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A mathematical model was proposed to study the microkinetics of esterification reaction of oleic acid with ethanol over prepared HY zeolite catalyst. The catalyst was prepared from Iraqi kaolin source and its properties were characterized by different techniques. The esterification was done under different temperature (40 to 70˚C) with 6:1 for mola...
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... esterification reaction of oleic acid in batch reactor was carried out in a laboratory scale reactor as shown in Figure 1. The apparatus used for the experiment consists of 500 ml three neck flat bottom glass flask and electrical heater with magnetic stirrer arrangement to achieve a perfect contact among the reactants. ...
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... esterification reaction of oleic acid in batch reactor was carried out in a laboratory scale reactor as shown in Figure 1. The apparatus used for the experiment consists of 500 ml three neck flat bottom glass flask and electrical heater with magnetic stirrer arrangement to achieve a perfect contact among the reactants. ...
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Nanocrystalline ZSM-5 and micro-mesoporous ZSM-5/MCM-41 composite zeolite were synthesized by hydrothermal treatment-conventional method. Micro-mesoporous ZSM-5/MCM-41 were synthesized using alkaline leaching (treatment) method and two step crystallization. Loading of synthesized composite zeolite with transition metals copper and cobalt was conduc...
Nanocrystalline ZSM-5 and micro-mesoporous ZSM-5/MCM-41 composite zeolite were synthesized by hydrothermal treatment-conventional method. Micro-mesoporous ZSM-5/MCM-41 were synthesized using alkaline leaching (treatment) method and two step crystallization. Loading of synthesized composite zeolite with transition metals copper and cobalt was conduc...
The Biodiesel synthesis of castor oil by H-zeolite-catalyzed esterification and CaSiO 3 catalyzed transesterification was investigated. This research consisted of several steps: preparation, synthesis and characterization of catalyst and biodiesel. Zeolite catalyst was activated by H 2 SO 4 1M. CaSiO 3 catalyst precursors obtained from the impregna...
Citations
... This means that the effect of external mass transfer resistance was eliminated when a stirring rate of 400 rpm was applied. A similar phenomenon was also reported in previous studies (Abbas et al., 2016). To avoid the potential impact of the diffusion limitations on AcH conversion, all catalytic tests were carried out using a stirring rate of 400 rpm. ...
The global market for organic esters was estimated at around $89.4 billion in 2022, and is expected to continue to grow, reaching $127.4 billion in 2029. The wide application of mineral acids as homogeneous catalysts for the synthesis of organic esters causes several economic and environmental problems. For this reason, a lot of effort is undertaken to make esterification a more sustainable process. Nowadays, particular attention is paid to the development of new solid acid catalysts containing sulfonic acid groups (–SO3H) supported on organic polymers. This study fits into this scientific trend and aims at providing insight into the factors affecting the reactivity of –SO3H species anchored on hyper-cross-linked polymers (HCPs). For this purpose, polymers characterized by different cross-linking densities but with a comparable surface area of ca. 540-620 m2/g and a similar pore size of ca. 3.7 nm were applied as supports for anchoring of –SO3H through post-synthetic sulfonation. The loading of sulfonic acid species in all prepared catalysts varied from 1.19 to 2.22 mmol/g. Catalytic activity of the sulfonated HCPs (sHCPs) was evaluated in esterification of acetic acid with different alcohols. It was found that the key factors affecting the reactivity of –SO3H supported on HCPs are hydrophilicity of the polymer surface and the localization of the sulfonic acid species on the external surface of the polymer matrix. The latter was the most favoured during the post-synthetic sulfonation of the polymer characterized by the highest cross-linking density. In the case of this material, the –SO3H species were approximately 7 times more reactive than those of Amberlyst-15 (TOF = 11.36 vs. 1.57 h‒1, respectively). The most efficient sHCP used in this study reached approximately two times higher conversion of benzyl alcohol than Amberylst-15 (53.6 vs. 27.5% of n-butanol conversion) despite of the significantly lower loading of sulfonic acid species in the former polymer (2.22 vs. 4.66 mmol/g, respectively). It was also established that the catalytic esterification on the surface of sHCPs proceeded according to the Langmuir-Hinshelwood mechanism, in which chemisorption of the alcohol is the rate-determining step. Moreover, sHCP catalysts could be reused four times without significant deactivation.
... The discovery of natural zeolites, which are crystalline microporous aluminosilicates marks the beginning of advanced porous materials research [4]. Zeolites are widely used in petroleum refineries and chemical and petrochemical industries [5] because they have major economic benefits and are environmentally friendly [1,[6][7][8][9][10][11][12][13][14]. New zeolites with layered structures (MCM-22, MCM-36, MCM-49, and MCM-56) have medium pore sizes and various physicochemical characteristics [15]. ...
