Fluid Catalytic Cracking Catalyst Research Articles

Investigation on the Hydrothermal Condition in Synthesis of Active Matrix from Metakaolin: Physicochemical Properties and Intrinsic Cracking Activities

The current trends in research and development of FCC catalyst is focused on the formulation of active matrices that serve as pre-crackers, with the objective of reducing the diffusional resistance of the longer chain hydrocarbon molecule in the feed. In this study, an aluminosilicate active matrix was synthesised from metakaolin using hydrothermal method. The experimental variables that were varied were hydrothermal temperature, in the range of 80 to 110 °C, and hydrothermal time, in the range of 12 to 72 hours, to investigate the best conditions for synthesising the active matrix. Subsequently, the active matrix was subjected to a series of analyses, including X-ray fluorescence, X-ray diffraction, N2 physisorption, NH3-temperature programmed desorption, Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetry, with the objective of determining its composition, crystal characteristics, surface characteristics, acidity, functional groups, material structure, and thermal characteristics. Additionally, the active matrix was tested for its intrinsic cracking activity using the micro activity test (MAT). The results indicate that the best temperature for hydrothermal synthesis of the active matrix is 80 °C. The active matrix synthesised with a heating time of 24 hours demonstrated the highest light cycle oil yield, reaching 38.9 wt%. Meanwhile, the active matrix synthesised at 48 hours exhibited the most favourable characteristics, with a specific surface area of 144.23 m2/g and a pore volume of 0.9933 cm3/g, as well as the highest cracking conversion of 70.0 wt%. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Recycling of a spent residue-fluid-catalytic cracking catalyst into an adsorbent for the removal of copper(II) ions from wastewater

The recycling of spent residue fluid catalytic cracking (RFCC) catalysts into adsorbents addresses both waste management and environmental pollution. Herein, we aimed to extract metals from spent RFCC catalysts, subject them to hydrothermal treatment and washing processes, and characterized by XRD, FT-IR, XPS, BET and SEM techniques, which also evaluating their efficiency as adsorbents. The spent RFCC catalyst was washed for 3 h and hydrothermally treated at 100 °C for 24 h, resulting in RFCC-A with a surface area of 81.77 m²/g and an average diameter of 66.81 nm, the cation-exchange capacities of up to 4300 – 5325 meq/100 g. The washing process removed 40 % – 46 % of vanadium and 12 % – 13 % of nickel. The derived adsorbent demonstrated a Cu(II) ion removal capacity of 120 mg/g from wastewater within 1 h at pH 4, and a total adsorption capacity of 831.68 mg/g after three regenerations. The primary removal mechanism was cation exchange involving electrostatic attraction. The manufacturing cost of the adsorbent was 59.5 USD/kg, equating to 0.50 USD/g Cu(II), with regeneration costs under 1 USD/g Cu(II). These findings indicate that using spent RFCC catalyst-derived adsorbents is cost effective and environmentally beneficial.

Promoting fine particle removal in cyclone by spray agglomeration and heterogeneous condensation

By adding a spray chamber in front of the cyclone separator, spray agglomeration and heterogeneous vapor condensation were combined to improve the removal effect of the cyclone separator on fine particles, which is used for the deep treatment of high-humidity industrial flue gas and fine particles. Fine particles can form agglomerates through the capture effect of micron droplets, and can also grow in size through heterogeneous vapor condensation in supersaturated water vapor environment, thus being effectively removed by cyclone separators. Supersaturated water vapor environment was a necessary condition for heterogeneous vapor condensation. Numerical simulation results showed that supersaturated water vapor environment can be formed in the spray chamber when the relative humidity of the original flue gas was high, and the higher the relative humidity, the higher the supersaturation and the larger the supersaturation area. The experimental results indicated that spray agglomeration and spray coupling heterogeneous condensation increased the particle removal efficiency of the cyclone separator by 11.6 % and 22.6 %, and the removal efficiency in the 2–4 μm “fish-hook” range was increased by 21.6 % and 41.7 %, respectively. This technology was successfully applied for the first time in the deep treatment of the tail gas in Fluid Catalytic Cracking (FCC) catalyst production industry, which can ensure that the particle emission concentration was within 20 mg/Nm3.

