Catalyst For Esterification Reaction Research Articles

Sugar derived hydrochar catalysts for enhanced biodiesel production via esterification

Sugars and sugar alcohols are renewable raw materials which can be used for char production. Their acid-catalyzed hydro-carbonization results in the formation of carbon materials with acidic functional groups on the surface, which makes them suitable to be used as heterogeneous catalysts in esterification reactions. Hydrochars materials were prepared by low-temperature slow carbonization of glycerol, xylitol, sucrose, and glucose in the presence of different amounts of H2SO4 (mass ratios from 1 to 4). The hydrochars were extensively characterized and tested in the methanolysis reaction of oleic acid. All the carbon materials were amorphous with features of polyaromatic sheets with hydroxyl (–OH), carboxylic acid (–COOH), and sulfonic (−SO3H) functional groups. The effect of the oleic acid water content on catalytic performance was studied, showing a strong inhibition effect due to the hygroscopic character of catalysts induced by sulfonic groups and other surface groups with oxygen. Under the conditions evaluated (5 % wt. of catalyst, methanol/oleic acid = 9 M ratio, methanol reflux temperature) the sucrose-derived catalyst prepared with the highest H2SO4 content showed the best performance, leading to methyl oleate yield > 90 % after 2 h of reaction, which is only achieved by the majority of analogous catalysts reported in the literature after 4 to 8 h of reaction. The data showed that there is a correlation between the methyl ester yield and the graphitization of the catalyst, as this makes the catalyst more hydrophobic, which is an advantage in esterification catalysts.

A Novel PolyHIPE‐like Catalyst for Esterification Reactions: on the Synthesis of Sulfonated Poly(styrene‐co‐n‐acylglycerol) and its Use for Efficient Conversion of Oleic Acid to Methyl Oleate

AbstractThe current work describes the synthesis of a new polyHIPE‐like sulfonated poly(styrene‐co‐n‐acylglycerol) and its use as an efficient heterogeneous catalyst to convert oleic acid into methyl oleate in esterification reactions. This new environmentally friendly polymer incorporates n‐acylglycerol macromonomer as a versatile strategy for glycerol valorization. Macroporous micrometric polymer particles are synthesized through suspension polymerization process without using porogenic agents. polyHIPE‐like copolymers formed with different feed compositions of styrene and n‐acylglycerol are chemically modified via sulfonation reactions to form a highly efficient catalyst for esterification of oleic acid to methyl oleate, exhibiting conversions lying in the interval from 52% to 96%, depending mainly on the amount of n‐acylglycerol macromonomer into the copolymer chains. The experimental results indicate the great potential of this new heterogeneous catalyst based on modified poly(styrene‐co‐n‐acylglycerol) to be successfully employed in esterification reactions of vegetable oils intended for the production of long chain alkyl esters of carboxylic acids, widely used as biofuels.

Nano-silica melamine trisulfonic acid as an efficient and reusable heterogeneous catalyst in esterification reactions

Nano-silica melamine trisulfonic acid as an efficient and reusable heterogeneous catalyst in esterification reactions

Empirical Modeling and Optimization of Base Activated Ngbo Catalysts in Esterification Reaction Using Response Surface Methodology

In this work, Box-Behnken’s Response Surface Methodology (RSM) was applied to study the esterification reaction effectiveness of base-activated Ngbo clay catalyst. The esterification was monitored based on temperature, time duration, amount of reactant, catalyst weight, and particle size. The Box-Behnken’s Response Surface Methodology indicates that the base clay-catalyzed esterification reactions proceed through dual Acid-complex and Alcohol- complex mechanisms, with the alcohol mechanism dominating. The acetic acid and ethanol esterification efficiencies by base-activated Ngbo clay catalyst optimized using RSM models indicated the esterification percentage was ˃99%. The predicted and experimental values under the same conditions showed less than 5% difference, thereby making the Box-Behnken design approach an efficient, effective, and reliable method for the esterification of acetic acid with ethanol. The produced catalyst was optimized using A-One way ANOVA modelled, which indicated that the correlation coefficient of the regression was 0.9940. The result implied that 99.40% of the total variation in the esterification reaction was due to the experimental variables. The obtained data in this study indicated that this process could be applied in the esterification of acetic acid to avoid the drawbacks of corrosion, loss of catalyst, and environmental problems.

