Acidic Exchange Resin Research Articles

Properties of Polyurethane Coatings Based on Linseed Oil Phosphate Ester Polyol

Linseed oil was epoxidized using hydrogen peroxide (H2O2), acetic acid (AcOH) and ion exchange resin Amberlite IR-120 as a catalyst. Epoxidized oil was separately dissolved in isopropyl alcohol (IPA) or diethylene glycol butyl ether (DGBE) and phosphorylated with different amounts of phosphoric (H3PO4) acid (1%, 2%, 3% and 5%). The formation of phosphate polyesters was confirmed by Fourier-transform infrared (FTIR) and 31P nuclear magnetic resonance (NMR) spectra. Based on the synthesized polyols, polyurethane (PU) coatings were prepared. PU coating based on linseed oil diethylene glycol ester polyol was used as the reference. For the characterization of coatings, mechanical tests and thermogravimetric analysis (TGA) were used. The flammability parameters of wood samples with PU coatings at a heat flux of 35 kW/m2 were determined. It was found that PU coatings based on IPA polyols had higher mechanical characteristics, char residue upon thermal decomposition and flame retardancy.

Catalytic activity dependence on morphological properties of acidic ion-exchange resins for the simultaneous ETBE and TAEE liquid-phase synthesis

Resin acid capacity and specific volume of the swollen polymer are the key properties that determine its catalytic activity.

The kinetics of nickel recovery from ferrous containing solutions using an Iminodiacetic acid ion exchange resin

This paper reports on the investigation of the loading rate of nickel onto an iminodiacetic acid ion exchange resin (TP207XL) under the finite solution volume condition in the presence of ferrous in a batch loading system. A hybrid correlation model (McKevitt, 2012) was applied for nickel-ferrous displacement loading data. The experimental fit parameters of the hybrid correlation were used to successfully predict the results of the batch loading experiments by applying the finite difference model. The finite difference model was applied to predict the loading behavior of nickel in the presence of ferrous in the batch system using the modified Helfferich number and the linear isotherm equation. As confirmed, the ion exchange reaction examined in this study was predominantly controlled under some combination of intraparticle diffusion/ion exchange reaction. Regarding the hybrid correlation fit parameters (Dapp=9.95×10−12m2/s, α=0.65), these parameters correlated well with the loading behavior of nickel onto resin.

Lignosulfonate-based macro/mesoporous solid protonic acids for acetalization of glycerol to bio-additives

The enclosed paper introduces a novel, scalable and environmentally benign process for making strongly acidic solid meso/macroporous carbon catalysts from Na-lignosulfonate (LS), a byproduct from sulfite pulping. Ice-templated LS was converted to strongly acidic macro/mesoporous solid protonic acids via mild pyrolysis (350–450°C) and ion/H+ exchanging technique. The synthesized materials were extensively characterized by FT-IR, Raman, XRD, XPS, TGA, FE-SEM, TEM and N2-physisorption methods. These LS derived materials exhibited a macro/mesoporous and highly functionalized heteroatom doped (O, S) carbon structure with large amounts of surface OH, COOH and SO3H groups similar to the sulfonated carbon materials. Further, these carbon materials showed excellent potential as solid acid catalysts upon acetalization of glycerol with various bio-based aldehydes and ketones (acetone, methyl levulinate and furfural), easily outperforming the commercial acid exchange resins (Amberlite® IR120 and Amberlyst® 70). Most importantly, the optimum LS catalyst exhibiting a large specific surface area demonstrated exceptional potential for continuous solketal production (liquid phase atmospheric pressure operation) maintaining its activity (glycerol conversion≥91%) and structural features even after 90h time on stream.

Role of ion‐exchange resins as catalyst in the reaction‐network of transformation of biomass into biofuels

AbstractThe use of acidic ion exchange resins in the transformation of biomass into biofuels is revised and their potential application is presented. Relationships between morphology and structure of resins and their catalytic activity for some existing reactions of the transformation network from sugars to biofuels are observed. In the synthesis of 5‐hydroxymethyfurfural and levulinic acid, catalytic activity of resins increases when the crosslinking content is decreased for both macroreticular and gel‐type resins. Gel‐type resins with low crosslinking were found to be the most suitable resins for direct esterification of levulinic acid with linear alcohols. However, for the alcoholysis of furfuryl alcohol, macroreticular resins are better than gel‐type ones. Deactivation probably due to humins formation is the main drawback for industrial application. © 2017 Society of Chemical Industry

Dehydration of 1-octanol to di-n-octyl ether in liquid phase with simultaneous water removal over ion exchange resins: Effect of working-state morphologies

