Catalyst Amberlyst Research Articles

Esterification of decanoic acid with methanol using Amberlyst 15: Reaction kinetics

ABSTRACTMethyl decanoate is used as a surrogate fuel. The surrogate fuels are structurally similar to actual biodiesel. We synthesized methyl decanoate in a small batch reactor by esterification reaction using decanoic acid and methanol on solid acid catalyst Amberlyst 15 used in dry state. The outcome of different reaction parameters including catalyst loading, temperature, molar ratio, stirrer speed, water concentration effect, and adsorption on catalyst pellets were studied for optimization of rate of conversion. The effect of external and internal diffusion limitations on catalyst granules was calculated theoretically from the reaction kinetics data. An analysis of the reaction kinetics revealed that the esterification reaction was rate controlled by adsorption of methanol on the solid acid catalyst and the reaction can be modeled as Eley–Rideal model. Activation energy of the esterification reaction was 39.4 KJ/mol. Reaction enthalpy and entropy were found to be 29.81 kJ/mol and 87.38 J/mol. K, respectively.

Greening the esterification between isosorbide and acetic acid

This contribution deals with the investigation of greener conditions for the preparation of 2,5-diacetyl-isosorbide from the bio-based substances isosorbide and acetic acid. The influence of solvent, catalyst and reactant ratio on the course of the isosorbide conversion and selectivity to 2,5-diacetyl-isosorbide as well as to the intermediate 2-acetyl-isosorbide is examined. It was found that the conventionally used solvent toluene can be substituted by the greener solvent n-propyl acetate. Additionally, the homogeneous acid catalyst p-toluene sulfonic acid can be replaced by the heterogeneous catalyst Amberlyst-15, resulting in an easier isolation of the desired 2,5-diacetyl-isosorbide, this being an important precursor for the vasodilatory drug isosorbide-5-nitrate.

A Non-Precious Metal Promoting the Synthesis of 5-Hydroxymethylfurfural

In this work, a new kind of catalyst was prepared for synthesis of 5-hydroxymethylfurfural. Copper ions were incorporated into manganese oxide octahedral molecular sieves (K-OMS-2). The catalysts Cu-K-OMS-2 were characterized by measuring FTIR spectra, scanning electron microscope images, X-ray diffraction patterns, and temperature-programmed desorption (TPD) and temperature-programmed reduction (TPR) profiles. Thermogravimetric analysis (TGA) demonstrated that the stability of Cu-K-OMS-2 is almost the same as that of K-OMS-2. XRD patterns showed that introducing copper ions did not change the structure of K-OMS-2, but copper ions had an effect on the morphology of K-OMS-2 as illustrated by SEM images. TPD profiles demonstrated that both K-OMS-2 and Cu-K-OMS-2 possess basic and acidic sites, and Cu-K-OMS-2 has weak acidic sites. One-pot synthesis of 2,5-diformylfuran (DFF) from fructose was investigated under the catalysis of Cu-K-OMS-2 together with a commercial catalyst Amberlyst 15. The effect of reaction time and temperature on the DFF yield was investigated, and reaction temperature had an effect on the DFF yield. The effect of atomic ratio of Cu to Mn of Cu-K-OMS-2 on the DFF yield was also investigated. The DFF yield was improved 34.7% by Cu-K-OMS-2 in comparison to K-OMS-2, indicating the promotion effect of copper on the DFF yield. Consecutive use of Cu-K-OMS-2 demonstrated that after 6 cycles, the loss of DFF yield was 6.3%, indicating a good reusability of Cu-K-OMS-2.

Polydopamine-Mediated Formation of MnSn(OH)6 on Cryptomelane-Type Manganese Oxide for Catalyzing Glucose Isomerization to Fructose

Efficient isomerization of glucose into fructose contributes to the utilization of biomass producing 5-hydroxymethylfurfural (HMF). In this work, we have explored a novel catalyst for isomerization of glucose into fructose. By the mediation of polydopmaine (PDA), MnSn(OH)6 was formed on cryptomelane-type manganese oxide (OMS-2). The composite MnSn(OH)6/PDA@OMS-2 can efficiently catalyze the glucose isomerization to fructose, with a yield of fructose 47 ± 1.6%. When used together with the Bronsted acid catalyst Amberlyst-15, the HMF yield from glucose was 53 ± 2.5%. Consecutive use of the composite demonstrated that after eight cycles the activity can be retained in terms of the yield of fructose. The mechanism of polydopamine-mediated formation of MnSn(OH)6 has been investigated. The desired yield of fructose has been obtained by MnSn(OH)6/PDA@OMS-2, and the preparation of the catalyst has also shown advantages, including low cost and easy preparation, short preparation time (36 h), and low temperature (≤...