Preparation of Ti Material Supported SBA-15 Functionalized with Sulfonic Acid Environmental Friendly Catalyst: Application for Esterification Process

Kinetics of catalytic esterification between propionic acid and n-butanol has been studied in a batch reactor by using a Ti-supported SBA-15 catalyst with sulfonic acid. The synthesized catalyst is used to test the efficacy of catalyst for esterification reaction. The SBA-15 acidity is tied to incorporation of Ti and -SO3H groups through and the use of Si/Ti with Si/S molar ratios. The results are mesoporous materials with a typical hexagonal structure of the Ti SBA-15 and wide areas and high pore diameters that are operated with sulfonic groups. The addition of SBA to Ti leads mainly to catalytic materials with Bronsted and Lewis acid sites. Ti SBA-15 is the most effective catalyst for sulfonic acid, with the highest consents of Lewis acid sites and deactivation resistance and low hydrophilicity. The effect of temperature, catalyst amount, and molar ratio on reaction kinetics has been studied. The conversion of propionic acid is found to be 91% at 115°C at a 2 : 1 ratio of n-butanol to propionic acid molars with 2% of sulfonic acid supported Ti SBA-15. The Eley-Rideal kinetic model is used to fit the experimental data. The activation energy and kinetic factor are found to be 29.63 kJ mol–1 and k o 0.549 L2 g-1 mol-1, respectively.

Optimization of Acid Activated Ngbo Clay Catalysts in Esterification Reaction Using Response Surface Methodology

In this study, Box-Behnken”s Response Surface Methodology (RSM) was applied to study the esterification reaction effectiveness of acid activated Ngbo clay catalyst. The esterification were monitored based on the process conditions of temperature, duration, amount of reactant, catalyst weight and particle size. The Box--Behnken’s Response Surface Methodology indicates that the acid clay-catalysed esterification reactions proceed through dual mechanisms of Acid-complex and Alcohol-complex mechanisms with the Alcohol mechanism dominating. The esterification efficiencies of acetic acid and ethanol by acid activated Ngbo clay catalyst optimized using RSM models indicated the estimated esterification percentage of ˃99%. The predicted and experimental values under the same conditions showed less than 5% difference thereby making the Box-Behnken design approach an efficient, effective and reliable method for the esterification of acetic acid with ethanol. The produced catalyst was optimized using A-One way ANOVA modelling, which indicated correlation coefficient of the regression of 0.9940, which implies that 99.40% of the total variation in the esterification reaction was attributed to the experimental variables. The result obtained indicated that the process could be applied in the esterification of acetic acid to avoid the drawbacks of corrosion, loss of catalyst and environmental problems.

Encapsulation of heteropolyacids within hollow microporous polymer nanospheres for sustainable esterification reaction

Herein, the Keggin structural phosphotungstic acid (HPW) has been successfully encapsulated within hollow microporous polymer nanospheres (H-MPNs) by a “ship-in-bottle” approach. The H-MPNs are formed by self-assembly induced by hyper-crosslinking of polylactide-b-polystyrene (PLA-b-PS). The obtained catalysts (HPW@H-MPNs) exhibit more sustainable availability than the previously reported HPW-supported catalysts in esterification reaction. This excellent sustainability can be attributed to the stable microporous channels in H-MPNs which are smaller than the molecular size of HPW, thereby effectively preventing the HPW from leaking out. Moreover, such catalysts also perform well in terms of catalytic activity and universality because of the combination of a hollow structure in the interior and permeable pore channels in the shells. This type of polymer carrier and general encapsulation method may provide a new strategy for developing more sustainable catalysts for various chemical reactions.

