Search Results (14)

Feedstock quality has been proven to be the single variable that most affects fluid catalytic cracking (FCC) unit performance, but catalyst characteristics have also been reported in the literature to have a considerable effect on cracking process performance. How these two main variables of the FCC process complement each other in the search for ways to optimize the performance of the FCC unit is the subject of current research. Twenty-one feedstocks with K_W-characterizing factors ranging from 11.08 to 12.06, Conradson carbon contents ranging from 0.05 to 12.8 wt.%, and nitrogen contents ranging from 800 to 3590 ppm (wt/wt) (basic nitrogen from 172 to 1125 ppm (wt/wt)) were cracked on 21 catalysts with micro-activity between 67% and 76% (wt/wt) in a laboratory-based advanced catalytic evaluation (ACE) unit at a reaction temperature of 527 °C, catalyst–to-oil ratios between 3.5 and 12.0 wt/wt, and a catalyst time on stream of 30 s. Some of the feeds and catalysts tested in the laboratory FCC ACE unit were also examined in a commercial short-contact-time FCC unit resembling a UOP side-by-side design. It was found that conversion can be very well predicted in both the laboratory ACE and the commercial FCC units using multiple linear correlations developed in this work from information about the following feed properties: K_W-characterizing factor, nitrogen content, and micro-activity of the catalyst. The coke on the catalyst that controls the catalyst-to-oil ratio and the regenerator temperature in the commercial FCC unit could be calculated using the correlations developed in this work for the laboratory ACE and commercial FCC units, based on feed characteristics and catalyst micro-activity. Due to the greater slope of the Δ coke/Δ micro-activity dependence observed in the ACE FCC unit, the more active catalysts show weaker results compared to the less active catalysts at a constant coke yield. In contrast, catalysts with higher activity are preferable for operation in the commercial FCC plant because they provide higher conversion at the same coke yield due to the lower slope of the Δ coke/Δ micro-activity relationship. Full article

Chemical recycling via catalytic pyrolysis is constrained by coke deposition and costly catalyst make-up. We investigate polypropylene (PP) and low-density polyethylene (LDPE) conversion over a spent FCC equilibrium catalyst (AXL) and, critically, quantify the re-activation energy landscape of the resulting coke. Using a semi-batch reactor (350 °C) and thermogravimetric analysis to 1100 °C combined with the Ozawa–Flynn–Wall method, we distinguish soft and hard coke under inert, oxidative, and sequential N₂ to air regimes. LDPE yields mainly gas (70.7 wt%) with 5.5 wt% coke, whereas PP favors liquids (47.1 wt%) with 3.4 wt% coke. LDPE-derived coke is softer (71% of total; E_A = 170 kJ mol⁻¹ soft) than PP coke (60% soft; E_A = 166 kJ mol⁻¹), evidencing a more refractory PP residue. Oxygen lowers E_A to ~155 kJ mol⁻¹ for both polymers. We introduce a simple TGA-based “softness ratio” to guide regeneration severity and show that a refinery-waste FCC catalyst delivers selective plastic-to-fuel conversion while enabling energy-aware regeneration protocols. The framework directly supports scale-up by linking polymer structure, coke quality, and atmosphere-dependent re-activation energetics. Full article

This study investigated the combustion profiles and oxidation mechanisms of coke on spent FCC catalysts from two Sinopec refineries and compared the effects of O₂/N₂ and O₂/CO₂ atmospheres. Using the Coats–Redfern method combined with nonlinear regression, the kinetics of coke oxidation were analyzed for the activation energies derived from the modified D3 and F2 models. Both these models yielded results that agreed with the previous reports. Selection of the suitable kinetic model was significantly influenced by specific properties of the coke on spent FCC catalysts. Furthermore, a computational model revealed that on an industrial scale, external mass transfer predominated the intrinsic kinetics; the differences observed in the O₂/N₂ and O₂/CO₂ environments were primarily due to variations in oxygen diffusion. These findings highlight the potential of optimizing FCC catalyst regeneration processes through alternative oxidation environments and the use of catalytic additives. Full article

