Equilibrium FCC Catalyst Research Articles

Efficient processing of crude oil using direct cracking at high temperatures over modified FCC catalysts

The direct cracking of Bach Ho crude oil, having API gravity of 41°, over equilibrium FCC catalyst (Ecat), modified FCC catalyst (HT-FCC) and ZSM-5 additive were studied at 620–650 °C using short-contact-time micro activity testing unit. HT-FCC catalyst was prepared by the treatment of Ecat with oxalic acid in reflux condition. This treatment largely improves the porosity while keeping the particle size of Ecat. Hence, it leads to an important enhancement in catalytic cracking activity. Due to high activity of HT-FCC catalyst, the direct cracking of crude oil can be performed at a low catalyst-to-oil ratio (C/O) which helps to decrease the yield of dry gas. At 620–650 °C, C/O of 1.5–2.5, 18–23 wt.% of light olefins, 3–6 wt.% of dry gas together with 51–59 wt.% of gasoline yields can be obtained with HT-FCC catalyst. ZSM-5 addition favors the conversion of gasoline to light olefins. Compared to the results reported in literature, the use of HT-FCC and ZSM-5 catalysts at 650 °C, low C/O of 1.5 shows promising performances: (i) much lower dry gas yield (8%), (ii) high light-olefins yield (32%) while maintaining high gasoline yield (43%), and (iii) high BTXs content in gasoline (45%).

Method and apparatus for forming electrode catalyst layer by electrospray method

The conversions of oxygenated compounds of bio-oils (alcohols, phenols and aromatic ethers) on a equilibrium FCC catalyst were studied at 500 °C during 60 s in a fixed bed laboratory reactor. Methanol, phenol and 2,6-dimethoxyphenol were dissolved in water and 1,2,4-trimethoxybenzene in benzene at 5 %wt. Identical experiments were performed over inert SiC. Conversions were very different, the highest one being that of 1,2,4-trimethoxybenzene (95.7 %wt.), followed by 2,6-dimethoxyphenol (75.0 %wt.), methanol (60.8 %wt.) and phenol (54.9 %wt.). Deoxygenation in all the reactants was from dehydration and decarboxylation. The highest yield of hydrocarbons (47.1 %wt.) and coke (16.0 %wt.) were from 1,2,4-trimethoxybenzene, which, together with methanol, yielded mainly aromatics in the gasoline range. On the contrary, phenol and syringol yielded C4-hydrocarbons with high content of olefins. The highest amounts of oxygenated compounds were produced by 2,6-dimethoxyphenol. The thermal conversions were similar to the catalytic ones in the only case of 1,2,4-trimethoxybenzene, but much lower with the other reactants. In comparison to the catalytic experiments, thermal tests yielded much more hydrocarbons with 1,2,4-trimethoxybenzene, and oxygenated compounds with 2,6-dimethoxyphenol, than the other reactants. These tests could help in the prediction of specific contributions by these reactants if bio-oils are co-processed in FCC units or upgraded over acidic catalysts.

Performance of Equilibrium FCC Catalysts in the Conversion of the SARA Fractions in VGO

Fil: Fals Guerra, Jayson. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Santa Fe. Instituto de Investigaciones en Catalisis y Petroquimica Ing. Jose Miguel Parera. Universidad Nacional del Litoral. Instituto de Investigaciones en Catalisis y Petroquimica Ing. Jose Miguel Parera; Argentina

Upgrading jet fuel using spent FCC equilibrium catalyst

Upgrading jet fuel using spent FCC equilibrium catalyst

Exploration on Spent FCC Catalyst for Decolorization of Vegetable Oil

In the present work, an FCC equilibrium catalyst (E-cat) was used as a decolorizer in decolorization of vegetable oil. E-cat is an excellent and stable decolorizer, which can even be directly applied to the decolorization of vegetable oil after being discharged. The process conditions were investigated and optimized, mainly the bleaching temperature, time, and E-cat amounts. The spectrophotometric method was used to calculate the decolorization rate after detecting the absorbance of vegetable oil. As the bleaching time, temperature and E-cat amounts increase, the effects on the decolorization of rapeseed oil by E-cat were all improved to varying degrees. The best decolorization utility of E-cat was performed at 115°C and an E-cat ratio of 5wt% for 40min, the decolorization rate of the rapeseed oil was 93.3%. Compared with the fresh FCC catalyst with high catalytic activity, the decolorization capability of E-cat was not much reduced. It indicates that the structural characteristics of E-cat are more desirable in the decolorization of vegetable oil, as evidenced by the alkali treatment test.