Trimetallic@Cyclodextrin Nanocomposite: Photocatalyst for Degradation of Amoxicillin and Catalyst for Esterification Reactions

The industry is looking for new materials which can respond to specific applications that exclusively advance materials can provide. In this context, nanoparticles and nanocomposites opened an interesting method for designing specific properties which can be modulated according to the requirements. The preparation of biomolecules supported trimetallic nanoparticles and some other derives is a good example of the complex systems that can be designed for getting exclusive properties. This study is based on the preparation of new cyclodextrin supported Fe/La/Zn trimetallic nanocomposite by the microemulsion technique. Photocatalytic degradation of amoxicillin was performed using cyclodextrin-Fe/La/Zn. 78% of amoxicillin photodegradation along 4 hours of photoirradiation was achieved. Finally, the catalytic nature of new material was explored for oxidation and esterification reactions. The present study revealed that this advanced multifunctional nanomaterial can be successfully employed for environmental remediation and catalytic activities.

Catalytic Activity of Char Obtained from Fast Pyrolysis in Esterification Reactions

In this study different pathways for obtaining activated carbon with catalytical activity were analysed. Industrially fast pyrolysis is an efficient way of lignocellulosic biomass processing, since in this process various important high value chemicals are obtained. Biochar is obtained as the by-product in fast pyrolysis process from which activated carbon can be acquired with further chemical activation. Different methods for chemical activation of biochar were tested with the obtained activated charcoals being used as a catalyst in esterification reactions to evaluate their potential use as a heterogenic catalyst. Highest catalytical activity was observed when biochar was pre-treated with sulfuric acid at 80 °C for 24 hours. The obtained activated charcoal could be used as a catalyst for up to five times with no noticeable decrease in catalytic activity.

MWCNTs/SnZrMoP nano-composite as Ba (II)-selective electrode and heterogeneous catalyst for esterification of primary alcohols

The present investigation covers the synthesis, characterization and applications of a novel nano-composite of multiwalled carbon nanotubes–tin zirconium molybdophosphate (MWCNTs–SnZrMoP) ion exchanger. The synthesized material was characterized by various instrumental techniques viz. Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), and thermogravimetric/ differential thermal analysis (TGA/DTA). The nano-composite exhibited an ion exchange capacity of 2.56 meq g−1, which is higher than its inorganic counterpart SnZrMoP (1.95 meq g−1). The distribution studies confirmed that the as-synthesized nano-composite was selective for barium ions. The nano-composite was employed to fabricate an ion-selective electrode which showed a sub-Nernstian response for barium ions in the concentration range 1 × 10−7 M—1 × 10−1 M, with a response time of 11 s. The average slope of the calibration curve was observed to be 23.3 mV/decade with 1.78 × 10−8 M as limit of detection (LOD). The synthesized material was also used as a heterogeneous catalyst in esterification reactions of some primary alcohols due to its high mechanical, thermal and chemical stability. The esters produced were characterized by nuclear magnetic resonance (1H-NMR) and FT-IR techniques.

MODIFICAÇÃO QUÍMICA DO POLIPROPILENO ATRAVÉS DA INTRODUÇÃO DE GRUPOS SULFÔNICOS PARA APLICAÇÃO COMO CATALISADOR EM REAÇÕES DE ESTERIFICAÇÃO

CHEMICAL MODIFICATION OF POLYPROPYLENE THROUGH THE INTRODUCTION OF SULPHONIC GROUPS FOR APPLICATION AS CATALYST IN ESTERIFICATION REACTIONS. In this work, the chemical modification of pristine polypropylene was carried out through sulfonation reactions with concentrated sulfuric acid (PPS1) and fuming sulfuric acid (PPS2), for production of heterogeneous catalysts used in esterification reactions. Fourier transform infrared spectroscopy, elemental analysis, degree of substitution and ion exchange capacity showed that both sulfonation agents were effective to promote the functionalization of polypropylene, with the fuming sulfuric acid capable of promoting a greater chemical modification. The materials catalytic activity in esterification reaction of oleic acid with methanol was evaluated at 100 ºC, methanol: oleic acid molar ratio of 78:1 and with 5 wt% of catalyst (referred to oleic acid weight). It was observed that reaction catalyzed by PPS1 converted 68.02% of oleic acid to methyl oleate in 3 hours of reaction, while PPS2 reached 86.47% conversion in five hours, showing even greater catalytic efficiency than the commercial ion exchange resin, Amberlyst 15. Therefore, the conditions employed for the sulfonation of polypropylene were satisfactory to produce materials with acid characteristics necessary to catalyze the esterification reaction of oleic acid with methanol.