Biodiesel production by pervaporation-assisted esterification and pre-esterification using graphene oxide/chitosan composite membranes

Abstract In this study, a series of novel graphene oxide/chitosan (GO/CS) composite membranes was successfully synthesized and fully characterized. The performance of GO/CS composite membrane was then evaluated by integrating with the esterification of acetic acid with ethanol or the pre-esterification of palmitic acid with methanol, both essential in biodiesel production. Typically, esterification and pre-esterification are reversible reactions, which are limited by chemical equilibrium, resulting in a low product yield. In our study, reaction and separation were conducted in two separated steps or in a single one by means of a catalytic membrane. The preferential removal of water through the membrane in a PV-assisted process enhanced the conversion. The results show clearly that temperature, wt% of embedded GO within a polymeric CS-based membrane, and initial ratio of alcohol/acid are important parameters to enhance conversion because it acts on the kinetics of both pervaporation and esterification/pre-esterification. The enhanced catalytic membrane of the PV-assisted pre-esterification can only be observed when a proper amount of Amberlyst-15 catalyst is used. Additionally, the results of PV-assisted esterification/pre-esterification show that the ratio of water removal (by membrane) and water production (by esterification) rates play a significant role in evaluating the catalytic membrane. Under specific conditions, the conversions of PV-assisted esterification and pre-esterification by the catalytic membrane could be higher than those without PV-assisted up to 8% and 20%, respectively. This process could offer a key technology for biodiesel production in the future.

THE SYNTHESIS OF GLYCEROL CARBONATE FROM BIODIESEL BYPRODUCT GLYCEROL AND UREA OVER AMBERLYST 36

The increasing use of biodiesel as renewable fuels leads to the increasing of glycerol amount as a byproduct of biodiesel production. One of the glycerol derivative products that is environmentally friendly and renewable is glycerol carbonate. Glycerol carbonate is commonly used as a raw material for polymers, surfactants, emulsifiers, lubricants, paints, also used in the cosmetics and pharmaceutical industries. In this study, the research was carried out by using a batch reactor with a three-neck flask equipped with reverse cooling, thermometers, mercury stirrer, and heating mantle with the conditions of the reaction temperature around 373 413 K, mole ratio of reactants of urea: glycerol were 1:0,5, 1:1, 1:1,5, 1:2 and 1:4 and the concentration of catalyst were 1%, 2%, 3%, 4% and 5% respectively. Reaction was done for four hours. The results showed that the formation of glycerol carbonate from glycerol and urea using a catalyst Amberlyst 36 is affected by the catalyst concentration, reaction temperature and the ratio of reactants used. The highest glycerol conversion was obtained at 55.07% at a temperature of 393 K with mole ratio of urea and glycerol 1:0,5 and the percentage of catalyst 3% of the amount of glycerol.

Investigation about Energy Saving for Synthesis of Isobutyl Acetate in the Reactive Dividing-Wall Column

The reaction kinetic and chemical equilibrium for the production of isobutyl acetate via transesterification between methyl acetate and isobutanol is investigated as the presence of catalyst Amberlyst-15. The experimental kinetic parameters are obtained by the application of the Arrhenius equation. The novel reactive dividing-wall distillation process for production of isobutyl acetate via transesterification is proposed on the basis of a conventional reactive distillation process. The reactive dividing-wall distillation process is simulated and investigated for saving more energy and reducing the total annual cost (TAC) of the process. The energy consumption and the TAC of the reactive dividing-wall distillation process can be reduced by 26.40% and 18.25%, respectively, in comparison with the conventional RD process.