The behavior of the surface Si/(Si+Al) ratio in the FCC catalyst deactivation

Herein, the surface Si/(Si+Al) ratio of a series of FCC catalysts was studied by X-ray Photoelectron Spectroscopy (XPS). Firstly, some of the interferences of the XPS signals from Si, and Al elements were studied and fixed by using the Multiple Linear Regression method (MLR). Subsequently, the Si/(Si+Al) ratio of a set of FCC catalysts was analyzed and this information was correlated with the surface area analysis (BET method). This work showed that the surface Si/(Si+Al) ratio of low deactivated FCC catalyst was lower than its bulk Si/(Si+Al) ratio, suggesting that there is a high content of Al2O3 on the surface of the catalyst when it is slightly deactivated. The surface Si/(Si+Al) ratio of the FCC catalyst increased as the surface area decreased (total and microporous) due to the deactivation of the catalyst; it means that the surface Si/(Si+Al) ratio is strongly affected by the deactivation of the catalyst. The surface Si/(Si+Al) ratio of the equilibrium FCC catalyst samples (Ecat) were very similar to their bulk Si/(Si+Al) ratio. This fact suggests that the surface Si/(Si+Al) ratio of an FCC catalyst progressively increases up to reach the bulk Si/(Si+Al) ratio, therefore the surface Si/(Si+Al) ratio is related to the FCC catalyst deactivation phenomenon.

The Role of Magnetic Susceptibility in Detecting Iron Poisoning in FCC Equilibrium Catalyst Samples and Its Combination with Other Macroscopic Bulk Analysis Techniques

In the last years, iron poisoning has gained more attention in fluid catalytic cracking operations across the globe. While more and more insights into the mechanisms of its deactivating effects on FCC catalyst particles are available, the early detection of Fe poisoning of FCC catalysts is complicated by the various sources of Fe. This paper describes the use of magnetic susceptibility determinations and digital microscopy for this purpose. The application of magnetic susceptibility shows that the magnetic properties of FCC catalysts change at about 0.30 wt % added Fe indicating that the deleterious effects of the contaminant Fe occur beyond this limit. The combination with inverse gas chromatography and mercury porosimetry determinations confirm the pore restricting effects by Fe poisoning.

Thermal and catalytic cracking of whole crude oils at high severity

The catalytic and thermal cracking of three types of whole crude oils, having API gravity at 34° (AL), 39° (AXL) and 51° (ASL), were investigated via a fixed-bed micro-activity test (MAT) unit at high temperature between 600 and 650 °C. Equilibrium FCC catalyst (E-Cat)/ZSM-5 additive was used for catalytic cracking tests at 30 s and catalyst/oil (C/O) ratio of 2.0–6.0. For both thermal and catalytic cracking of all crude oils, the increase in reaction temperature resulted in higher conversion and enhanced yields of C2-C4 light olefins, LPG, coke, and dry gas at the expense of naphtha, heavy cycle oil (HCO), and light cycle oil (LCO). In thermal cracking, the yields of C2-C4 olefins at 650 °C were as follows: AL (22.8 wt.%) > AXL (19.0 wt.%) > ASL (18.8 wt.%) associated with naphtha yields of 34.4, 38.1 and 48.0 wt.%, respectively. Compared with thermal, catalytic cracking over E-Cat/ZSM-5 enhanced conversion, doubled the yields of light olefins and showed an increase in aromatics content of naphtha fraction. Contrary to thermal cracking, the yields of C2-C4 olefins in catalytic cracking were as follows: ASL (42.9 wt.%) > AXL (41 wt.%) > AL (39.1 wt.%) associated with naphtha yields of 31.7, 27.5, and 23.0 wt.%, respectively.