Silica-based mesoporous materials are a class of porous materials with unique characteristics such as ordered pore structure, large surface area, and large pore volume. This review covers the different types of porous material (zeolite and mesoporous) and the physical properties of mesoporous materials that make them valuable in industry. Mesoporous materials can be divided into two groups: silica-based mesoporous materials and non-silica-based mesoporous materials. The most well-known family of silica-based mesoporous materials is the Mesoporous Molecular Sieves family, which attracts attention because of its beneficial properties. The family includes three members that are differentiated based on their pore arrangement. In this review, the major applications of the Mobil Mesoporous Molecular Sieves family, such as catalysts, adsorbents, and drug delivery agents, have been surveyed. Furthermore, the synthesis of the Mesoporous Molecular Sieves materials, the silica sources, the importance of templates, and the mechanisms of the synthesis are discussed herein. Members of this material family are characterized by many physicochemical properties that are closely related to their high silica content, crystalline structure, and pore arrangement. Commonly, the members of this family have large surface areas, high pore volumes, small pore sizes, and narrow and uniform particle size distributions. These properties enable numerous industrial applications and opportunities for scientific studies to further develop existing materials or manufacture new ones.
... The importance of zeolite is due to its distinctive properties, including its high and tunable acidity, relatively high surface area, high thermal stability, and the size of microporous pores, which allow a smooth transfer of the reactant and product compounds through it [11][12][13]. Various types of zeolites have been as catalysts in the study of the esterification reaction such as; NaY zeolite [9,14], HY zeolite [15,17], ZSM-5 [18], FAU-type zeolite [19], modified ZSM-5, and 13X zeolite and its modified version [12,20]. ...
The study involved the removal of acidity from free fatty acid via the esterification reaction of oleic acid with ethanol. The reaction was done in a batch reactor using commercial 13X zeolite as a catalyst. The effects of temperatures (40 to 70 °C) and reaction time (up to 120 minutes) were studied using 6:1 mole ratio of pure ethanol to oleic acid and 5 wt. % of the catalyst. The results showed that acid removed increased with increasing temperature and reaction time. Also, the acidity removal rises sharply during the first reaction period and then changes slightly afterward. The highest acidity removal value was 67 % recorded at 110 minutes and 70 °C. An apparent homogeneous reversible reaction kinetic model has been proposed and solved with the experimentally obtained kinetics data to evaluate reaction rate constants versus temperature, pre-exponential factors, and activation energy values for the forward and the backward esterification reactions. The activation energies were 34.863 kJ/mol for the forward reaction and 29.731 kJ/mol for the backward reaction. The thermodynamics of the activation step of the forward and reverse reactions was studied based on the hypothesis of forming a complex material that decomposes into a product. The activation steps were studied using Eyring bimolecular collision theory approach, and both ΔH* and ΔS* were determined for forward and backward esterification reactions. The enthalpies of activation were 32.141 kJ/mol and 27.080 kJ/mol for the forward reaction and the backward reaction, and the entropies of activation were - 193.7 and -212.7 J/mol. K for the forward reaction and the backward reaction, respectively.
... An increase in the surface of the catalyst reduces the required amount of the catalyst. Currently, nanocatalysts are used for biodiesel synthesis, including Al-Sr [12], K 2 O/c-Al 2 O 3 [13], Ca/Fe 3 O 4 @SiO 2 [14], mixed oxide SiO 2 /ZrO 2 [15], La 2 O 3 [16], NaY zeolite [17,18], HY-zeolite [19], MCM-48 [20], 13X-Zeolite and its derivative [21,22], CaO [23], and manganese doped zinc oxide [24]. ...