Selective and efficient dimerization of isobutene over H3PO4/activated carbon catalysts

Dimerization of isobutene to branched C8 olefins (precursors of high octane gasoline additives) was performed over eco-friendly activated carbon catalysts impregnated with phosphoric acid, under continuous gas phase operating conditions. A series of catalysts differing in phosphoric acid loading were prepared by incipient wetness impregnation and tested in the reaction carried out at various temperatures (100–260°C), with the use of an isobutene/isobutane mixture at a molar ratio of 4:1 as a feedstock. The conversion and selectivity patterns obtained for a selected sample evolved visibly with the reaction temperature and the best results were obtained at 180°C. The effect of phosphoric acid loading on the catalytic activity of the samples at this temperature was investigated and discussed. For the sake of comparison also other acidic activated carbons and the commercially available catalyst Amberlyst 15 were tested. The high H3PO4-loaded materials exhibited excellent catalytic performance in the process (high isobutene conversion, good selectivity to C8 products and high catalyst stability) which was assigned to a combination of acidic and textural properties of the materials obtained.

Fatty Acid Chain Combined with Cycloaliphatic Rings via Amberlyst‐15: A Promising Structure for a High Biocontent Epoxy Design

Fatty acid chain grafted with terpene rings via catalyst Amberlyst-15 has been demonstrated as a promising structure for the design of biobased epoxy, by which high biocontent (80 wt %) product with excellent optical (transmittance = 90%), mechanical (tensile strength = 64 Mpa) and processing (viscosity = 2.7 Pa s) properties were achieved through UV-curing in seconds. Additional Supporting Information may be found in the online version of this article. Supporting Information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

ESTERIFICATION OF RENEWABLE LEVULINIC ACID TO LEVULINATE ESTERS USING AMBERLYST-15 AS A SOLID ACID CATALYST

Levulinic acid (LA) is a versatile biomass-derived building block as it can be used for the synthesis of organic chemicals as alternative to the depleting fossil fuel resources. Levulinate esters, obtained from catalytic esterification of LA with alcohol, can be used in many applications such as fragrance and fuel additives. In this study, ion-exchange resins Amberlyst-15 was employed as solid acid catalyst for esterification of LA with methanol for methyl levulinate (ML) production. The effect of reaction time, catalyst loading, and molar ratio of LA to methanol, was investigated on LA esterification to ML at the reflux condition. The optimum ML yield of 82% was obtained from reaction conducted at reflux temperature for 5h, using 30% of Amberlyst-15 loading, and 1:20 of LA to methanol molar ratio. The reusability of Amberlyst-15 for ML production was examined for five successive reactions. In addition, Amberlyst-15 catalyst, employed in the esterification of LA with ethanol and 1-butanol for ethyl levulinate (EL) and butyl levulinate (BL), respectively, registered good performance. Yields of 71% and 55% have been obtained for EL and BL, respectively. Amberlyst-15 is a promising solid acid catalyst for production of biomass derived levulinate esters at mild process conditions.

Intensification of esterification of non edible oil as sustainable feedstock using cavitational reactors

Using sustainable feed stock such as non-edible oil for the biodiesel production can be one of the cost effective approaches considering the ever growing interest towards renewable energy and problems in existing approaches for production. However, due to the high free fatty acid content, non-edible oils require considerable preprocessing before the actual transesterification reaction for biodiesel production. The present work focuses on intensification of the esterification reaction used as preprocessing step based on acoustic and hydrodynamic cavitation also presenting the comparison with the conventional approach. Karanja oil with initial acid value as 14.15mg of KOH/g of oil has been used as a sustainable feedstock. Effect of operating parameters such as molar ratio, catalyst loading, temperature and type of catalyst (sulfuric acid and Amberlyst-15) on the acid value reduction has been investigated. The maximum reduction in the acid value (final acid value as 2.7mg of KOH/g of oil) was obtained using acoustic cavitation at optimum molar ratio of oil to methanol as 1:5 and 2% sulfuric acid loading at ambient temperature. In the case of hydrodynamic cavitation, acid value reduced upto 4.2mg of KOH under optimized conditions of first stage processing. In the second stage esterification using hydrodynamic cavitation and conventional approach, the final acid value was 3.6 and 3.8mg of KOH/g of oil respectively. Energy requirement analysis for ultrasound and conventional approaches clearly established the superiority of the ultrasound based approach. The present study clearly demonstrated that significant intensification benefits can be obtained in terms of the reduction in the molar ratio and operating temperature for the case of acoustic cavitation as compared to the conventional approach with somewhat lower effects for the hydrodynamic cavitation.