Canola oil/glycerol mixtures in a continously operated FCC pilot plant and comparison with vacuum gas oil/glycerol mixtures

Catalytic cracking of glycerol/canola oil mixtures was conducted in a continuously operated FCC pilot plant at TU Wien. The range of mixtures was from pure canola oil to pure glycerol with several mixtures in between. The aim of this research was to prove if the addition of glycerol to the feed can be feasible and to determine changes in product quality. The set riser temperature was 550 °C and the selected feedrate was 2.7 kg/h. As bed material a zeolite-based commercially available FCC-equilibrium catalyst was used. Utilizing a 7 lump model the products were characterized. Viable products like cracking gas (C1–C4) and the gasoline lump (paraffins, olefins and aromatics) were analyzed in detail. The experiments showed that product distribution was mainly dependent on the glycerol content in the feed. The gas, gasoline and LCO + residue lump decreased dramatically. Non-viable products like water, coke and carbon oxides, on the other hand, increased significantly. Hence, it was concluded that under set conditions and parameters glycerol might only be beneficial to the FCC process in small admixtures because of possible control coke-make. Additionally, a comparison was made between experiments using canola oil/glycerol mixtures and VGO/glycerol mixtures.

Effect of the FCC Equilibrium Catalyst Properties and of the Cracking Temperature on the Production of Fuel from HDPE Pyrolysis Waxes

The catalytic cracking of high-density polyethylene pyrolysis waxes has been investigated with the aim of promoting the production of fuels. The runs have been conducted in a CREC riser simulator r...

Equilibrium FCC catalysts to improve liquid products from biomass pyrolysis

Abstract A commercial equilibrium FCC catalyst of the octane-barrel type was subjected to lixiviation treatments with both acidic (HNO3) and basic (NaOH) solutions in order to modify its textural and acidic properties. The alkaline lixiviation doubled the mesopore volume in the commercial catalyst, while the acidic treatment increased the concentration of crystalline component in the catalyst. The catalytic performances of the parent and modified catalysts in the immediate conversion of vapors from pine sawdust fast pyrolysis were evaluated in a fixed bed reactor at 550 °C using mass catalyst to bio-oil and tar ratios from 3 to 8. The modified catalysts both produced more hydrocarbons and less coke than the parent commercial catalyst. In turn, comparing the modified samples, the one subjected to alkali treatment was more effective in deoxygenating the pyrolysis vapors, resulting in higher hydrocarbon yields (up to 13.2%) and lower coke yields than the acid modified catalyst, a fact assigned to the higher mesoporosity which improves the diffusion transport of bulky coke precursor molecules. The acid modified catalyst allowed a higher extension of the reaction pathway, the selectivity to aromatic hydrocarbon products being much higher (up to 95.5% of hydrocarbons in the gasoline boiling range).

Conversion of Arabian Light Crude Oil to Light Olefins via Catalytic and Thermal Cracking

The thermal and catalytic cracking of Arabian Light crude oil, which has a density of 34° API, were evaluated in a fixed-bed microactivity test (MAT) unit between 550 and 650 °C. For the catalytic cracking, two catalysts were used, a steamed commercial MFI catalyst (M-cat) and an equilibrium FCC catalyst (E-cat). Thermal and catalytic cracking were compared at the same conversion, 34%, at 650 °C. For both, as the temperature increased, the yields of light olefins, LPG, dry gas, and coke increased, associated with a consistent decrease in heavy ends (LCO and HCO). The naphtha yield for catalytic cracking decreased as temperature increased; however, for thermal cracking, it was nearly constant. The superiority of catalytic cracking over thermal cracking for the propylene yield was interpreted in terms of mechanisms of free radicals and carbenium ions. Thermal cracking gave a higher yield of ethylene. At high temperature (650 °C) and catalyst to oil (C/O) ratio of 4, the olefins yield decreased in the order ...

Gasoline sulfur reduction additives – model component study

ABSTRACTZnAl2O4, MgAl2O4, and CuAl2O4 spinel based additives were characterized and evaluated in micro activity test unit at the fluid catalytic cracking unit conditions along with base equilibrium FCC catalyst at 10 weight percent concentration by using once through hydrocracker unit bottom feed (base feed) and the base feed spiked with thiophene model component. The sulfur shifting in liquid products such as light cycle naphtha, heavy cycle naphtha, light cycle oil and clarified oil were studied. Each additive was studied for their hydrogen transfer, aromatization, alkylation functionalities and preferential sulfur components cracking /removal.