This study evaluates the impact of the catalyst-to-oil (C/O) ratio in the 1 to 7 range on the catalytic cracking of vacuum gas oil (VGO). Experiments are conducted using fluid catalytic cracking (FCC)-type catalysts, in a mini-fluidized bench-scale Riser Simulator reactor invented at the Chemical Reactor Engineering Centre (CREC), University of Western Ontario. The CREC Riser Simulator replicates FCC industrial operating conditions such as temperature, species partial pressure, and reaction times. The results indicate that increasing the C/O ratio above 5 slightly impacts VGO conversion, increases light gases yield, decreases light cycle oil (LCO) yield, and stabilizes gasoline yield. These findings align with temperature-programmed desorption (TPD) data, showing how the retention of a larger number of acid sites at a C/O of 7 boosts light gas production and reduces LCO selectivity. These elevated C/O ratios also lead to higher coke formation. The results reported together with future studies conducted by our research team on the impact of higher catalyst flows, larger potential catalyst attrition, higher catalyst loading in the cyclones, and excess heat generated in the catalyst regenerator unit, are of critical value for establishing the impact of C/O ratios in the overall FCC refinery operation. Full article

Regeneration has been considered as an ideal way for the post-treatment of waste FCC catalyst (ECat). In this work, the degeneration mechanism of ECat was firstly researched and attributed to the increasing of strong acid sites accessibility of ECat in contrast with fresh FCC catalyst by adsorption FTIR. Based on the proposed degeneration mechanism, ECat was successfully regenerated through suitable weakening for strong acid sites by boron modification. Characterization and evaluation results suggested that, the strong acid sites of regenerated ECat (R-ECat) were apparently decreased by boron modification which had significantly improve the heavy oil catalytic cracking performance of R-ECat. Because of the excellent performance, R-ECat in this work could successfully substitute for partial fresh FCC catalyst in FCC unit, which would provide a practicable way for the reutilization of ECat. Full article

In the FCC conversion of heavy petroleum fractions as atmospheric residues, the main challenge for refiners to achieve the quantity and quality of various commercial products depends essentially on the catalyst used in the process. A deep characterization of the catalyst at different steps of the process (fresh, regenerated, and spent catalyst) was investigated to study the catalyst’s behavior including the physicochemical evolution, the deactivation factor, and kinetic–thermodynamic parameters. All samples were characterized using various spectroscopy methods such as N₂ adsorption–desorption, UV-visible spectroscopy, Raman spectroscopy, LECO carbon analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray fluorescence (XRF), nuclear magnetic resonance spectroscopy (NMR¹³C) analysis, and thermogravimetric analysis. The results of the N₂ adsorption–desorption, UV-vis, Raman, LECO carbon, and SEM imaging showed that the main causes of catalyst deactivation and coking were the deposition of carbon species that covered the active sites and clogged the pores, and the attrition factor due to thermal conditions and poisonous metals. The XRD and XRF results showed the catalyst’s physicochemical evolution during the process and the different interlinks between catalyst and feedstock (Nickel, Vanadium, Sulfur, and Iron) elements which should be responsible for the coking and catalyst attrition factor. It has been found that, in addition to the temperature, the residence time of the catalyst in the process also influences catalyst structure transformation. NMR¹³C analysis revealed that polyaromatic hydrocarbon is the main component in the deposited coke of the spent catalyst. The pyridine-FTIR indicates that the catalyst thermal treatment has an influence on its Brønsted and Lewis acid sites and the distribution of the products. Thermogravimetric analysis showed that the order of catalyst mass loss was fresh > regenerated > spent catalyst due to the progressive losses of the hydroxyl bonds (OH) and the structure change along the catalyst thermal treatment. Moreover, the kinetic and thermodynamic parameters showed that all zones are non-spontaneous endothermic reactions. Full article

Olefins are crucial building blocks for petrochemical industry, serving as raw materials for the production of various products such as plastics, synthetic fibers, detergents, solvents, and other chemicals. In FCC, heavy petroleum feedstocks are injected into a catalytic cracking unit, where they are mixed with a catalyst. The catalyst aids in breaking down the large hydrocarbon molecules into smaller fragments, including olefins like Propylene and Ethylene. These polymerization reactions occur at high temperatures. They demand that heat removal occurs as quickly as possible in order to control the reactor temperature and to avoid “hot spots” in the Regenerator or localized oxidation reactions (and to avoid creep rupture of the regenerator steel cladding). The cooling of the regenerator cladding surface can be achieved by impinging water droplets (spray), ejected from a spray nozzle. Spray cooling can provide uniform cooling and handle high heat fluxes in both a single phase and two phases. This research provides a thermal hydraulic design of regenerator spray cooling systems. In the framework of this research, Fire Dynamics Simulator (FDS) software was applied in order to simulate the temperature field and the water vapor mass fraction. A COMSOL Multiphysics finite element code was used in order to calculate the temperature field inside the regenerator cladding. The calculated surface temperatures and heat transfer convective coefficient, obtained using FDS software, were validated successfully against COMSOL numerical results and previous results in the literature. The numerical simulations were carried out for two cases. The first case was carried out at a distance of 0.5 m, and the second case was carried out at a distance of 0.2 m. A grid sensitivity study was carried out on the FDS model. Numerical integrations were carried out over time in order to calculate the average temperatures. The difference between these four average temperatures, calculated by applying different grids, is less than 7.4%. The calculated surface temperatures and heat transfer convective coefficient were validated successfully against COMSOL numerical results and previous research. It was shown that the calculated temperatures decrease in the second case. The water spray system managed to cool the steel wall more effectively as the water spray system approaches the steel cladding. Full article

