Kinetic Modeling of Esterification Reaction of Free Fatty Acids Present in Macauba Oil Using a Cationic Resin as Catalyst

The cost of raw materials has the largest contribution to the final price of biodiesel produced by traditional routes, currently adopted in most industrial scale processes. That contribution comes from the need to use edible and noble oils, with low acidity, such as soybean oil. This work proposes＇the use of Macauba oil, a vegetable oil in focus in the State of Minas Gerais, Brazil, in which the current extractive yield generates a raw material with high acidity, therefore, not suitable to be used in biodiesel production. To make it technically feasible, a cationic exchange resin, the Purolite CT275DR, was used as a catalyst for esterification reaction with samples of Macauba oil, aiming to reduce its acidity. The resin can be reused, regenerated and easily removed from the reaction product, reducing costs with catalyst and purification stages. As a result of this work, in a sample of oil with an initial acidity of about 10% m/m were achieved acidity reductions up to 97% by using cationic resins as catalyst, demonstrating its potential use in the oil pretreatrnent step. Additionally, the data collected during all the analysis made it possible to define the chemical kinetic of the esterification reaction.

Decomposition mechanisms of nuclear-grade cationic exchange resin by advanced oxidation processes:Statistical molecular fragmentation model and DFT calculations

The treatment and disposal of radioactive waste are presently facing great challenges.Spent ion exchange resins have become a focus of attention due to their high production and serious environmental risks.In this paper,a simplified model of cationic exchange resin is proposed,and the degradation processes of cationic resin monomer initiated by hydroxyl radicals(·OH)are clarified by combining statistical molecular fragmentation(SMF)model and density functional theory(DFT)calculations.The prediction of active sites indicates that the S-O bonds and the C-S bond of the sulfonic group are more likely to react during the degradation.The meta-position of the sulfonic group on the benzene ring is the most active site,and the benzene ring without the sulfonic group has a certain reactivity.The C11-C14 and C17-C20 bonds,on the carbon skeleton,are the most easily broken.It is also found that dihydroxy addition and elimination reactions play a major role in the process of desulfonation,carbon skeleton cleavage and benzene ring separation.The decomposition mechanisms found through the combination of physical models and chemical calculations,provide theoretical guidance for the treatment of complex polycyclic aromatic hydrocarbons.

Synthesis of cation exchange resin-supported iron and magnesium oxides/hydroxides composite for nitrate removal in water

In this study,we reported on the concept and practical use of cation exchange resin(CER)for removing anions in water via pretreating the CER with metal salts.The cation exchange resinsupported iron and magnesium oxides/hydroxides composite(FeMg/CER)was synthesized and introduced as a new and potential adsorbent for selective removal of nitrate ion in the water environment.Characteristics of FeMg/CER were determined by techniques such as Fouriertransform infrared spectroscopy,scanning electron microscopy,and Xray diffraction.The results showed that FeMg/CER material had a high nitrate adsorption capacity of 200 mg NO_(3)^()·g^(1)with a fast equilibrium adsorption time of 30 min at pH 5.In addition,it had good durability of at least 10 times of regeneration,which could be applied to practical water and wastewater treatment.

Kinetic and thermodynamic studies of the esterification of acidified oil catalyzed by sulfonated cation exchange resin

This study describes the kinetics and thermodynamics of the esterification of acidified oil with methanol catalyzed by sulfonated cation exchange resins（SCER）. The effects of the mass ratio of methanol to acidified oil,reaction temperature,and catalyst loading were studied to optimize the conditions for maximum conversion of free fatty acids（FFAs）. The results showed that the optimal conversion rate of FFAs was 91.87% at the mass ratio of methanol to acidified oil of 2.5：1.0,reaction temperature of 65.0 °C,catalyst loading of 5.0 g and reaction time of 8.0 h. The external and internal mass transfer resistances were negligible based on the experimental results and a pseudo-homogeneous kinetic model was proposed for the esterification. The activation energy and thermodynamic parameters including G,S and H were determined. The conversion rates of FFAs obtained from the established model were in good agreement with the experimental data.

