Fluid Catalytic Cracking Catalyst Research Articles

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.

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.

Fabrication of spent FCC catalyst TiO2-V2O5 composite material and its electrocatalytic performance

Fabrication of spent FCC catalyst TiO2-V2O5 composite material and its electrocatalytic performance

Elucidating the interaction of FCC catalyst components: the discrete roles of matrix and binder on zeolite structure

Abstract Zeolite Y is the active phase of the modern fluid catalytic cracking (FCC) catalyst. However, a functional and active FCC catalyst comprises, in addition to zeolite Y, matrices and a binder that introduce some levels of synergistic interaction between the catalyst components, impacting its activity. This study investigates the interactive properties of a zeolite-matrix-binder composite on a typical FCC catalyst using various characterization techniques. Characterization of synthesized FCC catalyst samples reveals changes in the structural composition of zeolite Y dependent upon the type and ratio of binder materials. The binder is important in the crystallization of the final composite. Acidic binder induces dealumination of zeolite, leading to amorphization, loss of Brønsted acid sites, framework structure impairment, and the formation of defective sites. TEM indicates the formation of zeolite-matrix interfaces upon binding of zeolite by the matrix. Depending on the extent and severity of thermal processing, the clay–alumina–silica binder undergoes dehydroxylation to varying degrees by cross-linking of terminal hydroxyl groups between neighboring binder particles, which contributes to the increased thermal and mechanical stability of the bound catalysts.

Use of spent fluid catalytic cracking catalyst (FCC) in Limestone Calcined Clay Cement (LC3) systems: Studies in pastes and mortars

This study evaluates the substitution of calcined clay for a waste from the petrochemical industry, spent fluid catalytic cracking catalyst (FCC), as a source of reactive aluminosilicates in Limestone Calcined Clay Cements (LC3) systems. Three carbonate types were used to make cement-type LC3: a high-purity calcium carbonate, waste from the marble industry, and another from a dolomite soil source. LC3 blends were prepared by mixing 50 wt% OPC, 5 wt% calcium sulfate dihydrate, 30 wt% FCC and 15 wt% from each carbonate source. A mixture than substituting the carbonate source for a siliceous source was prepared to analyse the influence of carbonate phases in LC3 systems. The hydration process of the LC3 blends was studied by X-ray diffraction, thermogravimetric analyses, isothermal calorimetry and FESEM. Mechanical properties were studied by measuring compressive strength at 7, 28 and 90 days. The obtained results corroborated that the mortars prepared with LC3 cements using the FCC obtained higher compressive strength than the control mortar prepared with ordinary Portland cement (OPC) at 28 and 90 curing days. It has been demonstrated that FCC is a by-product that can substitute calcined clay, and the different sources of carbonates such as high purity, waste or contaminated with magnesium do not interfere with the performance of this type of cement.

Catalytic dehydrogenation cracking characteristics of vacuum residue over solid basic catalyst

The basic calcium aluminate with appropriate catalytic cracking activity, excellent anti-coking performance, and hydrothermal stability is of great potential for the utilization of heavy oil. However, there is a lack of systematic research on the catalytic dehydrogenation cracking characteristics of vacuum residue (VR) over solid basic catalyst. Thus, by combining the TG and Py-GC/MS methods, the dehydrogenation cracking behavior of S-VR was investigated. The results indicated that S-VR cracking on calcium aluminate leads to less coking and higher olefin content in liquid products compared with FCC catalyst and quartz sand. Then, the activation energy Ea is computed from the catalytic dehydrogenation cracking of S-VR on calcium aluminate. The results show that the Ea values from Friedman and OFW methods range from 68 to 143 kJ∙mol−1 and 114 to 192 kJ∙mol−1, respectively. After that, the molecular-level carbon number distributions of the products obtained from cracking S-VR on different reaction conditions are investigated, and the optimal reaction temperature and the heating rate are 650 °C and 1000 °C/s, respectively. Finally, the free radical regulation theory was constructed to explain the catalytic dehydrogenation cracking mechanism of basic calcium aluminate catalyst.

Recycling of Spent FCC Catalysts: Conversion of Leached Residues to Zeolite ZSM-5.

