Catalytic Cracking Of Palm Oil Research Articles

Catalytic Cracking of Palm Oil: Effect of Catalyst Reuse and Reaction Time of the Quality of Biofuels-like Fractions

This work systematically investigated the influence of catalyst reuse and reaction time on the yield and quality of organic liquid products (OLP) obtained in a cracking pilot plant at 450 °C and 1.0 atm. The distillation of OLP produced 04 (four) distilled fractions (gasoline, kerosene, and green diesel). The biofuels-like fractions are liquid mixtures with high content of hydrocarbons (alkanes, alkenes, and aromatics) with potential application as substitutes for fossil fuels in internal combustion motors. The quality of the biofuels was certified by physical-chemical analysis and FT-IR and GC-MS analysis. The experimental results showed the feasibility of applying the spent sodium carbonate twice in the catalytic cracking of vegetable oils. The physical-chemical properties (density, viscosity, acid value, saponification value, and flash point) of OLP decrease as the reaction time increases. The distillation of OLP yields 62.35% (wt.), producing green-like gasoline, kerosene, and diesel fractions rich in hydrocarbons. Therefore, biofuel-like fractions produced by distillation of OLP have a great potential for replacing partially petroleum-derived fuels.

Kinetic Study Of Palm Oil Catalytic Cracking Over A Zeolite-based Catalyst

A study on catalytic cracking of palm oil (RBDPO) over an equilibrium zeolite-based catalyst to produce gasoline fraction was carried out. The effect of contact times between the feed and catalyst was studied by experimenting with WHSV in the range of 6 h-1 to 25 h-1, and the effect of catalytic reaction temperatures was observed at 490 °C, 510 °C, and 530 °C. The results show that yields of gasoline fraction tend to decrease with the decrease of WHSV, due to “over-cracking” of gasoline fraction into gaseous products. A four-lump kinetic model consisting of gasoline fraction, gaseous products, and coke was applied to derive sets of reaction rate equations. A numerical method was used to estimate the kinetic parameters.

Low-temperature synthesis of three-pore system hierarchical ZSM-5 zeolite for converting palm oil to high octane green gasoline

Microporous zeolite commonly suffers from a slow diffusion rate due to its restricted micropore channel, especially for bulky molecules. In this case, hierarchical zeolite has emerged as an essential functional material because of its excellence in alleviating the diffusion issue and improving the catalytic performances. In this research, hierarchical ZSM-5 zeolite with a three-interconnected-pore system (3 PS, micro-meso-macro) has been synthesized at a low temperature (90 °C) in the presence of CaCO3 nanoparticles. The low-temperature condition leads to the formation of the highly crystalline ZSM-5 particles with intercrystalline mesopores having a pore size distribution ranging from 3 to 6 nm. Moreover, the resulting zeolites also exhibit void spaces in a macroscale (20 nm–80 nm) created from the removal of CaCO3 nanoparticles. Moreover, the catalytic tests on the catalytic cracking of palm oil demonstrate the superior activity of the trimodal porous ZSM-5 in producing high octane gasoline compared to the ZSM-5 with two pore system (2 PS), and one-pore system (1 PS). A three-interconnected-pore system enhances the accessibility of reactant molecules to and the product molecules out of the active sites within the ZSM-5 crystals. As a result, the 3 PS catalyst produces a remarkable gasoline yield (25–26%) with exceptional aromatic content (>90%) and a research octane number (RON) of 114 with a less amount of cokes deposited during the reaction. Ultimately, the 3 PS catalyst also possesses the highest stability as it can maintain the catalytic performance up to the third cycle.

Effect of HCl/γ-Al2O3 and HCl/Ni/γ-Al2O3 Catalyst on The Cracking of Palm Oil

Fuel oil has a deficit every year. Therefore, a substitute fuel is needed, which can be obtained more efficiently. One of the alternative fuels that have been widely researched is biofuel. Catalytic cracking is a method of producing biofuels such as biogasoline (C5-C9), bioavtur (C10-C15) and green diesel (C16-C22). This research aims to produce biofuels by catalytic cracking of palm oil using HCl/γ-Al2O3 and HCl/Ni/γ-Al2O3 catalysts (1, 3, 5 and 7%). The catalyst was prepared by wet impregnation and characterized by x-ray diffraction, Brunauer Emmett teller and ASTM-D664. The reaction cracking process was operated at a constant temperature of 370 °C, 50 ml volume, and 1 atm pressure. The best catalyst for cracking palm oil is HCl/Ni/γ-Al2O3 (5%) with a yield of 81%, selectivity to biogasoline at 6.41%, bioavtur at 33.81%, and green diesel at 20.33%.