The Use of Natural Zeolite as A Catalyst for Esterification Reaction Between Glycerol and Oleic Acid

Natural zeolite in Indonesia generally divided into 2 types, which are mordernite and clinoptilolite. As far the use of zeolites is very limited. This experiment tries to use both types of natural zeolites to find out its work. The purpose of this experiment is testing the performance of mordenite natural zeolite from Bayah-Indonesia and clinoptilolite from Lampung- Indonesia in the esterification reaction between glycerol and oleic acid integrated by several variable that affect the reaction. The experiment will be done by using three-neck rounded flask batch reactor. The result showed that modernite zeolite has a better performance compared to clinoptilolite zeolite. To get the oleic acid conversion of 70%, clinoptilolite zeolite needs 4% catalyst of glycerol weight and reactant ratio of 6:1 mole of glycerol/mole of oleic acid, Meanwhile the mordernite zeolite only needs 2% catalyst of glycerol weight with reactant ratio of 4:1 mole of glycerol/mole of oleic acid.Keywords: natural zeolite; glycerol; reaction; diffusion

Preparation of mesoporous silica supported sulfonic acid and evaluation of the catalyst in esterification reactions

Sulfonic acid group was chemically bonded on either amorphous or highly ordered mesoporous silica surface through hydrothermal treatment with Na2SO3/NaHSO3 aqueous solution followed by acidification after the silica was grafted with surface propyl-chloride group. N2 adsorption–desorption was used for the characterization of the topology properties of the mesoporous silica–SO3H catalysts and the acid amount was studied by titration. Solid NMR and FTIR techniques were employed for detection of the surface groups and covalently bonded propyl–SO3H species was identified. The solid acid catalyst was evaluated in esterification reactions between various carboxylic acids and short-chain alcohols and the results demonstrated that the mesoporous silica–SO3H catalyst shows not only a high activity comparable to that of reported KIT-6-120–SO3H catalyst, but also an excellent recyclability (without deactivation after reused for eight times in lauric acid esterification with ethanol). The good performance and strong acidic character of the catalyst was correlated with the large pore size, well accessible acid sites as well as covalently grafted active structure on the catalyst.

Ion Exchangers as Catalyst in Esterification Reaction: A Review

Ion Exchangers as Catalyst in Esterification Reaction: A Review

Potential of Acid-Activated Bentonite and SO3H-Functionalized MWCNTs for Biodiesel Production From Residual Olive Oil Under Biorefinery Scheme