Physical mixture of MCM-41/ZSM-5 as an active catalyst component for maximization of propylene in Catalytic cracking of VGO

ABSTRACTThe performance of a novel catalyst additive containing highly porous MCM-41 and ZSM-5 zeolite was investigated using a commercial equilibrium FCC catalyst in catalytic cracking of vacuum gas oil. The catalytic tests were assessed in a fixed-bed microactivity test unit at reaction temperatures 500–620 °C. The highest propylene yield of 23.8 wt% was achieved at 600 °C. The propylene yield increased from 14.49 wt% to 23.8 wt% when the temperature rose from 500 to 600 °C; however the gasoline yield fell from 22.47wt% to 16.49 wt% by increasing the temperature from 580 °C to 620 °C, respectively.

Catalytic cracking of heavy fractions from the pyrolysis of waste HDPE and PP

In the present paper, automotive waste plastics were considered as a potential source of fuels and chemicals. The feedstock in the experimental tests was represented by the heaviest fractions from the distillation of pyro-oil from the pyrolysis of high-density polyethylene (HDPE-wax) and polypropylene (PP-wax). Due to their very high viscosity both polymer-waxes were, prior to processing, diluted in atmospheric gas oil (GO). Mixtures with hydrotreated vacuum gas oil (HVGO) were also prepared and processed under simulated fluid catalytic cracking conditions via a MAT-test. The product distribution was similar to the one shown by the commercial FCC process: light gases (C1, C2), LPG, gasoline fraction, light and heavy cycle oil. To maintain optimal performance a commercial FCC equilibrium catalyst (FCC-ECAT) was used. When processing HDPE and PP waxes, high yields of profiling products – propylene and gasoline were obtained. In the case of the PP-wax feed without HVGO, the yield of gasoline was even higher than in case of pure HVGO. When cracking HDPE-wax feed mixtures the product distribution was oriented more towards the production of propylene. The composition of liquid products considering all types of feedstock consisted mainly of iso-alkanes and aromatics. The calculated values of microactivity for the HDPE-wax and PP-wax feedstock, with or without HVGO, were significantly higher than in the case of pure HVGO.

Catalytic cracking of vacuum gasoil over -SVR, ITH, and MFI zeolites as FCC catalyst additives

The cracking behaviour of three medium-pore zeolites -SVR, ITH, and MFI, with varying Si/Al molar ratio, was evaluated using an equilibrium FCC catalyst (E-Cat) and a hydrotreated vacuum gasoil (VGO) in a microactivity test unit (MAT). The increase in the yield of light olefins (21–29wt% over E-Cat/additive vs. 16wt% over E-Cat) was accompanied by a drop in the yield of gasoline (26–39wt% over E-Cat/additive vs. 43wt% over E-Cat) due to the cracking of reactive species in gasoline fraction (mainly olefins and isoparaffins). With increasing Si/Al ratio in zeolites MFI-280 and –SVR-120, propylene yield passed through maxima reaching 13.5wt% and 12.8wt%, respectively, compared with 7.0wt% over E-Cat. Maximum propylene yield occurred partially due to gasoline over-cracking to light olefins (inverse relation with Si/Al ratio). The effect of MFI crystal size showed that large size crystals enhanced the yield of light olefins as compared to small size crystals due to secondary cracking of gasoline molecules. Results of kinetic study based on 4-lump model showed proportional relation between MFI Si/Al ratio and activation energy for the conversion of gasoline to gases. Activation energy increased from 14.2kcal/mol to 16.3kcal/mol as Si/Al ratio increased from 30 to 2000.

High performance of H3BO3 modified USY and equilibrium catalyst with tailored acid sites in catalytic cracking

Increasing the cracking ability of catalyst by adjusting its surface acid property is of great significance for oil refining industry. The effects of boric acid on the structure and surface acidity of ultra stabilized Y (USY) and FCC equilibrium catalyst during the modification were investigated. The structural and surface properties of the prepared samples were characterized by low-temperature N2 sorption, XRD, 27Al and 29Si MAS NMR, and FTIR using pyridine probe molecule. Modified USY and equilibrium catalyst possessed reduced Lewis acid sites. The Brönsted/Lewis acid ratios of USY increased from 0.64 to 1.56 after modification, at the same time, the microporous surface areas increased, due to the nonframework and framework dealumination during the modification. The catalytic cracking tests were performed on a bench-scale micro reactor at 500 °C and atmospheric pressure, using n-dodecane as a modeling reactant and vacuum gas oil as conventional feedstock. The results showed that modified samples with high Brönsted acid sites had better cracking abilities and increased hydrogen transfer activity than raw samples.