The pyrolysis process is a thermochemical recycling process that in recent years has gained importance due to its application in plastic waste, which is one of the biggest environmental problems today. Thus, it is essential to carry out kinetic and thermodynamic analyses to understand the thermocatalytic degradation processes involved in plastic waste mixtures. In this sense, the main objective of this study is to analyze the degradation kinetics of the specific mixture of polypropylene (25%) and polystyrene (75%) with 10% mass of regenerated FCC catalyst which was recovered from conventional refining processes using 3 heating rates at 5, 10 and 15 K min⁻¹ by thermogravimetric analysis (TGA). The obtained TGA data were compared with the isoconversional models used in this work that include Friedman (FR), Kissinger Akahira Sunose (KAS), Flynn–Wall–Ozawa (FWO), Starink (ST) and Miura–Maki (MM) in order to determine the one that best fits the experimental data and to analyze the activation energy and the pre-exponential factor; the model is optimized by means of the difference of minimum squares. Activation energy values between 148 and 308 kJ/mol were obtained where the catalytic action has been notorious, decreasing the activation energy values with respect to thermal processes. Full article

H-Oil gas oils have a higher density and higher nitrogen content, and consequently much lower reactivity than straight-run vacuum gas oils during fluid catalytic cracking (FCC). The conversion of H-Oil gas oils observed in a laboratory catalytic cracking unit at constant operating conditions showed a 20 wt.% lower conversion rate than straight-run hydrotreated vacuum gas oil. Thus, a revamp of commercial FCC units, and the selection of a higher activity catalyst with lower coke selectivity is needed to provide the stable trouble-free operation of the unit. The performed revamp of the commercial FCC unit allowed a stable operation at a higher throughput. It also allowed an increased riser outlet temperature from 532 to 550 °C; increased maximum allowable regenerator temperature from 705 to 730 °C; decreased afterburning from 12 to 6 °C; decreased NOx emissions in the flue gas from 250 to 160 mg/Nm³; improved catalyst regeneration; decreased catalyst losses to 0.0142 kg/t feed; and improved catalyst circulation at a higher throughput. It was confirmed in the commercial FCC unit that the H-Oil light vacuum gas oil is the least reactive H-Oil gas oil during catalytic cracking. Full article

Fluid catalytic cracking (FCC) is the workhorse of modern crude oil refinery. Its regenerator plays a critical role in optimizing the overall profitability by efficiently restoring the catalyst activity and enhancing the heat balance in the riser reactor. Improvement in the device metallurgy and process operations have enabled industrial regenerators to operate at high temperatures with a better coke burning rate and longer operating cycle. Today, the carbon content of regenerated catalyst has drastically reduced to less than 0.1 wt.%. However, the unit is still plagued with operational complexities and insufficient understanding of the underlying dynamic, multiscale intricacies. Recent process-intensification strategies provide insights into regenerator performance improvement potentials. In this review, the importance of the uniform distribution of spent catalysts through structural modification and operational manipulations of the catalyst distributor is discussed. The knowledge of the role of baffles in enhancing excellent gas–solid interaction has been increasing, but skepticism due to its complex hydrodynamic effects on gas–solid flows fends off operators from its application, a critical evaluation of its implication in the regenerators is covered. The understanding of the contribution of air/steam distributor design and feed gas injection techniques for even contact with spent catalyst leading to the improvement in FCC performance is also investigated. The reliability of FCC components is equally a big concern, as unplanned shutdown and enormous economic losses are being witnessed due to device failure. To this end, mitigation approaches to damaging afterburn and high-temperature erosion problems with respect to process control and geometric adjustment in the bed, freeboard, cyclone separators and collection ducts are explored. Emission limits for fluid catalytic cracking unit (FCCU) and products are consistently ratcheting downward; the commingled turnkey solutions to reducing pollutants generation are also reviewed. Full article