The commercial recycling of spent FCC catalyst typically focuses on recovering only 1-3 % of rare-earth elements, with the remaining residues often disposed of in landfills. Here, we present a novel method to close a recycling loop for spent FCC catalyst. The method involves a series of leaching steps: Firstly, the spent catalyst material is leached with HNO3 to remove rare-earth elements such as La; second, solvothermal leaching with HCl removes most of Al and impurities like Fe, Ni and V; finally, a third leaching with H2SO4 removes Ti. The solid residues are then used to synthesize ZSM-5 without the addition of any extra silicon or aluminum sources after mild activation. The impurities in the synthesis gel strongly modify the properties of the zeolite, with ZSM-5 crystals containing higher levels of impurities exhibiting lower crystallinities, surface areas, acidities, cracking activities, as well as larger particle sizes.

In vitro assessment of cytotoxicity of spent fluid catalytic cracking refinery catalysts on cell lines and identification of critical toxic metals

The Purpose of the present study was to quantify the responses of ten cell lines (HeLa, HepG2, HEK293, MDA-MB-231, A498, A549, A357, 3 T3, BALB-C3 T3, and NIH-3 T3) to spent fluid catalytic cracking catalysts (SFCCCs) from different petroleum refineries, and relate these responses to metal concentrations of SFCCC leachates (SFCCCLs). Cytotoxicity of SFCCCs were significantly different depending on cell lines. A357 and 3 T3 cell were the most sensitive, and A498 and HeLa cells were the least sensitive. HEK293 cells showed the least fluctuation in toxic response to different SFCCCLs among all cells. Cytotoxic IC50 values of SFCCCs to 7 kinds of cells were the most correlated with vanadium (V) concentration in SFCCCLs. V is the most critical toxic factor of SFCCC. Glutathione synthesis was induced in HepG2 cells exposed to higher concentrations of SFCCCLs. SFCCCLs with low concentration of V can induce the decrease of GSH/GSSG ratio in HepG2 cells, suggesting that high concentration of V inhibits the detoxification of glutathione.

Influence of Accelerators on Cement Mortars Using Fluid Catalytic Cracking Catalyst Residue (FCC): Enhanced Mechanical Properties at Early Curing Ages.

Supplementary cementitious materials (SCMs) have been used in the construction industry to mainly reduce the greenhouse gas emissions associated with Portland cement. Of SCMs, the petrochemical industry waste known as fluid catalytic cracking catalyst residue (FCC) is recognized for its high reactivity. Nevertheless, the binders produced using SCMs usually present low mechanical strength at early curing ages. This study aims to assess the effect of different accelerating additives (KOH, sodium silicate SIL, commercial additive SKR) on the mechanical strength of mortars containing FCC. The results show that after only 8 curing hours, the compressive strength gain of the FCC mortars containing SKR was over 100% compared to the FCC mortar with no additive (26.0 vs. 12.8 MPa). Comparing the compressive strength of FCC mortar containing SKR to the control mortar, the enhancement is spetacular (6.85 vs. 26.03 MPa). The effectiveness of the tested accelerators at 8-24 curing hours was KOH ≈ SIL < SKR, whereas it was KOH < SIL < SKR for 48 h-28 days. The thermogravimetric data confirmed the good compatibility of FCC and the commercial accelerator.

Effect of fast heating rate and alkaline catalyst on composition and characteristic of volatile products during catalytic upgrading of oil sand bitumen