The influence of the concentration of polar reactants and products on the working-state morphology of ion exchange catalysts has been investigated over different acidic ion-exchange resins for di-n-octyl ether (DNOE) synthesis from 1-octanol dehydration at 423–448K and atmospheric pressure in a batch reactor equipped with a Dean & Stark device. By removing water formed 1-octanol conversion was practically complete; the olefin formation being the main secondary reaction. When 1-octanol is completely consumed the working-state morphology of ion exchange resins changes, which influences the selectivities towards products. At this point, for microporous resins all reactions stop while with macroreticular ones DNOE decomposes and significant amounts of olefin dimers appears. The best selectivity to DNOE was found in gel-type and macroreticular resins with low crosslinking degree. Macroreticular resins with medium or high crosslinking give good results in olefin formation.

Carbon Dioxide as a Traceless Caramelization Promotor: Preparation of Prebiotic Difructose Dianhydrides (DFAs)-Enriched Caramels from d-Fructose.

Activation of a concentrated solution of d-fructose with carbonic acid, generated from carbon dioxide, induces the formation of difructose dianhydrides (DFAs) and their glycosylated derivatives (glycosyl-DFAs), a family of prebiotic oligosaccharides. Under optimized conditions, up to 70% of the active DFA species were obtained from a highly concentrated solution of fructose, avoiding the filtration step and contamination risk associated with the current procedures that employ heterogeneous catalysis with acid ion-exchange resins. The optimized CO2-promoted preparation of DFA-enriched caramel described here has been already successfully scaled up to 150 kg of d-fructose for nutritional studies, showing that implementation of this process is possible at a larger scale.

Liquid–Liquid–Solid Model for the Epoxidation of Soybean Oil Catalyzed by Amberlyst-16

The epoxidation of soybean oil is a hot topic for biorefinery. The process is nowadays performed in the presence of a strong mineral acid (H2SO4, H3PO4) that catalyzes both the epoxidation and the oxirane ring opening reactions, leading to high conversions and low selectivity. Moreover, the separation of such a catalyst needs neutralization steps, thus operation units. Previous studies revealed that Amberlyst-16, an acid exchange resin, is a stable and active catalyst in the epoxidation of soybean oil, showing high selectivity. In the present paper, a rigorous liquid–liquid–solid kinetic model has been proposed to interpret the kinetics of the soybean oil epoxidation reaction catalyzed by Amberlyst-16. The intrinsic kinetics of the overall reaction network has been investigated by taking into account all the occurring chemical and physical phenomena, overall dealing with the intraparticle diffusion limitations. From the data elaboration, it has been demonstrated that the unique role of the resin is to cat...

XPS characterization of tribo-layer formation on the steel lubricated with crude and epoxidized jatropha oil under boundary lubrication

PurposeThis study aims to characterize the composition of the tribo-layer formed during sliding of steel in the presence of crude jatropha oil (CJO) and epoxidized jatropha oil (EJO) under boundary lubricant application.Design/methodology/approachCJO was obtained from a local market and used as received. EJO was obtained by epoxidation process with peroxyformic acid catalyzed by acidic ion exchange resin. The tribological test was conducted by the four ball method according to ASTM 4192. Wear scars generated on the lower balls were used to characterize the tribo-layer. Energy-dispersive X-ray and X-ray photo spectroscopy analysis were conducted to characterize the tribo-layer composition.FindingsEJO shows a lower friction coefficient compared to CJO. Moreover, EJO also shows better wear preventive properties compared to CJO. The oxidation of CJO and EJO has lead chemisorption of the oil to steel surface to cause formation of protective layers for the steel surface. The layers were constructed from inorganic oxide in the form of iron oxides and silicon oxide together with organic layers in form of aldehyde, ketone and carboxylic acid. The formation and removal of this layer from rubbing sites are considered to affect wear-preventive and friction behaviour of steel lubricated with CJO and EJO.Originality/valueThis works highlights friction and anti-wear characteristics of CJO and EJO. This work also presents the composition of the tribo-layer that formed because of the sliding of steel lubricated with CJO and EJO. The method and result can be used for further investigation and development of lubricant.