Acids treatment for improving catalytic properties and activity of the spent RFCC catalyst for cracking of palm oil to kerosene-diesel fraction fuels

In this study, the reactivation and modification of the spent Residue Fluid Catalytic Cracking (RFCC) catalyst using sulfuric acid and citric acid as acids treatment was evaluated by varying the acid solution concentrations. The effect of acid types and acid-solution concentrations on structural, textural, and acidic properties of spent RFCC catalyst was observed using X-ray diffraction, X-ray fluorescence, N2-sorption and pyridine-probed Fourier transform infrared measurements. Catalytic cracking of palm oil was used to evaluate the catalytic activity of the acid-treated catalysts. All the results showed the different beneficial effects of the sulfuric acid- and citric acid- treatments on the physicochemical properties of the modified catalyst with an improvement of surface area and pore volume of catalysts as well as the crystallinity due to the metal and matrix material removal. The sulfuric acid-treated catalysts have higher Brønsted/Lewis (B/L) ratio than the citric acid treatment, while the citric acid-treated catalysts have lower B/L ratio due to the enhancement of Lewis acid site. The acid-treated catalysts showed better performance than the non-treated catalyst. The selectivity of the kerosene-diesel range product fraction increased with the acid concentrations treatment.

Analysis of CaCO3 Impregnation on HY Zeolite Surface Area, Pore Size, and Activity in the Catalytic Cracking of Palm Oil to Biofuels

Fossil energy sources are currently decreasing, requiring the development of alternative energy sources. Vegetable oil is a raw material for alternative renewable energy supplies. This study produced biofuels from vegetable oil using calcium carbonate (CaCO3)-impregnated HY catalysts. In addition, this study aimed to investigate the effect of CaCO3 impregnation on the surface area and the catalytic activity of catalysts in the palm oil cracking process to produce biofuels. The HY catalyst was modified by the wet impregnation method in 5 wt% CaCO3 solution and was further calcined at 550°C for three h. Furthermore, the catalysts were tested in a continuous fixed-bed catalytic reactor at 450°C. The catalyst properties were characterized using Brunauer–Emmett–Teller (BET) surface area, Barrett–Joyner–Halenda (BJH) for pore size distribution, and X-Ray Diffraction (XRD) for crystal structure and phases. The results showed that the addition of CaCO3 decreased surface area and pore volume; however, the pore size increased, which resulted in the production of heavy hydrocarbons. Interestingly, the introduction of CaCO3 enhanced the yield of Organic Liquid Product (OLP) and diesel-range hydrocarbons selectivity to reach 79.09% and 30.54%, respectively. Furthermore, the introduction of CaCO3 increased deoxygenation activity.

Simulation of Organic Liquid Product Deoxygenation through Multistage Countercurrent Absorber/Stripping Using CO2 as Solvent with Aspen-HYSYS: Process Modeling and Simulation.

In this work, the deoxygenation of organic liquid products (OLP) obtained through the thermal catalytic cracking of palm oil at 450 °C, 1.0 atmosphere, with 10% (wt.) Na2CO3 as a catalyst, in multistage countercurrent absorber columns using supercritical carbon dioxide (SC-CO2) as a solvent, with an Aspen-HYSYS process simulator, was systematically investigated. In a previous study, the thermodynamic data basis and EOS modeling necessary to simulate the deoxygenation of OLP was presented. This work addresses a new flowsheet, consisting of 03 absorber columns, 10 expansions valves, 10 flash drums, 08 heat exchanges, 01 pressure pump, and 02 make-ups of CO2, aiming to improve the deacidification of OLP. The simulation was performed at 333 K, 140 bar, and (S/F) = 17; 350 K, 140 bar, and (S/F) = 38; 333 K, 140 bar, and (S/F) = 25. The simulation shows that 81.49% of OLP could be recovered and that the concentrations of hydrocarbons in the extracts of absorber-01 and absorber-02 were 96.95 and 92.78% (wt.) on a solvent-free basis, while the bottom stream of absorber-03 was enriched in oxygenated compounds with concentrations of up to 32.66% (wt.) on a solvent-free basis, showing that the organic liquid products (OLP) were deacidified and SC-CO2 was able to deacidify the OLP and obtain fractions with lower olefin contents. The best deacidifying condition was obtained at 333 K, 140 bar, and (S/F) = 17.

