot plant (0.1 b/d). Hydrotreated and virgin vacuum gas oils (VGO), hydrotreated and virgin atmospheric residues (AR) were used as test‐feeds in a previous study. The yield of desired products, such as gasoline and light olefins, produced from virgin VGO cracking was 79 wt.‐%, which is much higher than that obtained from a conventional FCC process. In the case of hydrotreated VGO, the yield of desired products decreased to 76%, however. On the other hand, AR feeds exhibited a performance similar to VGO with a slight increase in coke formation. In this study microactivity test (MAT) results are reported in which the activity and selectivity of the Y‐zeolite based catalyst is evaluated. Kinetic modeling was also done based on a four‐lump reaction model.     

A Novel Strategy for Simulating the Main Fractionator of Delayed Cokers by Separating the De-superheating Process

Delayed coking is an important process in refinery to convert heavy residue oils from crude distillation units (CDUs) and fluid catalytic cracking units (FCCUs) into dry gas, liquefied petroleum gas (LPG), gasoline, diesel, gas oils and cokes. The main fractionator, separating superheating reaction vapors from the coke drums into lighter oil products, involves a de-superheating section and a rectifying section, and couldn't be simulated as a whole column directly because of non-equilibrium in the de-superheating section. It is very important to correctly simulate the main fractionator for operational parameter and energy-use optimization of delayed cokers. This paper discusses the principle of de-superheating processes, and then proposes a new simulation strategy. Some key issues such as composition prediction of the reaction vapors, selection of thermodynamic methods, estimation of tray efficiency, etc. are discussed. The proposed simulation approach is applied to two industrial delayed cokers with typical technological processes in a Chinese refinery by using PRO/II. The simulation results obtained are well consistent with the actual operation data, which indicates that the presented approach is suitable to simulate the main fractionators of delayed cokers or other distillation columns consisting of de-superheating sections and rectifying sections.     

Fluid catalytic cracking feed hydrotreatment and its severity impact on product yields and quality

This paper investigates the effect of fluid catalytic cracking (FCC) feed hydrotreatment and its severity increase on product yields and quality obtained in a commercial and a laboratory MAT FCC units. The hydrotreatment of Ural heavy vacuum gas oil reduces not only sulfur, nitrogen, Conradson carbon and metals content in the FCC feed but also increases the mononuclear aromatic hydrocarbons content by 8% absolute at almost no change in the total aromatics content. Regardless of this 8% increase of the mononuclear aromatics in the hydrotreated FCC feed the conversion increase in both commercial and laboratory MAT units was only 2%. The severity increase in the FCC feed hydrotreater leads to a higher conversion in the FCC, higher hydrogen transfer rate that results in higher isobutane/butylenes ratio, lower gasoline olefins content, and higher gasoline motor octane number. The hydrotreatment of the Ural heavy vacuum gas oil exhibited the same changes in FCC catalyst selectivities: lower coke and LCO selectivities and higher gasoline selectivity in both commercial riser FCC unit that has between 2 and 3 s time on stream, and the fixed bed reactor MAT unit, that has 30 s time on stream.     

流化床提升管中脱油油砂颗粒固含率的轴向分布

针对油砂直接流化焦化工艺,建立了一套大型冷模提升管循环流化床装置. 粒度测试结果表明,该脱油油砂颗粒属宽筛分混合颗粒,且细颗粒含量较多,粒度分布宽(1~>2000 mm). 在不同操作条件下,采用多点压力密度测量仪测定了提升管内压力梯度和截面平均固含率沿提升管轴向的分布. 实验结果表明,脱油油砂颗粒在提升管内截面的平均固含率随表观气速增大而减小,随颗粒循环强度增大而增大;固含率沿提升管轴向的分布为C型,即上下两端较浓、中间较稀,且沿提升管自上而下分为3个区域：颗粒约束返混区(>12 m)、充分发展区(4~12 m)和颗粒加速区(<4 m);在相同操作条件下,脱油油砂颗粒在提升管内截面的平均固含率高于FCC颗粒,加速段与约束返混段长度大于FCC颗粒;确定了脱油油砂颗粒在提升管内截面平均固含率的影响参数为ep', Fr及Hr/Dr;通过实验数据回归得到提升管内截面平均固含率轴向分布的经验模型,计算与实验值吻合较好.     

流化催化裂化反应器的技术进展

介绍并讨论了近期开发的流化催化裂化反应器,包括两段串联反应器、双提升管反应器、下行式反应器、多段进料反应器以及新型提升管反应器端口结构技术。以新型反应器为核心技术的各种催化裂化新工艺可以有效地提高催化裂化反应的转化率和选择性,减少非理想产品产率,也可以改善产品质量,生产环境友好的清洁燃料油品。此外新型提升管反应器端口结构还可以抑制设备结焦,延长流化催化裂化(FCC)装置的开工周期。     

Modeling of vaporization and cracking of liquid oil injected in a gas-solid riser

Vaporization and cracking of liquid oil injected in a gas-solid riser (fluid catalytic cracking riser reactor) was computationally studied in this work. Evaporation of a single drop injected in a stream of gas-solid mixture was analyzed first. A model for simulating evaporation of a drop considering heat transfer from the gas phase as well as from the solid particles was developed. The model relates the evaporation rate of droplet with rate of collisions of solid particles, specific heat capacities of solid and liquid, latent heat of vaporization, relative velocity of gas and liquid and temperatures of three phases. The understanding gained from such a model was then extended to simulate evaporation of liquid drops injected in FCC risers. The Eulerian-Lagrangian approach was used to simulate simultaneous evaporation and cracking reactions occurring in FCC riser reactors. A commercial CFD code, FLUENT (of Fluent Inc., USA) was used. Four and ten lump models were used for simulating cracking reactions. Appropriate user defined functions were developed to implement heterogeneous kinetics and heat transfer models in FLUENT. A special algorithm was developed to calculate accumulated coke on catalyst particles. A boiling point range was considered for simulating realistic oil feedstock. The model was first evaluated by comparing predicted results with published industrial data. The simulations were then carried out to understand influence of key design and operating parameters on performance of FCC riser reactors. The parameters studied included; initial oil droplet distribution, catalyst inlet temperature, catalyst to oil ratio and thermal cracking. The approach, model and results presented here would be useful for optimization of FCC operation, cost to benefit analysis of new FCC nozzles and related decision-making.     

流化床-提升管耦合反应器内固含率的轴向分布及流动发展

在耦合流化床反应器大型冷模实验装置上,考察了不同表观气速下FCC颗粒在耦合流化床内截面平均密度的轴向分布. 结果表明,反应器轴向固含率可分为底部流化床区域和上部提升管区域. 前者的密相区平均固含率随表观气速增大而减小;后者的平均固含率随表观气速Ug增大而增大,Ug<0.58 m/s时固含率分布均匀,Ug=0.70~1.04 m/s时提升管出口出现约束返混区(>8.62 m),Ug>1.16 m/s时提升管底部出现密度重整区(3.82~4.57 m)、加速平稳区(4.57~8.62 m)和出口返混区(>8.62 m). 确定了耦合反应器内提升管区域截面平均固含率的影响参数,并利用实验数据回归了平均固含率的轴向分布经验模型,计算值与实验值吻合较好.     

同轴双锥两级气固快速分离器冷态实验研究

下行循环流化床反应器要求气固分离器具有分离效率高、气相停留时间短、压力损失小、设备磨损小等特点。利用气固二相在惯性上的差别,提出了一种新型同轴双锥两级气固快速分离器,并以FCC(F lu id Catalytic Crack ing)为循环物料对该型分离器的分离特性进行了研究。结果表明,同轴双锥两级气固分离器的分离效率在98%以上,气固分离器的压力损失在100 Pa以下,设备磨损小,能够满足下行循环流化床反应器的要求。     

Correlation between feedstock SARA components and FCC product yields

Daqing, Shengli, Liaohe, Gudao, Dagang and Huabei vacuum residua were subjected to deep solvent fractionation by using the supercritical fluid extraction and fractionation, a novel separation technology recently developed by the State Key Laboratory of Heavy Oil Processing. Each residuum was fractionated to produce deasphalted oil (DAO) at four yield levels: 30, 40, 50 and 60 wt%. The saturates, aromatics, resins and asphaltenes (SARA) composition of each DAO sample was determined, indicating that the saturates and aromatic contents of DAO decreases with increased DAO yield.The DAO samples were reacted in a laboratory scale confined fluidized bed, fluid catalytic cracking (FCC) reactor. The results show that most of the gasoline yields originates from the saturate fraction of DAO. The aromatics fraction of DAO contributes to gasoline and diesel yields. Most of the coke yield is from resin fraction of DAO.Generalized empirical correlations were developed for predicting the FCC gasoline, diesel, light oil and coke yields as a function of feedstock SARA composition. These yield correlations can be used to set the upper limit of feedstock resins content for commercial FCC operations. The implications of feedstock properties on FCC products were discussed.     

CFD analysis of hydrodynamic, heat transfer and reaction of three phase riser reactor

Catalytic cracking reaction and vaporization of gas oil droplets have significant effects on the gas solid mixture hydrodynamic and heat transfer phenomena in a fluid catalytic cracking (FCC) riser reactor. A three-dimensional computational fluid dynamic (CFD) model of the reactor has been developed considering three phase hydrodynamics, cracking reactions, heat and mass transfer as well as evaporation of the feed droplets into a gas solid flow. A hybrid Eulerian-Lagrangian method was applied to numerically simulate the vaporization of gas oil droplets and catalytic reactions in the gas-solid fluidized bed. The distributions of volume fraction of each phase, gas and catalyst velocities, gas and particle temperatures as well as gas oil vapor species were computed assuming six lump kinetic reactions in the gas phase. The developed model is capable of predicting coke formation and its effect on catalyst activity reduction. In this research, the catalyst deactivation coefficient was modeled as a function of catalyst particle residence time, in order to investigate the effects of catalyst deactivation on gas oil and gasoline concentrations along the reactor length. The simulation results showed that droplet vaporization and catalytic cracking reactions drastically impact riser hydrodynamics and heat transfer.     

提升管-环流床耦合反应器环流床内的固含率分布

针对催化汽油辅助反应器改质降烯烃技术,在提升管-环流床耦合反应器大型冷模实验装置上,研究了上部环流床内局部固含率分布及操作条件的影响,采用径向不均匀指数分析比较了提升管上端耦合环流床及耦合常规流化床的流化质量. 结果表明,环流床内固含率随表观气速增加而减小,导流筒底部固含率随外循环强度增加而增加,中上部固含率受外循环强度影响较小,环隙内固含率随外循环强度增加略有降低. 当导流筒内表观气速Ug,d<0.85 m/s时,固含率径向分布的均匀性沿轴向向上逐渐变好,当Ug,d≥0.85 m/s时,则沿轴向向上先变好,在导流筒出口处又变差;环隙内固含率分布趋于均匀的程度依次为环隙中部>环隙下部>环隙上部. 相同条件下,环流床内固含率分布的径向不均匀指数小于常规流化床.     

催化裂化油浆固含量测定及组成分析

采用灰分法、过滤法、离心法测量了某重油催化裂化装置外甩油浆的固体颗粒含量,对几种方法在固含量测定方面的结果差异进行对比分析。实验结果表明,离心法测量的固含量约为2850μg/g,介于灰分法和过滤法之间。离心法结果显示,油浆中重组分与细粉颗粒存在较强的吸附作用,分离中能否准确得到焦粉是造成结果差异的主要原因。离心法耦合后续焙烧能够分离获得油浆中一定量的催化剂细粉颗粒,通过激光粒度仪、元素分析仪、XRD、BET、SEM-EDS等手段对分离得到的固体颗粒以及初始FCC催化剂进行了表征。FCC催化剂粒径集中在32～120μm之间,为规则的球形分布,油浆中的固体颗粒呈不规则的块状分布,粒径在0.4～40μm之间,其中催化剂细粉的粒径在1～30μm之间;催化裂化油浆中的固体颗粒组成主要有催化剂细粉、焦粉和碱金属K、Ca、无机盐和金属元素Sb、Fe等。     

提升管反应器进料混合段内气固两相流动特性(Ⅰ)实验研究

根据实际工业的操作条件 ,采用催化裂化催化剂及空气 ,在大型冷模实验装置上对催化裂化提升管进料混合段内射流相与颗粒相的速度场、浓度场进行了系统测试 .结果表明 ,由于旋涡场的诱导作用 ,喷嘴射流注入到提升管中以后将会产生二次流动 ,二次流先是发展扩大 ,随后又与主流逐渐汇合 .根据混合流场的分布特点 ,可以将这一极其复杂的流场由下到上分为上游影响区段、主射流影响区段、二次流影响区段、混合发展区段 4部分 ,各区段在径向上又可再分为 2或 3个区来表征有关参数的分布特点     

Effects of metal modifications of Y zeolites on sulfur reduction performance in fluid catalytic cracking process

The acidity of catalytically active component, e.g., ultra stable Y zeolite (USY), plays an important role in determining their cracking activity and selectivity. To develop advanced sulfur reduction catalytic cracking catalysts, different type of elements were used to modify USY and the resulting catalysts were evaluated in a confined fluidized bed reactor and a micro-activity testing unit. The relation between the acidity of the zeolite and the conversion of sulfur compounds as well as the distributions of fluid catalytic cracking (FCC) products were discussed. The results showed that the rare earth (RE) metal can stabilize the catalyst and increase the conversion, but cannot increase the selectivity to thiophene compounds; V can reduce the sulfur content by 36.3 m%, but decreases the overall conversion compared with the base catalyst. An optimum catalyst was obtained by the combined RE and V modification, over which the sulfur content in FCC gasoline can be decreased and the selectivity for the target products can be improved, with the sulfur content reduced by 30 m% and the selectivity to coke even decreased by 0.20 m% at a comparable conversion level of the base catalyst.     