Superacidic porous polymer catalyst and its application in esterification of carboxylic acid

Two solid acid catalysts, SAC1 and SAC2, with porous structure obtained from mesoporous hard template were synthesized and characterized by Fourier transform infrared spectroscopy, acid-base titration, nitrogen adsorption/desorption, scanning electron microscopy, and their catalytic activity in esterification of carboxylic acid. Acid-base titration showed that these catalysts have acidic concentration of 1.02–1.10 mmol/g. The catalytic test in esterification of 6-bromohexanoic acid with methanol showed that SAC1 with perfluorinated sulfonic acid is catalytically more active than SAC2 with aryl sulfonic acid. In spite of lower acid loading, SAC1 showed a comparable catalytic activity with commercially available solid acid catalyst Amberlyst 15 with higher acid capacity (4.80 mmol/g) due to high acidity and well-defined pore structure. SAC1 could be recycled up to three times without significant loss in activity.

Esterification of oleic acid with ethanol in the presence of Amberlyst 15

Biodiesel is a promising cleaner burning, less toxic and renewable energy carrier. It is made primarily by transesterification of refined vegetable oils, but biodiesel from these sources are becoming more expensive. Therefore, alternative raw materials are being evaluated, but a major difficulty in the production of biodiesel from these alternative feedstocks is the high concentrations of free fatty acids. This is mainly due to the saponification reaction which occurs with the most commonly used alkali catalysts. Therefore in this work a parameter screening of the esterification of oleic acid, a free fatty acid, with ethanol in the presence of the heterogeneous acid catalyst Amberlyst 15 wet ion exchange was conducted with the intent to produce biodiesel. The parameters screened were reaction temperature, catalyst amount and the ratio between moles of alcohol and moles of fatty acid while the reaction time was set to 6 h. It was found that higher temperature and catalyst amounts increased conversion; however, the ratio between moles of alcohol and moles of fatty acid that gave the highest final conversion was 1:1. The highest Biodiesel yield obtained was 53%. In addition a reuse test of the catalyst was in order to test its recyclability; however, the catalyst presented a reduction in its activity after a single use.

Renewable Gasoline, Solvents, and Fuel Additives from 2,3-Butanediol.

2,3-Butanediol (2,3-BD) is a renewable alcohol that can be prepared in high yield from biomass sugars. 2,3-BD was selectively dehydrated in a solvent-free process to a complex mixture of 2-ethyl-2,4,5-trimethyl-1,3-dioxolanes and 4,5-dimethyl-2isopropyl dioxolanes with the heterogeneous acid catalyst Amberlyst-15. The purified dioxolane mixture exhibited an anti-knock index of 90.5, comparable to high octane gasoline, and a volumetric net heat of combustion 34 % higher than ethanol. The solubility of the dioxolane mixture in water was only 0.8 g per 100 mL, nearly an order of magnitude lower than the common gasoline oxygenate methyl tert-butyl ether. The dioxolane mixture has potential applications as a sustainable gasoline blending component, diesel oxygenate, and industrial solvent.

Biodiesel production from a free fatty acid containing Karanja oil by a single-step heterogeneously catalyzed process

ABSTRACTKaranja oil, containing 6.2% free fatty acids (FFAs), was considered for biodiesel production using a single-step solid-phase acid catalyzed process. Different types of zeolites and Amberlyst15 catalysts were tested and biodiesel was produced. Under similar conditions, the highest biodiesel yield was achieved using an Amberlyst15 catalyst, which contained 3–5% of moisture. The effects of operating parameters of the reaction such as reaction temperature, catalyst amount, and methanol-to-oil ratio were studied. An increase of methanol:oil ratio revealed a non-monotonic increase in biodiesel yields. Similar non-monotonic behavior was observed when Jatropha oil was used. Leaching and catalyst reusability were also considered. No significant effects of leaching were observed and catalyst reusability appeared to be affected by methanol interactions. The presence of a co-solvent, Tetrahydrofuran (THF), increased the biodiesel yield. Furthermore, an optimum amount of THF (THF:methanol volume ratio of 1:2) gave rise to the highest biodiesel yield. A biodiesel yield of 93% was achieved at 120 °C using a single-step process with Amberlyst15 as a catalyst, THF as a co-solvent, and a methanol:oil ratio of 30:1.