Reactivation of the Spent Residue Fluid Catalytic Cracking (RFCC) Catalyst through Acid Treatment for Palm Oil Cracking to Biofuels

This work discusses the treated spent Residue Fluid Catalytic Cracking (RFCC) catalysts using sulfuric or citric acids to examine the impact of acid treatment on the catalyst physicochemical properties and structural characteristics. The catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), and Brunauer−Emmett−Teller-Barrett−Joyner−Halenda (BET-BJH) methods. The catalytsts were performed in a continuous fixed-bed reactor for catalytic cracking of palm oil. Changes of the catalyst characteristics and catalytic performance testing of the catalyst after the acid treatment for palm oil cracking process were discussed. It was found that the acid treatment on the spent RFCC catalyst can increase the surface area and pore volume of catalysts as well as the crystallinity. The closed pores in the spent RFCC are opened by acid treatment by eliminating heavy metals. Concerning to the catalytic performance, the acid-treated catalysts had better performance than the non-treated catalyst, which could increase selectivity of the kerosene-diesel range fraction from 47.89% to 55.41%. It was interested, since the non-treated catalyst could not produce gasoline fraction, while the acid-treated catalsysts could produce gasoline fraction at selectivity range of 0.57 – 0.84%. It was suggested that both sulfuric or citric acids treatment could increase the cracking performance of spent RFCC catalyst by shifting the product to lower hydrocarbons.

Simulation of Organic Liquid Products Deoxygenation by Multistage Countercurrent Absorber/Stripping Using CO2 as Solvent with Aspen-HYSYS: Thermodynamic Data Basis and EOS Modeling.

In this work, the thermodynamic data basis and equation of state (EOS) modeling necessary to simulate the fractionation of organic liquid products (OLP), a liquid reaction product obtained by thermal catalytic cracking of palm oil at 450 °C, 1.0 atmosphere, with 10% (wt.) Na2CO3 as catalyst, in multistage countercurrent absorber/stripping columns using supercritical carbon dioxide (SC-CO2) as solvent, with Aspen-HYSYS was systematically investigated. The chemical composition of OLP was used to predict the density (ρ), boiling temperature (Tb), critical temperature (Tc), critical pressure (Pc), critical volume (Vc), and acentric factor (ω) of all the compounds present in OLP by applying the group contribution methods of Marrero-Gani, Han-Peng, Marrero-Pardillo, Constantinou-Gani, Joback and Reid, and Vetere. The RK-Aspen EOS used as thermodynamic fluid package, applied to correlate the experimental phase equilibrium data of binary systems OLP-i/CO2 available in the literature. The group contribution methods selected based on the lowest relative average deviation by computing Tb, Tc, Pc, Vc, and ω. For n-alkanes, the method of Marrero-Gani selected for the prediction of Tc, Pc and Vc, and that of Han-Peng for ω. For alkenes, the method of Marrero-Gani selected for the prediction of Tb and Tc, Marrero-Pardillo for Pc and Vc, and Han-Peng for ω. For unsubstituted cyclic hydrocarbons, the method of Constantinou-Gani selected for the prediction of Tb, Marrero-Gani for Tc, Joback for Pc and Vc, and the undirected method of Vetere for ω. For substituted cyclic hydrocarbons, the method of Constantinou-Gani selected for the prediction of Tb and Pc, Marrero-Gani for Tc and Vc, and the undirected method of Vetere for ω. For aromatic hydrocarbon, the method of Joback selected for the prediction of Tb, Constantinou-Gani for Tc and Vc, Marrero-Gani for Pc, and the undirected method of Vetere for ω. The regressions show that RK-Aspen EOS was able to describe the experimental phase equilibrium data for all the binary pairs undecane-CO2, tetradecane-CO2, pentadecane-CO2, hexadecane-CO2, octadecane-CO2, palmitic acid-CO2, and oleic acid-CO2, showing average absolute deviation for the liquid phase () between 0.8% and 1.25% and average absolute deviation for the gaseous phase () between 0.01% to 0.66%.