The impact of spent fluid catalytic cracking catalyst on the selected mechanical and physical performances of cement mortars

This paper presents the results of research aimed for evaluating the impact of applicability of spent fluid catalytic cracking catalyst as a substitute of 20, 40, 60 and 80% of cement, by mass, in cement mortars on their selected mechanical and physical performances. It was demonstrated that substitution of 20% of cement mass with spent catalyst enhanced mortar’s compressive strength for 16.7%. Further addition of spent catalyst tended to decrease strength, whilst, simultaneously, rose the values of capillary absorption and water absorptivity because of deterioration of cement matrix structure, documented by SEM photos. Based on the research and literature data, it was proved that spent cracking catalyst might be a promising additive to cement in the amount not exceeding 40% of its mass considering its pozzolanicity

Roles of Catalysts and Feedstock in Optimizing the Performance of Heavy Fraction Conversion Processes: Fluid Catalytic Cracking and Ebullated Bed Vacuum Residue Hydrocracking

Petroleum refining has been, is still, and is expected to remain in the next decades the main source of energy required to drive transport for mankind. The demand for automotive and aviation fuels has urged refiners to search for ways to extract more light oil products per barrel of crude oil. The heavy oil conversion processes of ebullated bed vacuum residue hydrocracking (EBVRHC) and fluid catalytic cracking (FCC) can assist refiners in their aim to produce more transportation fuels and feeds for petrochemistry from a ton of petroleum. However, a good understanding of the roles of feed quality and catalyst characteristics is needed to optimize the performance of both heavy oil conversion processes. Three knowledge discovery database techniques—intercriteria and regression analyses, and artificial neural networks—were used to evaluate the performance of commercial FCC and EBVRHC in processing 19 different heavy oils. Seven diverse FCC catalysts were assessed using a cascade and parallel fresh catalyst addition system in an EBVRHC unit. It was found that the vacuum residue conversion in the EBVRHC depended on feed reactivity, which, calculated on the basis of pilot plant tests, varied by 16.4%; the content of vacuum residue (VR) in the mixed EBVRHC unit feed (each 10% fluctuation in VR content leads to an alteration in VR conversion of 1.6%); the reaction temperature (a 1 °C deviation in reaction temperature is associated with a 0.8% shift in VR conversion); and the liquid hourly space velocity (0.01 h-1 change of LHSV leads to 0.85% conversion alteration). The vacuum gas oil conversion in the FCC unit was determined to correlate with feed crackability, which, calculated on the basis of pilot plant tests, varied by 8.2%, and the catalyst ΔCoke (each 0.03% ΔCoke increase reduces FCC conversion by 1%), which was unveiled to depend on FCC feed density and equilibrium FCC micro-activity. The developed correlations can be used to optimize the performance of FCC and EBVRHC units by selecting the appropriate feed slate and catalyst.

FCC catalyst market revenue to reach $3.9 bn by 2031, driven by advancements in refining technologies

FCC catalyst market revenue to reach $3.9 bn by 2031, driven by advancements in refining technologies