Simultaneous etherification of isobutene with ethanol and 1-butanol over ion-exchange resins

The simultaneous liquid-phase etherification of isobutene with ethanol and 1-butanol to give ethyl tert-butyl ether (ETBE) and butyl tert-butyl ether (BTBE) has been studied, at temperatures in the range of 315–353K and at 2.5MPa, over six commercial acidic macroreticular ion-exchange resins as catalysts. The initial alcohol to isobutene molar ratio was varied in the range of 0.5–5.5 and the initial ethanol to 1-butanol molar ratio in the range of 0.5–2.0. Strongly acidic catalysts with a rigid polymer backbone structure enhance reaction rate. This fact, along with the reduced side reactions extent, makes Amberlyst™ 35 the most promising catalyst, among the tested ones, for the studied simultaneous etherification process. Irrespectively of the used catalyst, initial ETBE synthesis reaction rate is hardly sensitive to the variation of the ethanol to 1‐butanol molar ratio, whereas initial BTBE synthesis reaction rate strongly diminishes at high ethanol concentration. Preferential adsorption of ethanol over 1‐butanol on the catalysts active sites has been detected. As expected, both etherification reaction rates increase at increasing isobutene concentration. At 353K, the highest temperature, both etherification rates are affected by internal mass transfer resistances due to diffusion limitations even when small catalyst beads are used. The simultaneous process has been compared to the individual syntheses of ETBE and BTBE and it has been found that the isobutene selectivity towards ethers is enhanced in the simultaneous system.

Equilibrium and thermodynamic parameters for heterogeneous esterification of butyric acid with methanol under microwave irradiation

Synthesis of methyl butyrate was investigated in a microwave irradiated batch reactor in presence of acid ion-exchange resin catalyst,amberlyst-15. Methyl ester was heterogeneously produced by the reaction between butyric acid and methanol. Effect of reaction parameters oftemperature (323–343 K), catalyst loading (0–10.5% w/w), alcohol to acid ratio, M (1–5), and amount of molecular sieves added (0–13.5% w/w)on conversion were studied. Equilibrium conversion of 92.6% was achieved in 60 minutes under microwave irradiation. Equilibrium constants atvaried temperatures and dependency of equilibrium constant on temperature were studied. Equilibrium constant and equilibrium conversionshowed increase with the increase in temperature as expected as per le-Chatelier principle. Van’t Hoff plot for esterification of butyric acid waslinear with negative slope indicating that reaction was endothermic. Comparative study showed that microwave irradiated method for methylbutyrate synthesis to be very efficient and fast compared with conventional and ultrasound assisted routes under optimized reaction conditions.

Reaction Process of Resin-Catalyzed Methyl Formate Hydrolysis in Biphasic Continuous Flow

In the frame of process development for the generation of chemical energy carriers, we studied the synthesis of methanol and formic acid from methyl formate hydrolysis in a continuous-flow millireactor. The aim was to establish the link between kinetics and phase behavior in the biphasic liquid regime. Reaction performance using the acidic ion-exchange resin Amberlyst 15 as catalyst was examined at various operating conditions such as space velocity, catalyst particle size, temperature, and initial reactant ratio. Results revealed substantially higher yields without mass transfer impediment with feed compositions exceeding methyl formate saturation in water. The simultaneous decrease in methyl formate and increase in polar product concentrations sufficed to bring the initially biphasic mixture to a homogeneous system as confirmed by thermodynamic UNIFAC equilibrium calculations. The separate analysis of effluent liquid phases unveiled a quasi-homogeneous catalytic process rooted in an aqueous layer at the...

Equilibrium and thermodynamic parameters for heterogeneous esterification of butyric acid with methanol under microwave irradiation

Abstract Synthesis of methyl butyrate was investigated in a microwave irradiated batch reactor in presence of acid ion-exchange resin catalyst, amberlyst-15. Methyl ester was heterogeneously produced by the reaction between butyric acid and methanol. Effect of reaction parameters of temperature (323–343 K), catalyst loading (0–10.5% w/w), alcohol to acid ratio, M (1–5), and amount of molecular sieves added (0–13.5% w/w) on conversion were studied. Equilibrium conversion of 92.6% was achieved in 60 minutes under microwave irradiation. Equilibrium constants at varied temperatures and dependency of equilibrium constant on temperature were studied. Equilibrium constant and equilibrium conversion showed increase with the increase in temperature as expected as per le-Chatelier principle. Van't Hoff plot for esterification of butyric acid was linear with negative slope indicating that reaction was endothermic. Comparative study showed that microwave irradiated method for methyl butyrate synthesis to be very efficient and fast compared with conventional and ultrasound assisted routes under optimized reaction conditions.