Kinetic modeling of adsorption of vanadium and iron from acid solution through ion exchange resins

This study assessed the adsorption process and the reaction kinetics involved in the selective recovery of vanadium from an acid solution containing iron as an impurity.Four commercial resins were studied:Lewatit^(®)MonoPlus TP 209 XL,Lewatit^(®) TP 207,Dowex^(TM)M4195(chelating resin)and Lewatit^(®) MonoPlus S 200 H(strong cationic exchange resin).To investigate the effect of time on the adsorption process,batch experiments were carried out using the following initial conditions:pH 2.0,298 K,and a proportion of 1 g of resin to 50 mL of solution.The variation of pH over time was analyzed.Chelating resin released less H+ions as the adsorption occurred,resulting in a lower drop of pH when compared to S 200 H resin.Ion adsorption by the resins was also evaluated through FT-IR and SEM−EDS before and after the experiments.Among the evaluated kinetic models(pseudo-first order,pseudo-second order,Elovich and intraparticle diffusion models),the pseudo-second order model best fits the experimental data of the adsorption of vanadium and iron by all of the four resins.M4195 resin showed the highest recovery of vanadium and the lowest adsorption of iron.Kinetic data,which are fundamental to industrial processes applications,are provided.

Elements, Structure and Electrochemical Property of Carbon Derived from La^(3+) Adulterating Polystyrene Cation Exchange Resin

The polystyrene cation exchange resin was exchanged by La 3+ and then were carbonized to make resin carbon material. The electrochemical properties of the resin carbon material as the electrode of the lithium ion cell were investigated. The test results show that comparing with the polystyrene cation exchange resin without adulterating, the contents of hydrogen, oxygen and sulfur are changed obviously for the resin carbon material derived from the La 3+ adulterating polystyrene cation exchange resin. The contents of hydrogen and oxygen are increased, and the one of sulfur is decreased. The test results also indicate that it is more easily to form the stratum graphite minicrystal structure with bigger diameter for the La 3+ adulterating resin. According to the electrochemical test results, the electrode derived from La 3+ adulterating polystyrene cation exchange resin has much better electrochemical property, and the capacity of charge and discharge of the electrode is increased about 30 mAh·g -1 in average.

USE OF CATION EXCHANGE RESIN IN SYNTHESIS OF N-SUBSTITUTED-1-AMINOALKANEPHOSPHONATE AND-PHOSPHINIC ACIDS

Strongly acidic cation exchange resin(1x1,H form)has been successfully used as a catalyst in synthesis of diphenyl N-benzyloxycarbonyl-1-aminobenzylphosphonate, N-benzyloxycarbonyl-1-aminobenzylphenylphosphinic acid and N-p-tolylsulfonyl-1-aminobenzyl phenylphosphinic acid in high yields.

Cationized Melamine-formaldehyde Resin for Improving the Wet Strength of Paper

In this work, melamine-formaldehyde resin was cationized by adding modifiers so that the fibers closely bonded to improve their usability and the wet strength of paper was greatly improved. Triethanolamine and dimethylamine were added to modify the melamine-formaldehyde resin,respectively.The mechanism of the cationized resin was explored and the possible chemical reactions were deduced. It was concluded that,with the use of triethanolamine,the most optimum product was obtained by hydroxymethylation for 30 min with a temperature of 85℃ and p H of 9. 0 where n( melamine) ∶ n( formaldehyde) ∶ n( methanol) ∶ n( triethanolamine) was 100 ∶ 330 ∶ 450 ∶ 15. With the combined use of dimethylamine and methanol,the optimal product was acquired by condensation for 30 min at a temperature of 50℃ and p H of 2. 0 at melamine, formaldehyde, methanol, and dimethylamine molar ratio of100∶ 330∶ 350∶ 20. With the only use of dimethylamine,the optimal product was obtained by condensation at melamine,formaldehyde,dimethylamine molar ratio of 100∶ 330∶ 10. The wet tensile strength of fruit-bagging paper was improved by adding cationized melamine-formaldehyde resin. The zeta potential,charge density,and conductivity of the melamine-formaldehyde resin were also studied.

FACTORS AFFECT THE RELEASE OF PSEUDOEPHDRINE HYDROCHLORIDE FROM THE UNCOATED CATION EXCHANGE RESIN-BASED DRUG DELIVERY SYSTEM IN VITRO

In this paper, it was investigated that the effect of parameters such as the ionic strength, pH, counter-ion type of release medium, particle size, and cross linkage of cation exchange resin on the release of model drug pseudoephedrine hydrochloride (PE) from uncoated drug-resin complex. The drug-resin complex was prepared by the reaction of PE with strongly acidic cation exchange resin (001×4, 001×7, 001×14). The result showed that the loading of PE increased with the increase of temperatures. The release of PE from drug-resin complex at 37℃ was monitored in vitro. From the experiments, it was found that the release rate of PE depends on the pH, composition of the releasing media, increased at lower pH media or with increase of ionic strength of media. Moreover, the release rate of PE was inversely proportional to the cross-linkage and particle size of the cation exchange resin.