Selective conversion of spent cracking catalyst to faujasite-structured zeolites

Current recycling strategies for spent catalyst in Fluid Catalytic Cracking (FCC) focus on valuable rare-earth elements (REE) and sometimes include a reuse of spent materials by down-cycling, which hinders a circular economy. Herein, a new procedure for the selective conversion of spent FCC catalysts to FAU-type zeolite without secondary crystalline phases such as sodalite, zeolite P or zeolite A is reported. The steps include a leaching process of REE, followed by thermal activation with sodium hydroxide and acid treatment to get an aluminum-rich feed. The synthesis of FAU-type zeolites with varying Si/Al ratios uses the aluminum-rich catalyst feed and commercial water glass. The experiments show that incorporation of silicate from water glass into the zeolite structure is limited to zeolite products with Si/Al ratio ≤ 2.0. It indicates a flocculation of silicates in higher concentration in competition to the crystallization process of FAU-type zeolites. This is reinforced by the resulting crystals, covered and surrounded with small particles with morphology of silica. Moreover, a clear differentiation between zeolite Y and zeolite X is possible from materials properties with the definite evidence of a mixed phase. The kinetics of feed dissolution and incorporation of impurities, alumina and silica are controlled by the pre-treatment temperature, duration and silicon source. This enables flexible adjustment of the aluminum re-use from spent FCC catalyst, the amount of foreign elements (Fe, Ni, V), phase purity, Si/Al ratio, specific surface area and thermal stability of the final zeolite product. Structural and textural data of the resulting zeolites reveals high crystallinity > 80 %, Si/Al ratios of 1.6–2.0, and specific surface areas up to 780 m2/g.

Study on the influence of FCC waste catalysts on the interaction ability between asphalt and fillers

Fluid catalytic cracking (FCC) waste catalysts produced by petroleum cracking contain many harmful substances, such as heavy metals, and improper treatment can lead to environmental pollution. To solve this problem, this study investigated four types of FCC (LM, SH, A, SL) waste catalyst as a substitute filler for limestone mineral powder and examined their interactions with asphalt and fillers. The X-ray fluorescence (XRF), scanning electron microscope and specific surface area tests were conducted to compare the performance of FCC waste catalyst and fillers. Meanwhile, the effects of FCC waste catalyst on asphalt mastic composed of limestone mineral powder and asphalt were evaluated using surface energy, interaction parameters, and FTIR. Results show that there is little difference in the main components of the four waste FCC catalysts and limestone mineral powder. However, the surface roughness and specific surface area of the FCC catalysts are significantly greater than those of limestone. Moreover, the addition of FCC waste catalyst can improve the adhesion of asphalt with fillers and aggregates, and significantly enhance the interaction capabilities between the filler and the base asphalt, especially for SH. FTIR analysis confirms that the aforementioned improvements are achieved through physical interactions. This study reveals the effects of different FCC waste catalysts on asphalt mortar, and provides a theoretical basis for promoting the practical application of FCC waste catalysts in road engineering.

Single-step and stepwise pyrolysis to recover high-value chemicals from mixed polyolefins and polylactide

Biodegradable plastics are increasingly utilized due to environmental concerns but are typically disposed of together with conventional plastics. Valuable chemicals could be recovered from waste plastics by chemical recycling, but the mixing of different types of waste plastic affects the efficiency of the process. In this study, high-value chemicals were produced from a mixture of polyolefins and biodegradable polylactide by single and stepwise pyrolysis processes. The pyrolysis of polyolefins yielded fuel-like hydrocarbons, and the pyrolysis of polylactide yielded lactide and lactic acid. In the stepwise process, oxygenated compounds were only produced in the low-temperature step, and fuel-like hydrocarbons produced in the high-temperature step were not contaminated by oxygenated compounds. The influence of different catalysts on yields was investigated in the single-step and stepwise processes. The yield and selectivity of each product were significantly influenced by the type of catalyst and the composition of the plastic feedstock. Using a mixed feedstock of polyolefins and polylactide, low-temperature pyrolysis with a zeolite LTA catalyst favored the formation of lactide and lactic acid, while diesel-range hydrocarbons were obtained in the second step at a higher temperature. Aromatic and gasoline-range hydrocarbons were preferably produced from the single-step pyrolysis of polyolefins with spent FCC catalyst.

Co-pyrolysis of refinery oil sludge with biomass and spent fluid catalytic cracking catalyst for resource recovery.