Kinetic modeling for catalytic cracking of pyrolysis oils with VGO in a FCC unit

A 5-lump kinetic model is proposed and validated to mean the catalytic cracking of pyrolysis oils with equilibrium fluid catalytic cracking catalyst (E-CAT) in an advanced cracking evaluation (ACE-R) FCC unit. In the present work a blend of fast pyrolysis oil (FPO) with vacuum gas oil (VGO); hydrodeoxygenated oil (HDO) with VGO; and VGO are used as raw materials. The kinetic modeling of lumped systems is carried out using a sequential approach. This approach decreased the number of simultaneous equations and hence estimated parameters. A 5-lump model, derived from 3- and 4-lumps, is used to represent the experimental data and used to estimate the kinetic constants and hence the yields of gasoline, LPG, dry gases, coke and feedstocks. In the sequential approach, the kinetic parameters have been estimated for a 3-lump model, and then the information is used to estimate the 4-lump parameters using a 4-lump model. Finally, the kinetic constants obtained from 4-lump are used to estimate the kinetic parameters for 5-lump model. A set of new experiments have been performed for catalytic cracking of pure VGO and coprocessing of FPO with VGO and HDO with VGO, by varying WHSV from 6 to 24h−1, at a constant reaction temperature and C/O ratio of 530°C and 5, respectively. The optimized process conditions were maintained to produce higher gasoline yield from VGO by catalytic cracking over equilibrium FCC catalyst. The process parameters obtained from lumped modeling, for catalytic cracking of pure VGO, have been compared with the kinetic parameters obtained from 4-lumped model available in the literature, and approximately 2% deviation were found in the products yields with respect to experimental data.

Coupling Process of Heavy Oil Millisecond Pyrolysis and Coke Gasification: A Fundamental Study

To realize the clean and high-efficiency utilization of the inferior heavy oil, a novel conceptional process coupling heavy oil millisecond pyrolysis and coke gasification processes was proposed. The effects of reaction temperature and residence time on the flash pyrolysis behavior of vacuum residue (VR) were first investigated using Py-GC/TOF-MS. Results show that increasing the reaction temperature from 600 to 800 °C, as well as shortening the residence time from 400 to 200 ms could reduce the coke yield by approximately 28%. 1-Alkenes are the most abundant class in the cracked products, and the selectivity of total olefins in the light products from C3 to C16 could be over 75%. Then the cracking performance of VR over Y zeolite-based equilibrium FCC catalysts, silica sands, and calcium aluminate catalysts were studied by a fluidized bed reactor. Furthermore, the coked catalysts were gasified in steam and steam–O2 mixture atmosphere, respectively. Results show that the calcium aluminate catalyst has app...

Immediate catalytic upgrading of soybean shell bio-oil

The pyrolysis of soybean shell and the immediate catalytic upgrading of the bio-oil over an equilibrium FCC catalyst was studied in order to define its potential as a source for fuels and chemicals. The experiments of pyrolysis and immediate catalytic upgrading were performed at 550 °C during 7 min with different catalysts to oil relationships in an integrated fixed bed pyrolysis-conversion reactor. The results were compared under the same conditions against those from pine sawdust, which is a biomass source commonly used for the production of bio-oil. In the pyrolysis the pine sawdust produced more liquids (61.4%wt.) than the soybean shell (54.7%wt.). When the catalyst was presented, the yield of hydrocarbons increased, particularly in the case of soybean shell, which was four time higher than in the pyrolysis. The bio-oil from soybean shell produced less coke (between 3.1 and 4.3%wt.) in its immediate catalytic upgrading than that from pine sawdust (between 5 and 5.8%wt.), due to its lower content of phenolic and other high molecular weight compounds (three and five times less, respectively). Moreover, soybean shell showed a higher selectivity to hydrocarbons in the gasoline range, with more olefins and less aromatic than pine sawdust.