In this work, a high purity FAU-type zeolite catalyst was prepared from shale rock and modified as a
heterogeneous efficient catalyst for biodiesel production from sunflower oil. The characterization prop-
erties for both of the prepared catalysts were determined using X-ray diffraction (XRD), scanning electron
microscopy (SEM), energy-dispersive X-ray spectroscopy (EDAX), Brunauer–Emmett–Teller (BET), and
Fourier-transform infrared spectroscopy (FTIR). The incipient wetness impregnation method was adopted
for loading the catalyst with three base precursors: NaOH, KOH, and Ca(OH)3. Different factors affecting
transesterification reaction onto modified Na-K-Ca-FAU zeolite were investigated such as; temperature
(35, 45, 55, and 65 �C), catalyst concentrations (2, 3,4, 5, and 6 wt%) and the molar ratio of methanol
to sunflower oil (3:1, 6:1, 9:1 and 12:1). The optimum conditions of transesterification reactions were
obtained for reaction time (4 h) and agitation rate (700 rpm) in a batch reactor at 65 �C reaction temper-
ature, 5% catalyst concentration, and a 9:1 M ratio of methanol to oil. The experimental results showed
that the conversion of triglyceride in sunflower oil to fatty acid methyl ester (FIME) increased from 48.62
to 91.6% when the FAU zeolite was loaded with 15 wt% of the three bases. The properties of the produced
biodiesel were evaluated within the standard performance ASTM D-6751. This study shows that the three
base precursors (i.e., NaOH, KOH, and Ca(OH)3) were successfully loaded onto support FAU zeolite and
functioned as excellent catalysts for biodiesel production. Theoretical considerations for kinetic modeling
in the heterogeneous transesterification reaction were investigated using MATLAB programming. The
experimental and theoretical considerations for kinetic modeling were fitted well.
... An increase in the surface of the catalyst reduces the required amount of the catalyst. Currently, nanocatalysts are used for biodiesel synthesis, including Al-Sr [12], K 2 O/c-Al 2 O 3 [13], Ca/Fe 3 O 4 @SiO 2 [14], mixed oxide SiO 2 /ZrO 2 [15], La 2 O 3 [16], NaY zeolite [17,18], HY-zeolite [19], MCM-48 [20], 13X-Zeolite and its derivative [21,22], CaO [23], and manganese doped zinc oxide [24]. ...
In this work, a high purity FAU-type zeolite catalyst was prepared from shale rock and modified as a heterogeneous efficient catalyst for biodiesel production from sunflower oil. The characterization properties for both of the prepared catalysts were determined using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDAX), Brunauer–Emmett–Teller (BET), and Fourier-transform infrared spectroscopy (FTIR). The incipient wetness impregnation method was adopted for loading the catalyst with three base precursors: NaOH, KOH, and Ca(OH)3. Different factors affecting transesterification reaction onto modified Na-K-Ca-FAU zeolite were investigated such as; temperature (35, 45, 55, and 65 °C), catalyst concentrations (2, 3,4, 5, and 6 wt%) and the molar ratio of methanol to sunflower oil (3:1, 6:1, 9:1 and 12:1). The optimum conditions of transesterification reactions were obtained for reaction time (4 h) and agitation rate (700 rpm) in a batch reactor at 65 °C reaction temperature, 5% catalyst concentration, and a 9:1 M ratio of methanol to oil. The experimental results showed that the conversion of triglyceride in sunflower oil to fatty acid methyl ester (FIME) increased from 48.62 to 91.6% when the FAU zeolite was loaded with 15 wt% of the three bases. The properties of the produced biodiesel were evaluated within the standard performance ASTM D-6751. This study shows that the three base precursors (i.e., NaOH, KOH, and Ca(OH)3) were successfully loaded onto support FAU zeolite and functioned as excellent catalysts for biodiesel production. Theoretical considerations for kinetic modeling in the heterogeneous transesterification reaction were investigated using MATLAB programming. The experimental and theoretical considerations for kinetic modeling were fitted well.
... Silica is an inorganic chemical compound plentifully available in the earth incrustation [1]. Still, despite being abundant, silica is generally made by way of synthesis for use mainly in the preparation of different types of adsorbents [2][3][4] and catalysts [5][6][7][8][9][10][11][12][13][14][15] used in chemical applications. Silica generally exists as alkoxysilane compounds, which can harm health. ...
... 10 In this work, a comprehensive reaction mechanism was proposed and used to develop a kinetic model based on an empirical first order power law for a HDO reaction. From a non-linear regression algorithm based on Levenberg-Marquardt, the apparent activation energy of stearic acid, as well as C 15 , C 16 , C 17 and C 18 hydrocarbons were found to be 175.4 kJ mol -1 , 387.7 kJ mol -1 , 377.2 kJ mol -1 , 250.0 kJ mol -1 and 190.9 kJ mol -1 , respectively. ...