Purification method of rohitukine from the stem bark of Dysoxylum binectariferum

To develop a simple and rapid purification method of rohitukine from the stem bark of Dysoxylum binectariferum. A L9 （34） orthogonal test was designed to optimize the extraction condition. Rohitukine in the plant extract was purified by using solvent-solvent partition and cation exchange resion （CER）. Five different types of packing materials, including XAD-2 resin, polyamide, Sephadex LH-20, ODS and CER, were compared and CER showed the best capacity for rohitukine separation. The purification procedure was optimized as follows： the plant material powder was extracted with 70% ethanol （v/m = 60） by ultrasonic agitation for 60 min, then the 70% ethanol extract was dissolved in aqueous solution （pH 1, adjusted with 0.5 mol/L HCl） and extracted with equal volume of n-butanol. The aqueous layer was retained and the pH was adjusted to 10 with 25% aqueous ammonia and a solventsolvent partition was performed with equal volume of n-butanol. The obtained n-butanol extract was dissolved in aqueous solution （pH 1, adjusted with 0.5 mol/L HCl）, and purified by a CER column eluting with H2O and 70% ethanol （pH 10, adjusted with 25% aqueous ammonia）, successively. Rohitukine existed in 70% ethanol eluate, with a purity up to 53.3%. The method developed in this study provides a simple and rapid approach for the preparation of rohitukine from the stem bark ofD. binectariferum.

ISOLATION AND PURIFICATION OF ALKALOIDS FROM PLUMULA NELUMBINIS BY DOUBLE-COLUMN ADSORPTION CHROMOTOGRAPHY

The performance of adsorption and separation for liensinine, isoliensinine and neferine was studied by double-column adsorption chromatography using macroporous adsorption and cation exchange resins. The alkaloid extract with 49.2% total contents by mass representing 10.6% liensinine, 10.6% isoliensinine and 28.0% neferine respectively was prepared by D72 cation exchange resins, in which most of the impurities were water-soluble alkaloids. Furthermore,the alkaloid extract with 82.6% total contents by mass containing 33.1%, 15.0% and 34.5% of the three adsorbates respectively was prepared by double-column adsorption chromatography using AKS-W macroporous adsorption and D72 cation exchange resins. As a result, the content of single and total alkaloids has been greatly increased by the double-column adsorption chromatography.

Controlled Drug Release Studies of Atenolol Using Differently Sulfonated Acryloxyacetophenone and Methyl Methacrylate Copolymer Resins as Drug Carriers

2-Acryloxyacetophenone （AAP） was prepared and subjected to suspension polymerization with methyl methacrylate （MMA） using azobisisobutyronitrile （AIBN） as free radical initiator. The differently sulfonated AAP-MMA cross-linked copolymer cationic exchange resins were prepared by sulfonation with concentrated sulphuric acid at 70 ~C. Several characteristics of the prepared resins were evaluated, i.e. FTIR, the ion-exchange capacity （IEC）, thermo gravimetric analysis （TGA）, particle size distribution and microscopic morphology. The resin characteristics were altered with degree of sulfonation, providing that differently sulfonated resins could be prepared. The behavior of atenolol （ATL） loading and in vitro release in the USP stimulated gastric and intestinal fluids of the obtained resins were evaluated. The drug loaded in the resin increased with increasing degree of sulfonation and hence the drug binding site in resin employed. The drug release was lower from the resins with higher content of sulfonic group due to the increase in the diffusive path depth. The drug release was a little lower in stimulated gastric fluid （SGF） than in stimulated intestinal fluids （SIF）. The basic groups, ionized to a little greater extent in SGF and preferred binding with the resin rather than releasing. Hence, the differently sulfonated resins could be utilized as novel carriers for drug delivery.

Cation exchange resin supported nanoscale zero-valent iron for removal of phosphorus in rainwater runoff

Self-made cation exchange resin supported nanoscale zero-valent iron （R-nZVI） was used to remove phosphorus in rainwater runoff. 80% of phosphorus in rainwater runoff from grassland was removed with an initial concentration of 0.72 mg. L-1 phosphorus when the dosage of R-nZVl is 8 g per liter rainwater, while only 26% of phosphorus was removed when using cation exchange resin without supported nanoscale zero-valent iron under the same condition. The adsorption capacity of R-nZVI increased up to 185 times of that of the cation exchange resin at a saturated equilibrium phosphorous concentration of 0.42 mg. L-1. Various techniques were implemented to characterize the R-nZVI and explore the mechanism of its removal of phosphate. Scanning electron microscopy （SEM） indicated that new crystal had been formed on the surface of R-nZVI. The result from inductive coupled plasma （ICP） indicated that 2.1% of nZVI was loaded on the support material. The specific surface area was increased after the load of nanoscale zero-valent iron （nZVI）, according to the measurement of BET-N2 method. The result of specific surface area analysis also proved that phosphorus was removed mainly through chemical adsorption process. X-ray photoelectron spectroscopy （XPS） analysis showed that the new product obtained from chemical reaction between phosphate and iron was ferrous phosphate.