Biofuels Production from Catalytic Cracking of Palm Oil Using Modified HY Zeolite Catalysts over A Continuous Fixed Bed Catalytic Reactor

The increase in energy demand led to the challenging of alternative fuel development. Biofuels from palm oil through catalytic cracking appear as a promising alternative fuel. In this study, biofuel was produced from palm oil through catalytic cracking using the modified HY zeolite catalysts. The Ni and Co metals were impregnated on the HY catalyst through the wet-impregnation method. The catalysts were characterized using X-ray fluorescence, X-ray diffraction, Brunauer–Emmett–Teller (BET), Pyridine-probed Fourier-transform infrared (FTIR) spectroscopy, and Scanning Electron Microscopy (SEM) methods. The biofuels product obtained was analyzed using a gas chromatography-mass spectrometry (GC-MS) method to determine its composition. The metal impregnation on the HY catalyst could modify the acid site composition (Lewis and Brønsted acid sites), which had significant roles in the palm oil cracking to biofuels. Ni impregnation on HY zeolite led to the high cracking activity, while the Co impregnation led to the high deoxygenation activity. Interestingly, the co-impregnation of Ni and Co on HY catalyst could increase the catalyst activity in cracking and deoxygenation reactions. The yield of biofuels could be increased from 37.32% to 40.00% by using the modified HY catalyst. Furthermore, the selectivity of gasoline could be achieved up to 11.79%. The Ni and Co metals impregnation on HY zeolite has a promising result on both the cracking and deoxygenation process of palm oil to biofuels due to the role of each metal. This finding is valuable for further catalyst development, especially on bifunctional catalyst development for palm oil conversion to biofuels.

Exceptional Aromatic Distribution in the Conversion of Palm-Oil to Biohydrocarbon Using Zeolite-Based Catalyst

A series of four catalysts, i.e. ZSM-5 (Si/Al = 25) (Z1), a combination of ZSM-5 (Si/Al = 25) and zeolite Y (Si/Al = 25) (Z2), zeolite Y (Si/Al = 25) (Z3), and ZSM-5 (Si/Al = 80) (Z4), was successfully prepared for catalytic cracking of palm oil. All three catalysts utilized silica as a binder without other additional components. Catalytic cracking tests showed that the aromatic distribution was very high, according to the following order: Z4 (98%) > Z1 (90%) > Z2 (84%) > Z3 (60%). It was shown that ZSM-5 promotes the formation of aromatics better than zeolite Y does. From 98% of aromatics products in Z1, 71% were benzene, toluene, and xylene (BTX). It appears that the formation of aromatics needs milder acidity since a higher number of acids extends the cracking reaction, resulting in the formation of more gaseous and heavy aromatics products. The results of this study show potential for the sustainable production of bio-hydrocarbons with exceptional aromatic distributions, which may fulfill the demands of the petroleum, petrochemical, and fine chemical sectors.

Enhancing Brønsted and Lewis Acid Sites of the Utilized Spent RFCC Catalyst Waste for the Continuous Cracking Process of Palm Oil to Biofuels

Catalyst waste from the Residue Fluid Catalytic Cracking (RFCC) plant process can still be utilized to catalyze the catalytic cracking of palm oil to fuels. However, the catalyst waste should be re...

Effect of Temperature on Plasma-Assisted Catalytic Cracking of Palm Oil into Biofuels

Plasma-assisted catalytic cracking is an attractive method for producing biofuels from vegetable oil. This paper studied the effect of reactor temperature on the performance of plasma-assisted catalytic cracking of palm oil into biofuels. The cracking process was conducted in a Dielectric Barrier Discharge (DBD)-type plasma reactor with the presence of spent RFCC catalyst. The reactor temperature was varied at 400, 450, and 500 ºC. The liquid fuel product was analyzed using a gas chromatography-mass spectrometry (GC-MS) to determine the compositions. Result showed that the presenceof plasma and catalytic role can enhance the reactor performance so that the selectivity of the short-chain hydrocarbon produced increases. The selectivity of gasoline, kerosene, and diesel range fuels over the plasma-catalytic reactor were 16.43%, 52.74% and 21.25%, respectively, while the selectivity of gasoline, kerosene and diesel range fuels over a conventional fixed bed reactor was 12.07%, 39.07%, and 45.11%, respectively. The increasing reactor temperature led to enhanced catalytic role of cracking reaction,particularly directing the reaction to the shorter hydrocarbon range. The reactor temperature dependence on the liquid product components distribution over the plasma-catalytic reactor was also studied. The aromatic and oxygenated compounds increased with the reactor temperature.©2020. CBIORE-IJRED. All rights reserved