Herein, for the first time, we demonstrate a novel continuous flow process involving the application of tetralin as a hydrogen donor solvent for the catalytic conversion of oleic acid to diesel-like hydrocarbons, using an efficient and stable carbon-supported bimetallic PdCu catalyst. Using Pd60Cu40/C, where 60:40 is the molar ratio of each metal, at optimum reaction conditions (360 °C and WHSV = 1 h-1), 90.5% oleic acid conversion and 80.5% selectivity to C17 and C18 paraffinic hydrocarbons were achieved. Furthermore, a comprehensive mechanistic based kinetic modelling - considering power rate law, L-H and E-R models was conducted. Kinetic expressions derived from the three kinetic models were investigated in rate data fitting through nonlinear regression using a Levenberg-Marquardt algorithm. Based on the statistical discrimination criteria, the experimental data of the dehydrogenation reaction of tetralin was best fitted by an L-H rate equation assuming the surface reaction as the rate controlling step. On the contrary, the kinetic data of the oleic acid deoxygenation reaction was well correlated with an L-H rate equation assuming single site adsorption of oleic acid with dissociative H2 adsorption. It was found that the rate limiting step of the overall reaction was the hydrogenation of oleic acid with an activation energy of 75.0 ± 5.1 kJ mol-1 whereas the dehydrogenation of tetralin had a lower activation energy of 66.4 ± 2.7 kJ mol-1.
... Values of molecular diffusivity of fatty acid in plant oil have been measured by Smits 1976 who found values of 4.2 × 10 −6 cm 2 s −1 for oleic acid and 3.7 × 10 −6 cm 2 s −1 for stearic acid in groundnut oil at 130 °C. Abbas et al. 2016 found values of the molecular diffusivity of oleic acid in ethanol of 6.1 × 10 −6 cm 2 s −1 at 40 °C and 1.09 × 10 −6 cm 2 s −1 at 70 °C. Values of molecular diffusivity at other temperatures can be calculated with the Wilke-Chang equation. ...
Deacidification of a vegetable oil by extraction and regeneration of the solvent by means of adsorption was studied. This novel approach to solvent regeneration is posed as an alternative to distillation in systems with high solvent-to-feed ratios in which evaporation of large solvent amounts is economically unattractive. An example was chosen of deacidification of sunflower oil by extraction with methanol and regeneration of the alcohol by adsorption over activated carbon. The example has application for the biodiesel and technical oils industries. The results showed that high temperatures of extraction increased the acid–methanol partition coefficient but also the mutual solubility of oil and methanol. One extraction stage with a solvent-to feed ratio of 20 (vol:vol) reduced the oil acidity to acceptable values. Regeneration of the extract by adsorption over activated carbon was found to be efficient. For regenerating the bed, elution with a hot solvent was studied. Adsorbent regeneration was completed to a high degree, with elution temperature being the most important variable. For exploring the influence of process variables on the performance of extraction-adsorption, simulation was used. Necessary parameters for mass transfer and adsorption were fitted from breakthrough tests with the aid of a linear driving force model. Simulation results confirmed the viability of the proposed process as an alternative for solvent regeneration of extraction units.
... Also, mesoporous materials have very high surface areas with regular pore size dimensions which make them a good support as active phases. The functionalization of these mesoporous materials by active acidic or basic moiety several contributions were made by various researches [11][12][13][14]. The shorter diffusion distances in MCM-48 arising from the pore structure may influence the distribution of the tethered group over the surface during the functionalization process [14]. ...
... The functionalization of these mesoporous materials by active acidic or basic moiety several contributions were made by various researches [11][12][13][14]. The shorter diffusion distances in MCM-48 arising from the pore structure may influence the distribution of the tethered group over the surface during the functionalization process [14]. ...
MCM-48 zeolites have unique properties from the surfaces and structure point of view as it’s shown in the results ,and unique and very sensitive to be prepared, have been experimentally prepared and utilized as a second-generation/ acid - catalyst for esterification reactions of oleic acid as a model oil for a free fatty acid source with Ethanol. The characterization of the catalyst used in the reaction has been identified by various methods indicating the prepared MCM-48 is highly matching the profile of common commercial MCM-48 zeolite. The XRF results show domination of SiO2 on the chemical structure with 99.1% and agreeable with the expected from MCM-48 for it's of silica-based, and the SEM results show the cubic crystallographic space group compatible with Ia3d space group giving the hexagonal surface structure. The AFM test gave an average particle diameter of 97.51 nm and an average catalyst roughness of 0.855 nm. Esterification reaction of oleic acid with ethanol on MCM-48 has been carried in a batch reactor with 5% the prepared MCM-48 zeolite catalyst loading gives 81% of conversion after one hour at 353K
... The amount of linoleic acid (LA) molecules adsorbed is equal to the sum of the amount desorbed and the amount of linoleic acid consumed by the chemical reaction on the surface and intrisically. 37 According to the following assumptions, the reaction rate (1) is described as: ...
Strategies to improve molecular transport and accessibility of ZSM-5 zeolites were investigated for the model reaction of esterification of linoleic acid with methanol for biodiesel production.