Catalytic effects of V_(2)O_(5) on oxidative pyrolysis of spent cation exchange resin

Pyrolysis is a cost-effective and safe method for the disposal of radioactive spent resins.In this work,the catalytic effects of V_(2)O_(5) on the pyrolysis of cation exchange resin are investigated for the first time.The results show that it is a better catalyst than others so far studied and achieves a lowering of final pyrolysis temperature and residual rate simultaneously when aided by physical blending.The maximum reductions of the final pyrolysis temperature and the residual rate are 173℃and 11.9%(in weight),respectively.Under the action of V_(2)O_(5),low-temperature(445℃)removal of partial sulfonic acid groups occurs and the pyrolysis of the resin copolymer matrix is promoted.This is demonstrated by the analysis of pyrolysis residues at different temperatures by X-ray photoelectron spectroscopy(XPS)and element analysis.The catalytic activity of V_(2)O_(5) is determined by effects both at acid sites and oxidation-reduction centers via H2-TPR(temperature programmed reduction),V_(2)-TPD(temperature programmed desorption),CV_(2)-TPD,and NH3-TPD.The catalytic effect of oxidation-reduction centers in V_(2)O_(5) is achieved by close contact with the sulfur bond through chemisorption under the effect of acid sites.V_(2)O_(5) is also believed to be the reason for the removal of partial sulfonic acid groups at lower temperatures(445℃).V_(2)O_(5) is an effective catalyst for spent resin pyrolysis and can be further applied in industry.

Preparation and characterization of EVAL hollow fiber membrane adsorbents filled with cation exchange resins

EVAL hollow fiber membrane adsorbents filled with powder D061-type cation exchange resin were prepared through dry-wet spinning process,using hydrophilic copolymer EVAL as the fiber substrate.The microstructures of the membrane adsorbents were observed,and the pure water fluxes,BSA rejection,and static adsorption capacities of membrane adsorbents for BSA were measured.The effect of the resin-filled content on membrane performance has been discussed.The results showed that EVAL hollow fiber membrane adsorbents filled with D061-type cation exchange resins had good adsorption capacity,and the adsorption capacity increased with the quantity of the resin-filled content.The static protein adsorption capacity was 77.14 mg BSA/g membrane adsorbents when D061 resin loading content was 65%at pH 4.5.

Enzyme-assisted Extraction and Enrichment of Galanthamine from Lycoris aurea

Objective To explore the optimum condition for complex enzyme-assisted extraction of galanthamine from Lycoris aurea by L_9（3~4） orthogonal array design and separation effect of cation exchange resin on galanthamine. Methods Cellulase and pectinase solution was used as the extraction solvent. The effects of p H value of enzyme, amount of complex enzyme, dissociation time, and enzymatic hydrolysis temperature on the extraction results were investigated. Results The optimal conditions were obtained as follows： ratio of solid to liquid（g：mL） 1：10, pH value 4.5, amount of complex enzymes 4%, enzymatic hydrolysis temperature 50oC, and reaction time 2.0 h. Under these conditions, the extraction yield of galanthamine was 0.0294%. In addition, D-001 cation exchange resin was selected for separation of galanthamine. The separation conditions were that adsorption flow rate was 3 BV/h with reagent of pH2 and the desorption flow rate was 3 BV/h with 70% ethanol solution containing 1.5 mol/L ammonia. After separation, the content of galanthamine was increased to 12.31%. Conclusion The results provide a reference for industrial production of galanthamine.

Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors

N-nitrosodimethylamine（NDMA） precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine（DMA） and ranitidine（RNTD）, by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal（DMA 〉 78% and RNTD 〉 94%） observed at pH 〈 pk_a-1 when the molar ratio of exchange capacity to precursor was 4. The exchange order was obtained as follows： Ca^（2＋）〉 Mg^（2＋）〉 RNTD~＋〉 K~＋〉 DMA~＋〉 NH_4~＋〉 Na~＋. The partition coefficient of DMA~＋to Na~＋was 1.41 ± 0.26, while that of RNTD~＋to Na~＋was 12.1 ± 1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca^（2＋）were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes.