Fluid Catalytic Cracking Particles Research Articles

Numerical investigation of turbulent mass transfer processes in turbulent fluidized bed by computational mass transfer

Turbulent fluidized bed possesses a distinct advantage over bubbling fluidized bed in high solids contact efficiency and thus exerts great potential in applications to many industrial processes. Simulation for fluidization of fluid catalytic cracking (FCC) particles and the catalytic reaction of ozone decomposition in turbulent fluidized bed is conducted using the Eulerian–Eulerian approach, where the recently developed two-equation turbulent (TET) model is introduced to describe the turbulent mass diffusion. The energy minimization multi-scale (EMMS) drag model and the kinetic theory of granular flow (KTGF) are adopted to describe gas–particles interaction and particle–particle interaction respectively. The TET model features the rigorous closure for the turbulent mass transfer equations and thus enables more reliable simulation. With this model, distributions of ozone concentration and gas–particles two-phase velocity as well as volume fraction are obtained and compared against experimental data. The average absolute relative deviation for the simulated ozone concentration is 9.67% which confirms the validity of the proposed model. Moreover, it is found that the transition velocity from bubbling fluidization to turbulent fluidization for FCC particles is about 0.5 m·s–1 which is consistent with experimental observation.

Multiscale investigation of pore network heterogeneity and permeability of fluid catalytic cracking (FCC) particles

Pore network is regarded as one of the most important aspects of FCC (Fluid Catalytic Cracking) catalysts for delivering reactants to active sites and transporting out products, and the structure of which can significantly influence the process efficiency. In this work, six characterization methods complementing each other were employed to study the full-scale pore structure (0.4 nm − 20 µm) of fresh FCC particles, especially the X-ray computed tomography (CT) and focused ion beam-scanning electron microscope (FIB-SEM). To focus on nano-scale pores, 3D reconstruction of a whole FCC particle was achieved based on nano-CT, from which the pore network model (PNM) was successfully extracted. Then, permeability simulations along different directions and through various sub-volumes were carried out to demonstrate the anisotropy and heterogeneity of pore structure, respectively. It was also found that the tortuosity of the pores distributed in the outer layer of the FCC particle was more significant than that in the central part of the particle, which could be the mass transfer limiting region during catalysis. Comprehensive acknowledgment of pore structure provides guidance for the optimization of the design of FCC particles, and the multi-scale characterization strategy is a generic strategy for in-depth investigation of structured porous materials.

DPM Simulations of A-Type FCC Particles’ Fast Fluidization by Use of Structure-Dependent Nonlinear Drag Force

Nonlinear drag force has been a research frontier in complex gas-solid systems. The literature has reported that the commonly-used drag correlations often overestimate drag force and, thus, cause unrealistic homogeneous flow structures in gas-solid fluidized beds of fine particles. For solving this problem, the structure-dependent drag model, derived from energy-minimization multi-scale approach, is used in discrete simulations of fluid catalytic cracking particles in a small riser. The gas phase is dealt with by computational fluid dynamics. Particles are considered as a discrete phase and described by Newton’s second law of motion. Gas-particle phases are coupled according to Newton’s third law of motion. Simulations show that use of structure-dependent drag model results in drag reduction, the effect of which is not so apparent as that in simulations of the two fluid model. The particle clustering tendency, however, is more distinct and leads to more heterogeneous flow structures in riser flow with a much greater amplitude of outlet solid flux fluctuations. Moreover, the behaviors of particle and gas back-mixing can be captured in the present simulations, which was supported by past simulations and experimental data. The simulation time resolution is discussed. The spring constant can be artificially brought down for safe setting of larger time step when modelling the collision process between fine particles with a higher calculation load. To appropriately mimic the continuous decay of van der Waals force may, however, need a much smaller time step. There is also an obvious effect of space resolution on simulations. When using a grid size smaller than 3 times the particle diameter, the simulated clusters turn extraordinarily large, and the effect of gas-solid back-mixing turns insignificant.

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

AbstractDuring 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.

Flow of High Solids Density Suspensions in an 18 m High Circulating Fluidized Bed

The detailed distributions of solids holdup in an 18 m high-density circulating fluidized bed are mapped under various operating conditions with fluid catalytic cracking particles. Solids flux (Gs)...

Fine structural changes of fluid catalytic catalysts and characterization of coke formed resulting from heavy oil devolatilization

Coke formation from heavy oil cracking and the associated change in the porous structure of fluid catalytic cracking (FCC) catalysts has been studied using a comprehensive range of techniques, including 2D and 3D imaging and carbon/coke characterization techniques. The carbon/coke formed from heavy oil devolatilization has been investigated with a range of oil-to-FCC catalyst ratios (1:3, 1:2, 1:1, 2:1 and 3:1) to simulate the ageing of FCC catalysts in an operating oil refinery. Carbon/coke was formed on all used FCC catalyst samples and was found to generally increase in quantity with the increasing oil-to-FCC catalyst ratios. Coke formation has been correlated with the observed porosity change of the FCC catalyst. Higher quantities of carbon/coke formed on the FCC catalyst due to higher oil-to-FCC catalyst ratios (simulated increase in time on-stream) leads to a decrease of total pore volume and surface area. X-Ray computed tomography (X-Ray CT) studies allowed 3-dimensional imaging of used catalyst particles and showed that the zeolite component of the FCC catalyst remains evenly distributed throughout the FCC particle from the centre to the exterior for pristine and used FCC catalyst particles. This technique showed that while the interior porous structure of the FCC catalyst particle is not affected by the coking, the exterior porous structure is substantially modified for all used FCC catalyst samples. This process of pore collapse and/or clogging at the surface of the particles is likely to have a significant effect on the deactivation of FCC catalysts that is commonly observed. The deeper insight into this process gained through this study is important for understanding how FCC catalysts change with time-on-stream and eventually deactivate and may allow for future catalysts to be developed that are more resistant to deactivation.

Wavelet denoising and nonlinear analysis of solids concentration signal in circulating fluidized bed riser

Particles, particle aggregates, and reactor walls complicate the dynamic microstructures of circulating fluidized beds (CFBs). Using local solids concentration data from a 10-m-high and 76.2-mm-inner-diameter riser with FCC (Fluid Catalytic Cracking) particles (dp=67μm, ρp=1500kg/m3), this paper presents an improved denoising process for use before nonlinear chaos analysis. Using the soft-threshold denoising method in the wavelet domain with experimental empty bed signals as base data to estimate the denoising threshold, an efficient denoising algorithm was proposed and used for the dynamic signals in CFBs. Analysis shows that for the local solids concentration time series, high-frequency fluctuations may be one of the system properties, while noise interference can also make a low-frequency contribution. An exact denoising method is needed in such cases. The correlation dimension and Kolmogorov entropy were calculated using denoised data and the results showed that the particle behavior in the CFB is highly complex. Generally, two correlation dimensions coexist in a low-flux CFB. The first correlation dimension is low and corresponds to small-scale fluctuations that reveal a high-frequency pseudo-periodic movement, but the second correlation dimension is high and corresponds to large-scale fluctuations that indicate multi-frequency movements, including particle aggregation and breakage. At the same axial level, the first correlation dimensions change slightly with radial position, and the main tendency is high at the center but slightly lower near the wall. However, the second correlation dimensions show large changes along the radial direction, are again high in the core region, and after r/R≥0.6 (r as radial position, R as radius of the riser), the dimensions clearly drop down. This indicates that the particle behavior is more complex and has higher degrees of freedom at the center, but clusters near the wall are restrained to some degree because of wall effects.

Fluidity enhancement of hard-to-fluidize nanoparticles by mixing with hydrophilic nanosilica and fluid catalytic cracking particles: Experimental and theoretical study

As a low-cost method, hydrophilic SiO2 nanoparticles (NPs) and fluid catalytic cracking (FCC) coarse particles were used as assistant materials to improve the fluidity of Al2O3 and TiO2 hard-to-fluidize nanopowders. To decrease the strong electrostatic forces between the hydrophilic nanopowders, prepared samples were fluidized in the presence of methanol vapor. Results revealed that the amount of SiO2 NPs, increased from 5 to 50 wt. %, has a beneficial effect on the fluidization quality of the binary (hard-to-fluidize NPs + SiO2) and ternary (hard-to-fluidize NPs + SiO2 + FCC) mixtures. However, the amount of FCC particles when it varied from 15 to 30 wt. % in the ternary mixtures should meet the optimal point, beyond which the fluidization quality was declined due to the segregation phenomenon. The laboratory results showed that the cost-effective ternary samples fluidized more homogeneously with higher bed expansions compared to the binary samples. In this regard, (Al2O3 + 20 wt. % SiO2) + 15 wt. % FCC and (TiO2 + 20 wt. % SiO2) + 15 wt. % FCC ternary samples were proposed as the alternatives of Al2O3 + 50 wt. % SiO2 and TiO2 + 50 wt. % SiO2 binary mixtures, respectively.

Iron contamination of FCC catalysts: Quantification of different crystalline phases and valence states

Amongst the contaminant transition metals that deposit onto the fluid catalytic cracking (FCC) catalyst, iron is well-known for its accumulation on the outer surface, negatively affecting accessibility of reactants to the interior of the porous particles and even causing fluidization problems in the circulating unit. Earlier studies have been dedicated to understand the complex deposition mechanism of iron in FCC particles, but only a few was devoted to determine the crystalline phases and the valence states of the deposited Fe during its operation under alternate redox conditions. Besides, the co-existing structural iron in the manufactured catalyst (fresh) makes such studies even more challenging. To better elucidate this field, we present in this paper a combined investigation using X-ray fluorescence (XRF), electron paramagnetic resonance (EPR) and Mössbauer spectroscopy (MS) in fresh, artificially metalized samples and deactivated catalysts collected from the industrial FCC process (E-cat). Using as subsidiary information the characterization of fresh and laboratory impregnated samples submitted to different redox environments at 750 °C, the investigation of E-cats from two refineries working in partial and full burn regeneration mode allowed us to conclude that contaminant iron is mostly deposited as maghemite (γ-Fe2O3) with spinel structure in both its forms: the ferrimagnetic and the superparamagnetic phase, this latter associated to nanosized crystals. The structural Fe(III) in meta-kaolinite from the original catalyst is mostly transformed to Fe(II), indicating that in real FCC unit the regeneration conditions are not severe enough to fully oxidize the Fe species formed in the reductive conditions of the FCC cracking step. Moreover, evidences suggested that the ferrimagnetic form of maghemite is preferentially formed in the reaction zone and it is more or less converted in the regenerator into the superparamagnetic species, more resistant to the oxidizing condition.

Nanoscale Chemical Imaging of a Single Catalyst Particle with Tip-Enhanced Fluorescence Microscopy.

Determining the active site in real‐life solid catalysts remains an intellectual challenge and is crucial for exploring the road towards their rational design. In recent years various micro‐spectroscopic methods have revealed valuable structure‐activity data at the level of a single catalyst particle, even under reaction conditions. Herein, we introduce Tip‐Enhanced FLuorescence (TEFL) microscopy as a novel and versatile characterization tool for catalysis research. This has been achieved using a Fluid Catalytic Cracking (FCC) catalyst as showcase material. Thin sectioning of industrially used FCC particles together with selective staining of Brønsted acidity has enabled high‐resolution TEFL mapping of different catalyst regions. Hyperspectral information gained via TEFL microscopy reveals a spatial distribution of Brønsted acidity within individual zeolite domains in different regions of the FCC catalyst particle. Comparison of TEFL measurements from different FCC particles showed significant intra‐ and inter‐particle heterogeneities both in zeolite domain size and chemical reactivity.

Magnetophoretic Sorting of Single Catalyst Particles.

A better understanding of the deactivation processes taking place within solid catalysts is vital to design better ones. However, since inter-particle heterogeneities are more a rule than an exception, particle sorting is crucial to analyse single catalyst particles in detail. Microfluidics offers new possibilities to sort catalysts at the single particle level. Herein, we report a first-of-its-kind 3D printed magnetophoretic chip able to sort catalyst particles by their magnetic moment. Fluid catalytic cracking (FCC) particles were separated based on their Fe content. Magnetophoretic sorting shows that large Fe aggregates exist within 20 % of the FCC particles with the highest Fe content. The availability of Brønsted acid sites decreases with increasing Fe content. This work paves the way towards a high-throughput catalyst diagnostics platform to determine why specific catalyst particles perform better than others.

Magnetophoretic Sorting of Single Catalyst Particles

AbstractA better understanding of the deactivation processes taking place within solid catalysts is vital to design better ones. However, since inter‐particle heterogeneities are more a rule than an exception, particle sorting is crucial to analyse single catalyst particles in detail. Microfluidics offers new possibilities to sort catalysts at the single particle level. Herein, we report a first‐of‐its‐kind 3D printed magnetophoretic chip able to sort catalyst particles by their magnetic moment. Fluid catalytic cracking (FCC) particles were separated based on their Fe content. Magnetophoretic sorting shows that large Fe aggregates exist within 20 % of the FCC particles with the highest Fe content. The availability of Brønsted acid sites decreases with increasing Fe content. This work paves the way towards a high‐throughput catalyst diagnostics platform to determine why specific catalyst particles perform better than others.

Numerical Investigation of the Ability of Salt Tracers to Represent the Residence Time Distribution of Fluidized Catalytic Cracking Particles

For a long time, salt tracers have been used to measure the residence time distribution (RTD) of fluidized catalytic cracking (FCC) particles. However, due to limitations in experimental measurements and simulation methods, the ability of salt tracers to faithfully represent RTDs has never been directly investigated. Our current simulation results using coarse-grained computational fluid dynamic coupled with discrete element method (CFD-DEM) with filtered drag models show that the residence time of salt tracers with the same terminal velocity as FCC particles is slightly larger than that of FCC particles. This research also demonstrates the ability of filtered drag models to predict the correct RTD curve for FCC particles while the homogeneous drag model may only be used in the dilute riser flow of Geldart type B particles. Thus, the RTD of large-scale reactors can be efficiently investigated with our proposed numerical method as well as by using the old-fashioned salt tracer technology.

Single-Molecule Fluorescence Microscopy Reveals Local Diffusion Coefficients in the Pore Network of an Individual Catalyst Particle.

We used single-molecule fluorescence microscopy to study self-diffusion of a feedstock-like probe molecule with nanometer accuracy in the macropores of a micrometer-sized, real-life fluid catalytic cracking (FCC) particle. Movies of single fluorescent molecules allowed their movement through the pore network to be reconstructed. The observed tracks were classified into three different states by machine learning and all found to be distributed homogeneously over the particle. Most probe molecules (88%) were immobile, with the molecule most likely being physisorbed or trapped; the remainder was either mobile (8%), with the molecule moving inside the macropores, or showed hybrid behavior (4%). Mobile tracks had an average diffusion coefficient of D = 8 × 10–14 ± 1 × 10–13 m2 s–1, with the standard deviation thought to be related to the large range of pore sizes found in FCC particles. The developed methodology can be used to evaluate, quantify and map heterogeneities in diffusional properties within complex hierarchically porous materials.

Experimental Investigation on Gas‐Solid Behavior in Fluidized Beds with Superfine Particles

AbstractFluidized beds are commercially utilized in gas‐solid contacting processes such as the fluid catalytic cracking (FCC) process. Attempts have been made for bubbling fluidized beds to enhance the gas exchange between the bubble phase and the emulsion phase as well as to increase bubble holdup. Low‐density superfine particles 5070S were selected with average diameters of about 10 μm. Unlike agglomerate particulate fluidization of superfine particles on which other researchers have reported, the smaller bubbles, whose diameter is less than 10 mm, uniformly dispersed in the whole bed. Additionally, the gas exchange rate with 5070S became larger than with the FCC particles. Such a unique gas‐solid behavior is probably due to the proper density difference between particle aggregate and fluidizing gas.

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 liquid–solid mixing was not homogeneous during the limited liquid injection time.

FIB-SEM Tomography Probes the Mesoscale Pore Space of an Individual Catalytic Cracking Particle.

The overall performance of a catalyst particle strongly depends on the ability of mass transport through its pore space. Characterizing the three-dimensional structure of the macro- and mesopore space of a catalyst particle and establishing a correlation with transport efficiency is an essential step toward designing highly effective catalyst particles. In this work, a generally applicable workflow is presented to characterize the transport efficiency of individual catalyst particles. The developed workflow involves a multiscale characterization approach making use of a focused ion beam-scanning electron microscope (FIB-SEM). SEM imaging is performed on cross sections of 10.000 μm2, visualizing a set of catalyst particles, while FIB-SEM tomography visualized the pore space of a large number of 8 μm3 cubes (subvolumes) of individual catalyst particles. Geometrical parameters (porosity, pore connectivity, and heterogeneity) of the material were used to generate large numbers of virtual 3D volumes resembling the sample’s pore space characteristics, while being suitable for computationally demanding transport simulations. The transport ability, defined as the ratio of unhindered flow over hindered flow, is then determined via transport simulations through the virtual volumes. The simulation results are used as input for an upscaling routine based on an analogy with electrical networks, taking into account the spatial heterogeneity of the pore space over greater length scales. This novel approach is demonstrated for two distinct types of industrially manufactured fluid catalytic cracking (FCC) particles with zeolite Y as the active cracking component. Differences in physicochemical and catalytic properties were found to relate to differences in heterogeneities in the spatial porosity distribution. In addition to the characterization of existing FCC particles, our method of correlating pore space with transport efficiency does also allow for an up-front evaluation of the transport efficiency of new designs of FCC catalyst particles.

Agglomeration Mechanism of Nanoparticles by Adding Coarse Fluid Catalytic Cracking Particles

AbstractThe agglomeration mechanism of SiO2, TiO2, and ZnO nanoparticles by adding coarse fluid catalytic cracking (FCC) particles is studied. The core‐shell structure of agglomerates is revealed on the basis of experimental analyses. Nanoparticles can be fluidized by forming agglomerates of the core‐shell structure with coarse FCC particles. The porosity of core‐shell structure agglomerates and the average roundness value were found to be distinctly lower than those of pure nanoparticle agglomerates. In addition, the cohesion of the core‐shell structure agglomerates is far less than that of the agglomerates formed by pure nanoparticles. Due to the smaller porosity, irregular shape, and relatively low cohesion, the fluidization behavior of core‐shell structure agglomerates is better than that of pure nanoparticle agglomerates.

X-ray Fluorescence Tomography of Aged Fluid-Catalytic-Cracking Catalyst Particles Reveals Insight into Metal Deposition Processes.

Microprobe X-ray fluorescence tomography was used to investigate metal poison deposition in individual, intact and industrially deactivated fluid catalytic cracking (FCC) particles at two differing catalytic life-stages. 3 D multi-element imaging, at submicron resolution was achieved by using a large-array Maia fluorescence detector. Our results show that Fe, Ni and Ca have significant concentration at the exterior of the FCC catalyst particle and are highly co-localized. As concentrations increase as a function of catalytic life-stage, the deposition profiles of Fe, Ni, and Ca do not change significantly. V has been shown to penetrate deeper into the particle with increasing catalytic age. Although it has been previously suggested that V is responsible for damaging the zeolite components of FCC particles, no spatial correlation was found for V and La, which was used as a marker for the embedded zeolite domains. This suggests that although V is known to be detrimental to zeolites in FCC particles, a preferential interaction does not exist between the two.

Life and death of a single catalytic cracking particle.

Fluid catalytic cracking (FCC) particles account for 40 to 45% of worldwide gasoline production. The hierarchical complex particle pore structure allows access of long-chain feedstock molecules into active catalyst domains where they are cracked into smaller, more valuable hydrocarbon products (for example, gasoline). In this process, metal deposition and intrusion is a major cause for irreversible catalyst deactivation and shifts in product distribution. We used x-ray nanotomography of industrial FCC particles at differing degrees of deactivation to quantify changes in single-particle macroporosity and pore connectivity, correlated to iron and nickel deposition. Our study reveals that these metals are incorporated almost exclusively in near-surface regions, severely limiting macropore accessibility as metal concentrations increase. Because macropore channels are "highways" of the pore network, blocking them prevents feedstock molecules from reaching the catalytically active domains. Consequently, metal deposition reduces conversion with time on stream because the internal pore volume, although itself unobstructed, becomes largely inaccessible.