The study was devoted to exploring the fundamental study on the upgrading of Buton oil sand bitumen (OSB) via fast alkaline catalytic pyrolysis based on the fluid pyrolysis technology. The effect of fast heating rate on the composition and molecular distribution of volatile products from the high-temperature fast pyrolysis of OSB was investigated by Py-GC/TOF-MS that could simulate the fast heating rate of industrial fluid pyrolysis process. The results showed that the volatile products of OSB under heating rates ranging from 10 to 1000 °C/s had the similar species composition. It was found that there were the highest relative content of low-carbon alkenes (C2-C4) and light aromatics (C6-C8) in volatile products under the 1000 °C/s, indicating that the fast heating rate favored the production of light alkenes and aromatics. Subsequently, a laboratory-scale fluidized bed apparatus was employed to further gain insight into fast alkaline catalytic pyrolysis behaviors of OSB. The investigation on the yield distribution, fractional- and molecular-level chemical characteristic of volatile products obtained from the fast alkaline catalytic upgrading of OSB over calcium aluminate was carried out with the aid of the comparison with that over Y zeolite-based FCC catalyst and silica sand. The results revealed that three-phase products over calcium aluminate possessed the larger selectivity of C2−C4 alkenes, larger yield of light oil and the lower coke output, which were 51.88%, 45.49% and 7.96%, respectively. On basis of the chemical structure analysis of liquid products, the alkaline catalytic upgrading of OSB over calcium aluminate could heighten the content of chain alkyl structures as well as alkyl-substituents attached to aromatic ring in liquid products. This indicated that the fast heating rate and alkaline catalyst that adopted in catalytic upgrading process of OSB could play an energetic role in optimizing the composition of volatile products. The alkaline catalytic upgrading of OSB based on fluid pyrolysis technology with the fast heating rate could heighten the yield of low-carbon olefins and light oil and lessen coke yield, meanwhile modify the chemical structure characteristics of liquid products that were conducive to the generation of valuable chemicals (light alkanes and BTX) during secondary processing of liquid products.

Study on the Regeneration of Waste FCC Catalyst by Boron Modification.

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.

Co-processing of organic fraction from groundnut shell biocrude with VGO in FCC unit to produce petrochemical products

This research work explores the transformative potential of biomass leading to sustainable production of biocrude and its utilization in refinery and petrochemical sector for reducing reliance on fossil fuels. In this study, groundnut shell biomass was thermally converted in a customized continuous semi pilot auger reactor in temperature range of 400–700 °C. The optimum temperature for maximizing biocrude was studied, and detailed chemical analysis revealed that biocrude contains hydrocarbons and alcohols with a calorific value of 29 MJ/kg. Furthermore, this study demonstrates the performance of the FCC (Fluid Catalytic Cracking) catalyst and feedstock (H-T- VGO (Hydrothermal vacuum gasoline oil) & Biocrude) in a laboratory-scale utilizing ACE R + MM (Advanced Cracking Evaluation - Residue and Metals Management) unit under predetermined temperatures (515 °C, 525 °C) and a fixed cat-to-oil weight ratio (CTO = 6 w/w). The organic phase and FCC feedstock in different weight ratios from 5 to 20 wt % were blended. There are marginal changes in the yields of dry gas, LCO (light cycle oil) and HCO (heavy cycle oil), with significant increase in the yields of LPG (liquified petroleum gas) and gasoline. Bottoms have been reduced, and coke formation has been adjusted. However, this process requires prudent blending and temperature choices, with future recommendations including improvement in the quality of biocrude to enhance the yields of both LPG and gasoline along with reduced coke formation.

Enhancing light fuel production through catalytic pyrolysis of municipal mixed plastic waste over activated spent FCC catalyst

To address the issue of environmental pollution caused by waste plastics and increase their recycling utilization, a cost-effective chemical recycling method was employed in this study. It involved the use of spent fluid catalytic cracking (FCC) catalysts to convert waste plastics into valuable products. Sequential nitric acid treatment and pore expansion by ammonium hexafluorosilicate methods were employed to activate the spent FCC catalyst, with the aim of improving its physicochemical properties and enhancing the production of light fuel. The results demonstrated that activation treatment of the spent FCC catalyst improved the external surface area and meso-macroporous volumes of the activated catalysts. This process facilitated the initial cracking reaction of polyolefin macromolecules and alleviated the diffusion limitations of reactants and products within the pores of the catalyst, resulting in an increase in the yield of light fuels. Compared to the spent FCC catalyst, the activated catalysts exhibited 5.79–19.49% higher selectivities for light olefins and 21.67–29.76% higher yields for light fuels. These findings provide potential opportunities for the valuable utilization of waste plastics.