Application of acid-activated bentonite and SO3H-functionlized multiwall carbon nanotubes (SO3H-MWCNTs) for lowering free fatty acids (FFAs) content of low-quality residual olive oil, prior to alkali-catalyzed transesterification was investigated. The used bentonite was first characterized by Scanning Electron Microscopy (SEM), Inductively Coupled Plasma mass spectrometry (ICP-MS), and X-ray fluorescence (XRF), and was subsequently activated by different concentrations of H2SO4 (3, 5, and 10 N). Specific surface area of the original bentonite was measured by Brunauer, Emmett and Teller (BET) method at 45 m2/g and was best improved after 5 N-acid activation (95-98°C, 2 h) reaching 68 m2/g. MWCNTs was synthesized through methane decomposition (Co-Mo/MgO catalyst, 900°C) during the chemical vapor deposition (CVD) process. After two acid-purification (HCl, HNO3) and two deionized-water-neutralization steps, SO3H was grafted on MWCNTs (concentrated H2SO4, 110°C for 3 h) and again neutralized with deionized water and then dried. The synthesized SO3H-MWCNTs were analyzed using Fourier-Transform Infrared Spectroscopy (FTIR) and Transmission Electron Microscopy (TEM). The activated bentonite and SO3H-MWCNTs were utilized (5 wt.% and 3 wt.%, respectively) as solid catalysts in esterification reaction (62°C, 450 rpm; 15:1 and 12:1 methanol-to-oil molar ratio, 27 h and 8 h, respectively) to convert FFAs to their corresponding methyl esters. The results obtained revealed an FFA to methyl ester conversion of about 67% for the activated bentonite and 65% for the SO3H-MWCNTs. More specifically, the acid value of the residual olive oil was decreased significantly from 2.5 to 0.85 and 0.89 mg KOH/g using activated bentonite and SO3H-MWCNTs, respectively. The total FFAs in the residual olive oil after esterification was below 0.5%, which was appropriate for efficient alkaline-transesterification reaction. Both catalysts can effectively pretreat low quality oil feedstock for sustainable biodiesel production under a biorefinery scheme. Overall, the acid-activate bentonite was found more convenient, cost-effective, and environment-friendly than the SO3H-MWCNTs.

Optimization of Lignin-Based Biocatalyst Production from Pine Sawdust and Wheat Straw.

Pine sawdust and wheat straw are abundant lignocellulosic wastes that have been recently converted into bioethanol under a biochemical platform scheme whose main waste is lignin. Lignin can be transformed into a wide variety of high added-value products, including its functionalization as a catalyst. A key step in the synthesis of a lignin-based catalyst is the sulfonation reaction, whose operating conditions, namely, H2SO4 to lignin ratio (mL/g), temperature and time, have been arbitrarily chosen. In this contribution, an optimization methodology (i.e., Box-Behnken) is applied in order to found the operating conditions during the sulfonation reaction that maximizes the total acid sites density of lignin-based catalysts from pine sawdust and wheat straw. The optimization results show that the time in sulfonation reactions can be significantly reduced, compared to those previously reported, without affecting the performance of both catalysts in esterification reactions. These results could be further considered for energy and costs reduction purposes during the conceptual design engineering of the sulfonation reaction.

Biodiesel from Fatty Acids Found in Brazilian Native Cultures as Soybean and Cotton Using the Nanocatalyst Ni<sub>0.5</sub>Zn<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub>

Biodiesel is a biodegradable fuel derived from renewable biomass, such as soybean and cottonseed oil, which may be obtained by different processes and requires a material to catalyze the obtaining reactions. The irons spinel comes overlapping as excellent materials to catalyze the biodiesel production reactions. Thus, the purpose of this work was the use of Ni0.5Zn0.5Fe2O4 nanoferrite as a catalyst in esterification reactions. The nanoferrite was synthesized by combustion in large scale, 200g/batch, where time and the temperature of the reactions were measured, and characterized by XRD and measuring its surface area. The biodiesel was obtained from methyl and ethyl esterification of acidified soybean oil and cottonseed, at a temperature of 160°C for 1 hour, molar ratio 1:15, 3% of catalyst and analyzed by chromatography. The nanoferrite has shown peaks of greater intensity corresponding to a majority crystal phase of the spinel and a surface area of ​​64.17m2/g. The conversion results for the soybean oil were 99.08% in methyl route and 98.38% in ethyl route. For cottonseed oil were 88.79% in methyl route and 78.65% in ethyl route.