Catalytic co-pyrolysis of two different refinery oily sludge (ROS) samples was conducted to facilitate resource recovery. Non-catalytic pyrolysis in temperatures ranging from 500 to 600°C was performed to determine high oil yields. Higher temperatures enhanced the oil yields up to ~ 24 wt%, while char formation remained unchanged (~ 45%) for S1. Conversely, S2 exhibited a notably lower oil yield (~ 4 wt%) than S1. Pyrolysis oil of S1 consisted of phenolics (~ 50% at 600°C) whereas hydrocarbons were predominant in S2 oil (~ 80% at 600°C). Catalytic pyrolysis of S1 did not exhibit a substantial impact on oil yields but the oil composition varied significantly. High hydrocarbons, phenolics, and aromatics were obtained with molecular sieve (MS), metal slag, and ZSM-5, respectively. Catalytic co-pyrolysis of S2 with sawdust (SD) in the presence of MS enhanced the oil yield, and the resulting oil consisted of high hydrocarbons (~ 54%) and aromatics (~ 44%).

PP upcycling employing FCC spent catalyst: The role of contaminants, atmosphere and pressure

Innovative and sustainable approaches are being pursued to convert plastic waste into high-value fuels, particularly without using noble metal catalysts or external hydrogen sources. In this scenario, we explored the utilization of a spent fluid catalytic cracking (FCC) catalyst (ECAT), aiming to enhance the yield and quality of products through catalytic cracking of Polypropylene (PP) under different reaction conditions. Under a 20 bar H2 atmosphere, ECAT efficiently cracked PP into alkanes (71.6 %) and aromatics (25.5 %), with minimal alkenes (2.2 %) production. Similarly, under a 20 bar N2 atmosphere, ECAT achieved comparable conversion levels, producing mainly saturated hydrocarbons, which was intriguing. However, tests conducted at 1 bar N2 pressure showed that PP conversion remains unaffected but presents higher olefins’ yield and lower aromatics than ECAT. Thus, pressure seems to favor aromatization and in situ hydrogen transfer. By comparing the performance of ECAT with commercial CBV 712 zeolite, we propose that PP acts as an internal hydrogen source, eliminating the need for external supply improving efficiency and selectivity. Interestingly, mechanistic insights suggested that dehydroaromatization and hydrogen transfer within zeolite pores were dominant, and pressure (H2 or N2) could have helped it. In addition, contrary to previous studies that claim that metal contaminants in ECAT are essential for the hydrogenation process, our findings suggest that for this particular ECAT composition, we do not observe any boost in alkane yield due to the presence of these metals. Hence, our study comprehensively evaluates different strategies that can be employed to promote PP upcycling promoted by ECAT.

An Industrial Perspective for Sustainable Polypropylene Plastic Waste Management via Catalytic Pyrolysis—A Technical Report

Recycling plastics on an industrial scale is a key approach to the circular economy. This study presents a techno-economic analysis aimed at recycling polypropylene waste, one of the main consumer plastics. Specifically, it evaluates the technical and economic feasibility of achieving a large-scale cracking process that converts polypropylene waste into an alternative fuel. Pyrolysis is considered as a promising technique to convert plastic waste into liquid oil and other value-added products, with a dual benefit of recovering resources and providing a zero-waste solution. This study concerns a fast catalytic pyrolysis in a fluidized bed reactor, with the presence of a fluid catalytic cracking catalyst of low acidity for high heat transmission, for an industrial plant with a capacity of 1 t/h of polypropylene waste provided by the Greek Petroleum Industry. From the international literature, the operational conditions were chosen pyrolysis temperature at 430 °C, pressure at 1atm, heating rate at 5 °C/min, and yields of products to 71, 14, and 15 wt.%, for liquid fuel, gas, solid product, respectively. The plant design includes a series of apparatuses, with the main one to be the pyrolyzer. The catalytic method is selected over the non-catalytic because the presence of catalyst increases the quantity and quality of the liquid product, which is the main product of the plant. The energy loops of recycling pyrolysis gas and char as a low-carbon fuel in the plant were considered. The production cost, annual revenue, for 2023, are anticipated to reach €13.7 million (115 €/t) and €15 million (15 €/t), respectively, with an estimated investment equal to €5.3 million. The Payback Time is estimated to 2.4 years to recover the cost of investment. The endeavor is rather economically sustainable. A critical parameter for large scale systems is securing feedstock with low or negligible price.