Reaction Kinetics of the Formation of Poly(oxymethylene) Dimethyl Ethers from Formaldehyde and Methanol in Aqueous Solutions

Poly(oxymethylene) dimethyl ethers (OME) are attractive oxygenated fuel additives and physical solvents for the absorption of carbon dioxide. This works studies the synthesis of OME from formaldehyde and methanol in aqueous solutions. The reaction kinetics of OME formation is studied experimentally in a stirred batch reactor on a laboratory scale using the heterogeneous catalyst Amberlyst 46. The influences of the ratio of formaldehyde to methanol, the amount of water, and the temperature (303.15–363.15 K) are investigated. A model of the reaction kinetics is developed that differentiates two competing reaction mechanisms. The model explicitly accounts for the intermediates poly(oxymethylene) hemiformals and poly(oxymethylene) glycols.

Glycerol acetalization with formaldehyde using water-tolerant solid acids

The acid-catalyzed reaction of glycerol with aqueous formaldehyde was studied using various heterogeneous catalysts for the production of glycerol formal. Owing to the high amount of water involved in the reaction medium, three types of water-tolerant heterogeneous catalysts namely acid functionalized periodic mesoporous organosilicas (PMOs), zeolite ZSM-5 and a heteropoly compound Cs2.5H0.5PW12O40 as well as commercial catalyst Amberlyst-15 were used for glycerol acetalization. The activity of Cs2.5H0.5PW12O40 was found superior to that of the other catalysts and the glycerol conversion was over 70% within 60min of reaction time. The effects of different parameters including temperature, feed composition and catalyst content, were studied as well. The distribution of the two glycerol formal isomers could be controlled by changing reaction parameters. Optimum reactive parameters were studied to control the distribution of the acetal isomers aiming to reach a high selectivity to the six-member ring isomer.

Propylsulfonic acid functionalized mesoporous silica catalysts for esterification of fatty acids

The catalytic properties of 3 types of mesoporous silica SBA-15 (rope, rod and fiber), with 9.2nm or 12.1nm large mesopores, were examined with respect to their morphology and pore size. Commercially available Amberlyst-15 and the small pore sized MCM-41 were used for comparison. The catalysts were prepared by functionalization of the silica supports with propylsulfonic acid (Pr-SO3H) using post-synthesis grafting with 3-mercaptopropyltrimethoxysilane as a propyl-thiol precursor. All materials remained in a well-ordered hexagonal mesoporous structure after Pr-SO3H functionalization. The performance of the Pr-SO3H-functionalized mesoporous silicas was evaluated in terms of their catalytic activity in the esterification of oleic acid with short (methanol) and long (glycerol) chain alcohols, i.e., to test the effect of the pore size on the substrate conversion and product yield. The synthesized catalysts were highly active and the product composition could be tuned by selective choice of the mesopore size. The Pr-SO3H-functionalized rope-shaped SBA-15 gave the highest catalytic activity (in terms of the highest methyl oleate and triglyceride yields and oleic acid conversion level), which was higher than that obtained with the commercial Amberlyst-15 catalyst. A high acid amount, large specific surface area and a suitable pore size are the likely reasons for the high yield gained by Pr-SO3H-functionalized rope-shaped SBA-15 silica.

Friedel-Crafts Alkylation of Arenes Catalyzed by Ion-Exchange Resin Nanoparticles: An Expedient Synthesis of Triarylmethanes.

Friedel-Crafts alkylation of electron-rich arenes with aldehydes has been achieved in the presence of an active and selective Amberlyst-15 catalyst at the reaction temperature of 60 degrees C in solvent-free conditions. The catalyst exhibits a very high activity and offers the corresponding triarylmethanes in excellent yields with a high selectivity. The use of highly reactive and selective Amberlyist-15 makes this procedure simple, convenient, cost-effective, practical and environmentally friendly. This method provides an easy access to triarylmethanes in a single step using a readily available acidic ionic resin, which is a stable and easy to separate from the reaction mixture by a simple filtration technique.

Highly controllable and selective hydroxyalkylation/alkylation of 2-methylfuran with cyclohexanone for synthesis of high-density biofuel

Catalytic hydroxyalkylation/alkylation of hemicellulose-derived 2-methyfuran with lignin-derived cyclohexanone yields high-density biofuel precursor (FCF) with high yield of 89.1% over nafion-212. The reaction can also be controlled at the hydroxyalkylation stage to produce another precursor (FC) with yield of 76.0% with amberlyst-15 catalyst, low FC/cyclohexanone ratio and the presence of water solvent. After hydrodeoxygenation, two high-density biofuels with density of 0.804g/ml and 0.825g/ml were produced, respectively.