Effect of spray nozzle design on liquid-solid contact in fluidized beds

In industrial fluid cokers the feedstock, consisting of heavy bituminous hydrocarbons, is atomized with steam and injected into a hot fluidized bed of coke. Good and uniform contact of the liquid droplets with the solid particles is required to provide heat for the cracking reactions while minimizing mass transfer effects. Experiments in a pilot plant coker have suggested that the initial particle/liquid mixing, in the spray jet, is rather poor. Experiments in a X-ray scanner showed that liquid droplets and entrained particles accumulate just below the tip of the jet plume to form agglomerates.An experimental technique was used to quantitatively determine the quality of mixing with a variety of nozzle configurations including several novel designs. By improving spray stability, redistributing liquid droplets to the solids-rich region of the jet and increasing the surface area of the gas-liquid jet-fluidized bed interface, liquid/solid contact is improved.     

Equilibrium catalyst from a fluidized catalytic cracking unit separated by metal content by using carbon nanotubes and a biphasic system

During fluid catalytic cracking (FCC) operations FCC catalyst particles become contaminated with various metals. These metals impact FCC performance and currently requires equilibrium catalyst (ECAT) mixtures consisting of a blend of FCC particles with a time spent in the reactor ranging from minutes to several months to be continuously extracted and sold as low value products or sent to landfills. Here a unique method to recycle FCC ECAT particles is presented, which separates ECAT particles by metal content by synthesizing carbon nanotubes and nanofibers on the ECAT particles surface and using a biphasic system. ECAT with low metal content can be sent back to the FCC unit for further use while ECAT with high metal content can be used for other purposes. Further, we show these treated ECAT materials of high metals content will absorb oil on the surface of water and may prove useful for oil spill clean-up applications.     

下行式循环流化床用于催化裂化过程的数学模拟

采用十一集总动力学,结合气固流体力学行为和轴、径向扩散行为,建立了适合于提升管及下行式循环流化床催化裂化的数学模型,采用此模型对催化裂化过程计算的结果表明,下行床内目的产品选择性显著高于提升管,但在与工业提升管相同的操作条件下,下行床内原料转化率较低,优势不能发挥。适当增加下行床长度、增大床径、使物料循环反应、增加剂油比、提高反应温度或反应压力等可以改善下行床的反应效果。下行床用于催化裂化过程,与之较匹配的应该是具有更高活性的催化剂,研制新型高活性催化剂也是下行床推向工业的重要措施之一。     

Numerical Simulation of a Spouted Bed Using Computational Fluid Dynamics (CFD)

In this article, computational fluid dynamics (CFD) technology is used to model a spouted bed(SB). The multifluid Eulerian-Eulerian approach based on kinetic theory of granular flows and Gidaspow's drag model for the interaction between gas and particles are applied in the modeling. The effects of the SB properties—that is, cone angle, particle size, cylinder diameter, and static bed height of particles—on its dynamics performance are investigated. The simulated results—that is, flow pattern of particles, fountain height, voidage, and particle velocity of the spout zone—are presented. It is shown that periodic fluctuation of spouting appears in an SB with conical angle of 30° and inlet velocity at 16.6 m/s. When the SB cylinder diameter becomes 0.52 m, periodic fluctuation appears, too. The stable spouting of the SB with a 90° cone angle could be obtained at an inlet air velocity of 24.3 m/s. The fountain height of particles decreased with an increase in particle size and the static bed height of particles. It is kept at about 0.19 m when different SB cylinder diameters in the range of 0.36 to 0.48 m are used. In the spouting region, the voidage decreased with static particle height in bed, but the particle velocity increased. For a certain particle size, the voidage decreased with an increase in particle height, but the velocity of the particles increased. It was also found that the cylinder diameter did not affect the volume fraction of particles except for the cylinder diameter 0.52 m and the change in particle velocity was minimal in the spout zone. With the different static bed height of particles used, the voidage and particle velocity did not change much at the same level of spout zone.