Synthesis of customized zeolite X with outstanding CO2 selectivity over CH4 and N2 using facile activated spent fluid catalytic cracking catalysts

Efficient separation of CO2 from natural gas mixtures (CO2/CH4) and flue gas (CO2/N2) is pivotal for effective carbon capture and sequestration. Utilizing adsorbents derived from solid waste provides additional benefit for the carbon capture industry. This study introduces a convenient activation method at 200 °C for SFCC. Utilizing the activated SFCC as raw material under mild hydrothermal conditions, highly crystalline zeolite X (referred to as SFCC-X-200) of commercial quality with exceptional CO2 separation ability from CH4 and N2 is obtained. The static water adsorption rate of SFCC-X-200 meets the requirements of the national standard for commercial zeolite X (GB6287-86). Moreover, the ideal adsorbed solution theory (IAST) selectivity of SFCC-X-200 for CO2 from CO2/N2 (15/85, v/v) and CO2/CH4 (50/50, v/v) mixtures is significantly higher, at 797 and 199, respectively, compared to commercial X zeolite. SFCC-X-200 demonstrates tremendous potential for separating CO2/N2 and CO2/CH4 mixtures due to its outstanding adsorption capacity and selectivity, rapid attainment of adsorption equilibrium, complete desorption at ambient temperature, and extremely low cost.

The possibility of partial substitution of cement in cement mortars with the use of spent fluid catalytic cracking catalyst from polish oil refinery: mechanical performances and impact of the addition of superplasticizer

This paper presents the results of a study of the effect of spent catalytic cracking catalyst derived from polish oil refinery used as a partial replacement of cement (in the amount of 20, 40, 60 and 80% of cement mass) in the binder on the mechanical strength of cement mortars, prepared without and with superplasticizer. It was shown that the replacement of 20% of cement, by mass, with spent catalyst increased the compressive strength of mortars without and with superplasticizer dosage by 16.7% and 24.4%, respectively, and did not deteriorate the flexural strength of samples prepared with superplasticizer. With the increasing amount of spent catalyst (above 40% by weight of cement), a decrease in the strength of mortars was observed. This indicates that spent catalyst from catalytic cracking might be a promising material as a binder replacement in cementitious composites when used in smaller amounts (less than 40%).

Quantitative evaluation of anthropogenic sources and health risks of rare earth elements in airborne particulate matter

Rare earth elements (REEs) have emerged as contaminants in airborne particulate matter (PM); however, their anthropogenic sources remain poorly quantified, and associated health risks are unknown. This study investigates the REE distribution across eight sizes of airborne PM during July and December in Qingdao, a major Chinese port city. Our results reveal a single coarse-mode distribution with REE concentrations. In contrast, fine PM (size: 0.43–2.1 μm) exhibits notable enrichment of La and Ce compared to Al and other REEs. This study traces La and Ce enrichment to fluid catalytic cracking catalysts (FCCC)-related sources, including refinery and ship emissions, by comparing the REE fractionation in samples with potential sources. We quantify the contributions from FCCC-related sources to La (July: 33.6 % ± 3.2 %, Dec.: 46.4 % ± 5.2 %) and Ce (July: 16.5 % ± 14.3 %, Dec.: 30.3 % ± 12.2 %) by comparing measured concentrations with predictions derived from neighboring REEs, a method previously used exclusively in aquatic systems. For the first time, supply ratios of refinery and ship to FCCC-related La are calculated using a two-component mixing model based on the [La]FCCC/[V]anth, revealing the dominance of refinery emissions (July: 97.3 % ± 0.6 %, Dec.: 99.6 % ± 0.1 %). Furthermore, a global review of La and Ce anomalies that integrates published REE data with our findings reveals a widespread distribution of positive anomalies. The significantly positive correlation between La and Ce anomalies underscores FCCC-related emissions as a global source in fine PM, contributing 0–92 % (mean: 35 % ± 33 %) for La and 0–72 % (mean: 21 % ± 24 %) for Ce. Although the non-carcinogenic health risks of Ce are generally low globally, concerns should be raised in areas near source emissions, where Ce health risks sharply increased along with its concentrations. There is urgently need to establish a threshold value for La, owing to its global enrichment. This study provides novel insights into the sources and health implications of REEs in airborne PM.