Process simulation of organic liquid products fractionation in countercurrent multistage columns using CO2 as solvent with Aspen-Hysys

Fractionation of liquid phase products (OLP), obtained by thermal catalytic cracking of palm oil, simulated in multistage countercurrent absorber/stripping columns using SC-CO2 as solvent with Aspen-Hysys, at 333 K, 140 and 180 bar, and (S/F) = 12, 15, 17, 25, 30, 38. RK-Aspen EOS applied to correlate equilibrium data of binary systems (OLP)-i/CO2. Composition of OLP used to predict thermophysical properties and acentric factor of OLP compounds by group-contribution methods. The effect of pressure and (S/F) on process performance evaluated by computing the yield and recoveries of hydrocarbons, olefins, oxygenates, carboxylic acids. The regressions show that RK-Aspen EOS describe well phase equilibrium data, showing AAD between 0.8% and 1.25% and 0.01%– 0.66% for the liquid and gaseous phases. The best deacidifying conditions obtained at 333 K, 140 bar, and (S/F) = 17. Simulations show that SC-CO2 was able to deacidify OLP and to obtain fractions with lower olefins content.

Deacidification of organic liquid products by fractional distillation in laboratory and pilot scales

This work aims to investigate the de-acidification of organic liquid products, obtained by catalytic cracking of palm oil (Elaeis guineensis Jacq) using Na2CO3 as catalyst, by fractional distillation. The distillation of OLP carried out in laboratory, using columns of different heights with and without reflux, and in pilot scale. OLP and distillation fractions physicochemical characterized for density, kinematic viscosity, acid value, saponification value, refractive index, ester index, free fatty acids, flash point, and copper strip corrosion. The OLP analyzed by GC–MS and FT-IR, and light diesel-like fractions by FT-IR, NMR, and GC–MS. The experiments carried out in laboratory scale with and without reflux showed biofuels (distillates) yields between 62.15 and 76.41% and 71.65 and 89.44% (wt.), respectively, while that in pilot scale was 32.68% (wt.). For the experiments in laboratory scale, the yields of distillates decrease exponentially with column height, with and without reflux, while those of bottoms products increase exponentially. In addition, the yields of distillates and gas increase with increasing Na2CO3 content, while that of bottom products decrease. The yield of light diesel-like fractions, with and without reflux ranged between 48.82 and 63.18, and 20.23 and 21.43% (wt.), respectively. The column height had no significant effect on the density of distillation fractions, with and without reflux. The densities of gasoline, kerosene, and light diesel with reflux, superpose exactly those of kerosene, light diesel, and heavy diesel without reflux. The kinematic viscosity of distillation fractions decreases with increasing column height for the experiments with and without reflux, while the acid values decrease. For the distillation experiments in pilot scale, the acid values of gasoline, kerosene, and light diesel-like fractions were 0.33, 0.42, and 0.34mg KOH/g. FT-IR of distillation fractions in pilot scale and NMR of light diesel-like fraction in laboratory scale, column height of 50cm, under reflux identified the presence of aliphatic hydrocarbons and the absence of carbonyl groups. The GC–MS analysis identified in OLP composition 92.84% (area.) hydrocarbons and 7.16% (area.) oxygenates. The light diesel-like fraction contains 100% hydrocarbons with an acid value of 0.34mg KOH/g, density of 0.7862g/cm3, and kinematic viscosity of 1.52mm2s−1, proving the feasibility of OLP de-acidification by fractional distillation.