A Review of Catalyst Modification and Process Factors in the Production of Light Olefins from Direct Crude Oil Catalytic Cracking

Petrochemical feedstocks are experiencing a fast growth in demand, which will further expand their market in the coming years. This is due to an increase in the demand for petrochemical-based materials that are used in households, hospitals, transportation, electronics, and telecommunications. Consequently, petrochemical industries rely heavily on olefins, namely propylene, ethylene, and butene, as fundamental components for their manufacturing processes. Presently, there is a growing interest among refineries in prioritising their operations towards the production of fuels, specifically gasoline, diesel, and light olefins. The cost-effectiveness and availability of petrochemical primary feedstocks, such as propylene and butene, can be enhanced through the direct conversion of crude oil into light olefins using fluid catalytic cracking (FCC). To achieve this objective, the FCC technology, process optimisation, and catalyst modifications may need to be redesigned. It is helpful to know that there are several documented methods of modifying traditional FCC catalysts’ physicochemical characteristics to enhance their selectivity toward light olefins’ production, since the direct cracking of crude oil to olefins is still in its infancy. Based on a review of the existing zeolite catalysts, this work focuses on the factors that need to be optimized and the approaches to modifying FCC catalysts to maximize light olefin production from crude oil conversion via FCC. Several viewpoints have been combined as a result of this research, and recommendations have been made for future work in the areas of optimising the yield of light olefins by engineering the pore structure of zeolite catalysts, reducing deactivation by adding dopants, and conducting technoeconomic analyses of direct crude oil cracking to produce light olefins.

Catalytic conversion of biomass-plastic blend to high-quality bio-oil via co-pyrolysis using chicken eggshell waste as deoxygenation catalyst: A feasibility study

Energy shortages and reliance on fossil fuels have led to the discovery of new technologies to reduce the environmental impact by taking advantage of excess plastic and turning them into usable alternative fuels using the pyrolysis method. However, the oil produced contains highly oxygenated compounds, which are considered a downside to the fuel characteristics, along with a low by-product yield. Therefore, feasibility study of calcined eggshells as a deoxygenation catalyst in the co-pyrolysis of empty fruit bunch (EFB)/high-density polyethene (HDPE) blend and compare it quantitatively and qualitatively with bio-oil produced using a commercial zeolite-based catalyst, ZSM-5 and Fluid Catalytic Cracking (FCC) at 500 °C operating temperature, 10 ft3/min N2 flow rate, 10 wt% catalyst loading, 1:1 HDPE:EFB ratio and 75 g feedstock with 60 min operating time in a stainless-steel fluidised bed reactor. Natural and calcined chicken eggshells were characterised using TGA/DTG, while the bio-oil produced was characterised using GC–MS. By using FCC catalyst, the highest oil yield (13.2 wt%) with high oxygenated compounds was obtained. The oil with the highest hydrocarbon yield (61.62 %) and lowest oxygenated compound content (38.38 %) was obtained using a calcined chicken eggshell (CES) catalyst. Calcined chicken eggshell (CES) catalysts showed better performance than commercial catalyst in terms of the quality and average yield of bio-oil produced. This study confirmed that the presence of a catalyst in the co-pyrolysis of EFB and HDPE can improve the yield of bio-oil and enhance its quality.

Optimization of Process Parameters for Catalytic Pyrolysis of Waste Tyre using Reactivated Fluid Catalytic Cracking Catalyst

Optimization of Process Parameters for Catalytic Pyrolysis of Waste Tyre using Reactivated Fluid Catalytic Cracking Catalyst

Study on the kinetics of catalytic pyrolysis of single and mixed waste plastics by spent FCC catalyst

Study on the kinetics of catalytic pyrolysis of single and mixed waste plastics by spent FCC catalyst

Acid attack on alkali-activated mortars: A test proposal

The durability of new binders in construction is one of the keys for further applications. The acid attack resistance of alkali-activated mortars (AAMs) was tested. A test proposal was developed, and the selected AAMs (precursors: blastfurnace slag, vitreous calcium silicoaluminate, fly ash and spent FCC catalyst) were analyzed in terms of acid neutralization capacity (ANC), mass loss at a constant pH= 2, and mass loss of the cubes immersed in 1 molar nitric acid solution. The results were compared to the mortars prepared with ordinary Portland cement. The ANC values were generally higher when the calcium content of the binder increased. The attacked mortars were characterized by thermogravimetry and microscopy techniques. The proposed test, based on three complementary experiments, allows the analysis of AAMs´ stability and the identification of more resistant systems to acid attack.

Grace launches Paragon FCC catalyst technology for more sustainably produced fuels

Grace launches Paragon FCC catalyst technology for more sustainably produced fuels