FCC catalyst with enhanced mesoporosity, its preparation and use

FCC catalyst with enhanced mesoporosity, its preparation and use

Study on Pretreatment and Leaching Behaviors of Spent Fluid Catalytic Cracking Catalysts

Study on Pretreatment and Leaching Behaviors of Spent Fluid Catalytic Cracking Catalysts

IMPACT OF ALUMINOSILICATE WASTES ON THE HYDRATION, PHYSICAL AND MECHANICAL PROPERTIES OF CEMENT PASTE

The impact of aluminosilicate wastes (spent fluid catalytic cracking catalyst from oil companies and metakaolin containing waste from the production of expanded glass granules) on the hydration and compressive strength of the cement paste was analysed when a proportion of cement was replaced by one waste material or two waste materials. The article presents results of X-ray diffraction and thermal analysis of hardened cement pastes. It was determined that the spent catalytic cracking catalyst accelerates cement hydration because of its high surface area and pozzolanic activity; and metakaolin containing waste has a retarding effect. X-ray diffraction and thermal analysis showed that the specimens with metakaolin containing waste had the lowest amount of portlandite, and the compressive strength of these specimens was similar to that of the control specimens when a superplasticizer was used. It was found that a mix of aluminosilicate wastes has a different effect on cement hydration and makes it possible to adjust the hydration time of the binder within a certain interval.

IMPACT OF ALUMINOSILICATE WASTES ON THE HYDRATION, PHYSICAL AND MECHANICAL PROPERTIES OF CEMENT PASTE

The impact of aluminosilicate wastes (spent fluid catalytic cracking catalyst from oil companies and metakaolin containing waste from the production of expanded glass granules) on the hydration and compressive strength of the cement paste was analysed when a proportion of cement was replaced by one waste material or two waste materials. The article presents results of X-ray diffraction and thermal analysis of hardened cement pastes. It was determined that the spent catalytic cracking catalyst accelerates cement hydration because of its high surface area and pozzolanic activity; and metakaolin containing waste has a retarding effect. X-ray diffraction and thermal analysis showed that the specimens with metakaolin containing waste had the lowest amount of portlandite, and the compressive strength of these specimens was similar to that of the control specimens when a superplasticizer was used. It was found that a mix of aluminosilicate wastes has a different effect on cement hydration and makes it possible to adjust the hydration time of the binder within a certain interval.

Mild activation of spent fluid catalytic cracking (FCC) catalysts for the pilot synthesis of zeolite a with commercial quality and excellent Co2+ removal ability

Fluid catalytic cracking (FCC) plays a pivotal role in the transformation of crude oil into fuels and bulk chemicals, crucial within petroleum refining. However, it also generates a substantial volume of hazardous spent FCC catalysts. Thus, developing an effective method to convert these hazardous spent catalysts into high-value products is essential for the sustainable advancement of the petrochemical industry. In this study, we introduce a simple, mild, and environmentally friendly activation approach for spent FCC catalysts, followed by a straightforward synthesis of zeolite A meeting commercial standards. The resulting zeolite A (referred to as SFCC-A) exhibited high crystallinity, exceptional selectivity, and efficient Co2+ removal capabilities from wastewater. Even at a solid/liquid ratio of 1/1000 g·mL−1, a removal efficiency of approximately 99 % was achieved. SFCC-A demonstrated a high adsorption capacity (180.5 mg·g−1) for Co2+ and a broad operational pH range (4–8). Furthermore, the pilot synthesis was successfully scaled up to 100 L, maintaining consistent product performance compared to lab-scale production. Additionally, we investigated the evolution of species during the activation of spent FCC catalysts using multiple characterization techniques, elucidated the phase diagram of SFCC-A and the crystallization process under optimal conditions. The combination of a simple, mild, and eco-friendly activation method with a convenient synthesis process, yielding high-value zeolite A products, transforms spent FCC catalysts into valuable resources rather than hazards.