Thermal catalytic cracking of crude palm oil at pilot scale: Effect of the percentage of Na2CO3 on the quality of biofuels

In this study, the influence of catalyst content on the physical–chemical properties, yield, and chemical composition of organic liquid products (OLP) obtained by thermal catalytic cracking of palm oil (Elaeis guineensis, Jacq.) was studied at a pilot scale. The experiments were carried out in a reactor of 143L, running in batch mode at 450°C and 1 atm, using 5%, 10%, 15%, and 20% (w/w) Na2CO3 as the catalyst. Physical–chemical characterization of OLP was conducted for acid value, saponification value, specific gravity, refractive index, kinematic viscosity, copper strip corrosion, and flash point. The chemical composition of OLP was determined by gas chromatography–mass spectrometry (GC–MS). As the catalyst content increased, the kinematic viscosity of OLP decreased from 6.59 to 3.63mm2s−1 and the acid value from 51.56 to 1.26mg KOH/g. The GC–MS analysis showed that OLP comprise hydrocarbons (normal paraffin, olefin, and naphthenic) and oxygenated compounds (carboxylic acids, alcohols, ketones, and esters), with a high dependency on the catalyst level. As the catalyst content increased, the concentration of hydrocarbons increased, whereas the concentration of oxygenates decreased. The optimal sodium carbonate catalyst level was found to be 15% (w/w). This gave the highest rate of conversion into biofuel, of which around 60% was OLP, and produced biofuels with the lowest acid values. The physical–chemical properties were within the limits fixed by ANP No. 65 (Diesel S10 specification) due to their high hydrocarbon content (92.84%) and low oxygenate content (7.16%). The hydrocarbons produced had characteristics similar to those of petroleum diesel, offering the potential to replace petroleum fuels without requiring deacidification or deoxygenation pretreatment.

Catalytic Cracking Of Palm Oil To Gasoline Over Pretreated Cu–ZSM–5

compounds. Key words: Zeolite, H-ZSM-5, Cu-ZSM-5, hydrogen pretreatment, cracking

Hydrodynamic study of zeolite-based composite cracking catalyst in a transport riser reactor

A composite catalyst containing H-Y zeolite and kaolin suitable for catalytic cracking of palm oil for the production of biofuels was synthesized by sol–gel–sieve method. In this study, we report the results of the hydrodynamic studies using a composite catalyst in a transport riser reactor. The hydrodynamic study confirms that the pressure difference across the transport riser reactor varies with the superficial gas velocity and it becomes significant at the bend section of the reactor. The pressure buildup occurs when the superficial fluid velocity reaches bubbling fluidization velocity. A model incorporating different dimensionless groups correlated with the pressure difference in transport riser reactor at different operating conditions. The proposed model predicted the pressure drop within an average error of ±20% in a transport riser reactor.

Modeling and Simulation of Transport Riser Reactor for Catalytic Cracking of Palm Oil for the Production of Biofuels

The catalytic cracking of palm oil over rare earth-Y (REY) catalyst for the production of biofuels in a transport riser reactor at atmospheric pressure, temperature of 673–773 K, catalyst-to-oil ratio (CTO) of 5–10, is reported. The cracking was studied at different residence times and axial reactor lengths. In the present study, palm oil-based fatty acid mixture (FAM) cracking kinetics was found to be similar to the cracking kinetics of palm oil, because both FAM and palm oil consist of different fatty acids, with oleic acid as the major component. A six-lump, nonisothermal kinetic model for the plug-flow reactor was developed to analyze palm oil cracking data. The model includes unconverted palm oil, gasoline fraction, kerosene fraction, diesel fraction, gaseous product, and coke. A nonselective catalyst deactivation function was incorporated in the model. The experimental cracking activity data obtained in the microreactor were used for the evaluation of kinetic parameters. The product yields predicted...

Catalytic cracking of palm oil for the production of biofuels: Optimization studies

Oil palm is widely grown in Malaysia. Palm oil has attracted the attention of researchers to develop an 'environmentally friendly' and high quality fuel, free of nitrogen and sulfur. In the present study, the catalytic cracking of palm oil to biofuel was studied over REY catalyst in a transport riser reactor at atmospheric pressure. The effect of reaction temperature (400-500 degrees C), catalyst/palm oil ratio (5-10) and residence time (10-30s) was studied over the yield of bio-gasoline and gas as fuel. Design of experiments was used to study the effect of operating variables over conversion of palm oil and yield of hydrocarbon fuel. The response surface methodology was used to determine the optimum value of the operating variables for maximum yield of bio-gasoline fraction in the liquid product obtained.