Heavy petroleum industries, including the Fluid Catalytic Cracking (FCC) unit, are among some of the biggest contributors to global greenhouse gas (GHG) emissions. The FCC unit’s regenerator is where these emissions originate mostly, meaning the operation of FCC regenerators has come under scrutiny in recent years due to the global mitigation efforts against climate change, affecting both current operations and the future of the FCC unit. As a result, it is more important than ever to develop models that are accurate and reliable at predicting emissions of various greenhouse gases to keep up with new reporting guidelines that will help optimise the unit for increased coke conversion and lower operating costs. Part 1 of this paper was dedicated to reviewing the riser section of the FCC unit. Part 2 reviews traditional modelling methodologies used in modelling and simulating the FCC regenerator. Hydrodynamics and kinetics of the regenerator are discussed in terms of experimental data and modelling. Modelling of constitutive parts that are important to the FCC unit, such as gas–solid cyclones and catalyst transport lines, are also considered. This review then identifies areas where the current generation of models of the regenerator can be improved for the future. Parts 1 and 2 are such that a comprehensive review of the literature on modelling the FCC unit is presented, showing the guidance and framework followed in building models for the unit. Full article

Heavy petroleum industries, including the fluid catalytic cracking (FCC) unit, are useful for producing fuels but they are among some of the biggest contributors to global greenhouse gas (GHG) emissions. The recent global push for mitigation efforts against climate change has resulted in increased legislation that affects the operations and future of these industries. In terms of the FCC unit, on the riser side, more legislation is pushing towards them switching from petroleum-driven energy sources to more renewable sources such as solar and wind, which threatens the profitability of the unit. On the regenerator side, there is more legislation aimed at reducing emissions of GHGs from such units. As a result, it is more important than ever to develop models that are accurate and reliable, that will help optimise the unit for maximisation of profits under new regulations and changing trends, and that predict emissions of various GHGs to keep up with new reporting guidelines. This article, split over two parts, reviews traditional modelling methodologies used in modelling and simulation of the FCC unit. In Part I, hydrodynamics and kinetics of the riser are discussed in terms of experimental data and modelling approaches. A brief review of the FCC feed is undertaken in terms of characterisations and cracking reaction chemistry, and how these factors have affected modelling approaches. A brief overview of how vaporisation and catalyst deactivation are addressed in the FCC modelling literature is also undertaken. Modelling of constitutive parts that are important to the FCC riser unit such as gas-solid cyclones, disengaging and stripping vessels, is also considered. This review then identifies areas where current models for the riser can be improved for the future. In Part II, a similar review is presented for the FCC regenerator system. Full article

Fluid catalytic cracking (FCC) processes have been used widely in petroleum refineries. FCC regenerators play important roles for maintaining catalyst activity and supply the reaction heat. The regenerator efficiency is mainly connected to the hydrodynamics of the fluidized bed, because the gas and solid behaviors are very important factors in mass and heat transfer. The void properties, such as chord length, rising velocity, frequency, and fraction, have been determined in a large cold flow model (0.48 m-ID × 6.4 m-high) of the FCC regenerator, which was geometrically scaled down from a commercial FCC unit. The local void chord length, rising velocity, frequency, and fraction exhibit their maximum value along the radial direction of the bed. The cross-sectional mean void chord length, rising velocity, and fraction increase and the cross-sectional mean void frequency decreases with height in the bed. The variation of void properties in the FCC regenerator with turbulent fluidized bed exhibit similar trends to those in a bubbling fluidized bed. The void properties in the FCC regenerator have been correlated with the experimental parameter on the basis of bubbling bed concept. The predicted void velocities based on the correlations agreed well with the experimental data from present and previous studies. A modified bubbling fluidized bed model could describe the void properties in the regenerator operated in turbulent fluidized bed regime. Full article

ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC) process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam), FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives) are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated) activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n-Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C₁₂ cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F) ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas) olefins as the nature (Brønsted-to-Lewis ratio) of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at higher conversion levels. Coke remained low with both fresh and steam-deactivated P/ZSM-5 additives. Full article