Characterization and reactivity of zirconia-doped phosphate ion catalyst prepared by sol–gel route and mechanistic study of acetic acid esterification by ethanol

Phosphated zirconia prepared by sol–gel method has been used as catalyst in esterification reaction of acetic acid with ethanol. Optimization of different preparation parameters on the catalyst was studied, such as the effect of molar ratio n P/n Zr, surfactant assisted synthesis, calcination temperature, and the effect of the drying mode. Catalysts were characterized by N2 physisorption at −196 °C, X-ray diffraction, FTIR spectroscopy, and 31P MAS NMR spectroscopy. The obtained results show that an increase in phosphate content partially inhibits the development of tetragonal t-ZrP phase and leads to a rise of both specific area and pore size of the catalyst. Besides, the introduction of the surfactant in the preparation step develops this phase and enhances the size of pores, but decreases specific area. However, calcination of the catalyst allows the development of tetragonal ZrO2 phase and causes the disappearance of ZrP phase. The evacuation of the solvent at its supercritical conditions promotes the development of both tetragonal phase of zirconia and pore size but slows that of the phases related to the ZrP species. Catalytic properties of acid esterification by ethanol were correlated to catalyst characteristic data, suggesting that t-ZrP phase and doping agent-support interaction stabilize active sites of the catalyst. Kinetic and mechanism study shows that catalytic reaction occurs with a first order and takes place through Eley–Rideal mechanism in which adsorbed acetic acid species react with ethanol in fluid phase to form corresponding ester. Application of Eyring theory shows that the adsorption step is characterized by an endothermic character and a rapid associative mechanism occurs between adsorbed species and the second reactant. Eley–Rideal mechanism of acetic acid esterification by ethanol over xerogel catalyst XZrP0.05

DBU-Based Dicationic Ionic Liquids Promoted Esterification Reaction of Carboxylic Acid with Primary Chloroalkane Under Mild Conditions

A series of DBU-based (DBU = 1, 8-diazabicyclo [5.4.0] undec-7-ene) dicationic ionic liquids with different anions were successfully synthesized by the reaction of DBU and 1, 6-dichlorohexane. Therein, the dicationic ionic liquid 1, 1′-(hexane-1, 6-diyl)bis(1, 8-diazabicyclo [5.4.0]undec-7-enium) dichlorine (IL-1) was successfully employed as an efficient catalyst in esterification reaction of carboxylic acids with primary chloroalkanes under mild conditions without any additional basic reagents. Moreover, the optimum catalyst could be efficiently reused for five times without any significant change on the catalytic effect. The improved protocol is not only efficient, but also green and pollution-free.

Penentuan Konsentrasi Aktivator Asam Sulfat Terbaik pada Pretreatment Zeolit Alam Lampung (Zal) sebagai Katalisator untuk Reaksi Esterifikasi Gliserol dan Asam Asetat Menjadi Triacetin

Telah dilakukan penelitan untuk memperoleh konsentrasi aktivator asam sulfat terbaik pada tahapan pretreatment Zeolit Alam Lampung sebagai katalisator pada reaksi esterifikasi gliserol dan asam asetat membentuk triacetin. Proses pretreatment yang dilakukan adalah aktivasi secara kimia dimana zeolit direndam dalam asam sulfat dengan konsentrasi 0,2 ; 0,3 dan 0,4 N. Zeolit hasil aktivasi dianalisis rasio SiO2/Al2O3 dengan analisis XRF. Kemudian ketiga pretreated zeolit dengan variasi konsentrasi aktivator tersebut diuji kinerjanya sebagai katalis pada reaksi pembentukan triacetin dari gliserol dan asam asetat dengan waktu reaksi 90 menit dan dilakukan pengambilan sampel setiap 15 menit lalu dibandingkan dengan reaksi menggunakan katalis zeolit tanpa aktivasi serta reaksi tanpa katalis. Konversi tertinggi dan terbaik didapatkan pada katalis pretreated zeolit 0,2 N asam sulfat dengan konversi sebesar 11,75 %. Analisis XRF memberikan hasil bahwa semakin meningkat konsentrasi aktivator asam sulfat, semakin meningkat juga rasio SiO2/Al2O3 zeolit. Analisis FTIR menunjukkan perlakuan aktivasi pada zeolit tidak menimbulkan perubahan struktur yang signifikan.