Development of an Integrated Reaction–Distillation Process for the Production of Methylal

An integrated reaction–distillation process for the production of methylal from aqueous, methanolic formaldehyde solutions is developed. The process consists of a serial connection of a reactor in which the feed is converted to chemical equilibrium by a heterogeneously catalyzed reaction followed by a pressure-swing distillation sequence, in which a heterogeneously catalyzed reactive section as well as a vapor side draw are used. The catalyst is an acidic ion-exchange resin. The process yields methylal in purities over 0.999 g/g; methanol can be recovered in purities over 0.94 g/g, and water is withdrawn in a purity of 0.99 g/g. The conversion of formaldehyde is above 99.9%. The process development is carried out based on steady-state simulations with a model which explicitly accounts for the oligomerization reactions of formaldehyde in aqueous, methanolic formaldehyde solutions. The model is validated by a comparison to experiments that are carried out in a laboratory glass distillation column.

Epoxidation of Vernonia Oil in Acidic Ion Exchange Resin

In this study epoxidized vernonia oil (EVO) was synthesized by the epoxidation of vernonia oil using peroxyformic acid, formed in situ by the reaction of hydrogen peroxide and formic acid in the presence of an acidic ion exchange resin (Amberlite IR-120 hydrogen form) as the catalyst. This method of epoxidation has resulted in product with about 78% conversion. Acid exchange resin catalyzed epoxidation reactions are found to be promising in minimizing oxirane ring opening.

Kinetics of soybean oil epoxidation with peracetic acid formed in situ in the presence of an ion exchange resin: Pseudo-homogeneous model

A kinetic model was proposed for the epoxidation of vegetable oils with peracetic acid formed in situ from acetic acid and hydrogen peroxide in the presence of an acidic ion exchange resin as a catalyst. The model is pseudo-homogeneous with respect to the catalyst. Besides the main reactions of peracetic acid and epoxy ring formation, the model takes into account the side reaction of epoxy ring opening with acetic acid. The partitioning of acetic acid and peracetic acid between the aqueous and organic phases and the change in the phases? volumes during the process were considered. The temperature dependency of the apparent reaction rate coefficients is described by a reparameterized Arrhenius equation. The constants in the proposed model were estimated by fitting the experimental data obtained for the epoxidations of soybean oil conducted under defined reaction conditions. The highest epoxy yield of 87.73% was obtained at 338 K when the mole ratio of oil unsaturation:acetic acid:hydrogen peroxide was 1:0.5:1.35 and when the amount of the catalyst Amberlite IR-120H was 4.04 wt.% of oil. Compared to the other reported pseudo-homogeneous models, the model proposed in this study better correlates the change of double bond and epoxy group contents during the epoxidation process.

A new way to do an old reaction: highly efficient reduction of organic azides by sodium iodide in the presence of acidic ion exchange resin.

Organic azides are readily reduced to the corresponding amines by treatment with sodium iodide in the presence of acidic ion exchange resin. The process, optimal when performed at 40 °C and 200 mbar pressure on a rotatory evaporator, is extremely efficient, clean, and tolerant of a variety of functional groups.

Kinetics and Equilibrium Isotherm Studies for the Aqueous Lithium Recovery by Various Type Ion Exchange Resins

The characteristics of aqueous lithium recovery by ion exchange were studied using three commercial cation exchange resins: CMP28 (porous type strong acid exchange resin), SCR-B (gel type strong acid exchange resin) and WK60L (porous type weak acid exchange resin). CMP28 was the most effective material for aqueous lithium recovery; its performance was even enhanced by modifying the cation with K+. A comparison to Na+ and H+ form resins demonstrated that the performance enhancement is reciprocally related to the electronegativity of the cation form. Further kinetic and equilibrium isotherm studies with the K+ form CMP28 showed that aqueous lithium recovery by ion exchange was well fitted with the pseudo-second-order rate equation and the Langmuir isotherm. The maximum ion exchange capacity of aqueous lithium recovery was found to be 14.28 mg/g and the optimal pH was in the region of 4-10.

Technological aspects of vegetable oils epoxidation in the presence of ion exchange resins: a review

Abstract A review paper of the technology basics of vegetable oils epoxidation by means of peracetic or performic acid in the presence of acidic ion exchange resins has been presented. The influence of the following parameters: temperature, molar ratio of acetic acid and hydrogen peroxide to ethylenic unsaturation, catalyst loading, stirring intensity and the reaction time on a conversion of ethylenic unsaturation, the relative percentage conversion to oxirane and the iodine number was discussed. Optimal technological parameters, mechanism of epoxidation by carboxylic peracids and the possibilities of catalyst recycling have been also discussed. This review paper shows the application of epoxidized oils.

Heterogeneously catalyzed conversion of nordic pulp to levulinic and formic acids

Herein, one-pot conversion of cellulose to platform chemicals, formic and levulinic acids was demonstrated. The catalyst selected was an affordable, acidic ion-exchange resin, Amberlyst 70, whereas ...