Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor:Experimental and kinetic studies

The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor.The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure.The measurement data were regression with the pseudo-homogeneous(P-H),Eley-Rideal(E-R),and Langmuir-Hinshelwood(L-H)heterogeneous kinetic models.Independent adsorption experiments were implemented to gain the adsorption equilibrium constants of four components.Among the above three models,the L-H model exhibited the best fitting results.The stability of NKC-9 was evaluated by long-term running with the yield of methyl methacrylate no decrease during 3000 h operation.The structure and physicochemical properties of the new and used catalyst were performed by several characterizations including thermogravimetric analysis(TG),scanning electron microscope(SEM),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FT-IR)and so on.

Elution Behaviour of Monocarboxylic Acids on a Cation-exchange Resin Column

The retention mechanism of monocarboxylic acids on a cation-exchange resin column was investigated. It was assumed that both Donnan membrane equilibrium and adsorption equilibrium were involved in the chromatographic process. On the basis of the proposed mechanism, an equation was derived for correlating distribution coefficient, Kd, dissociation constant, Aa, and adsorption equilibrium constant, K, of the analyzed acid. By this approach, retention data for some aliphatic acids under different operating conditions were predicted. Results are reasonably in agreement with experiment.

Taste masking of ciprofloxacin by ion-exchange resin and sustain release at gastric-intestinal through interpenetrating polymer network

The aim of the study was to taste mask ciprofloxacin(CP)by using ion-exchange resins(IERs)followed by sustain release of CP by forming interpenetrating polymer network(IPN).IERs based on the copolymerization of acrylic acid with different cross linking agents were synthesised.Drug-resin complexes(DRCs)with three different ratios of drug to IERs(1:1,1:2,1:4)were prepared&evaluated for taste masking by following in vivo and in vitro methods.Human volunteers graded ADC 1:4,acrylic acid-divinyl benzene(ADC-3)resin as tasteless.Characterization studies such as FTIR,SEM,DSC,P-XRD differentiated ADC 1:4,from physical mixture(PM 1:4)and confirmed the formation of complex.In vitro drug release of ADC 1:4 showed complete release of CP within 60 min at simulated gastric fluid(SGF)i.e.pH 1.2.IPN beads were prepared with ADC 1:4 by using sodium alginate(AL)and sodium alginate-chitosan(AL-CS)for sustain release of CP at SGF pH and followed by simulated intestinal fluid(SIF i.e.pH 7.4).FTIR spectra confirmed the formation of IPN beads.The release of CP was sustain at SGF pH(<20%)whereas in SIF media it was more(>75%).The kinetic model of IPN beads showed the release of CP was non-Fickian diffusion type.

Tungsten removal from molybdate solutions using chelating ion-exchange resin:Equilibrium adsorption isotherm and kinetics

The equilibrium adsorption isotherm and kinetic of the sorption process for W and Mo on macro chelating resin D403 were investigated on single Na2 Mo O4 and Na2WO4 solutions.The sorption isotherm results show that the adsorption process of W obeys the Freundlich model very well whereas the exchange process with Mo approximately follows the Henry model.The kinetic experiments show that the intraparticle diffusion process was the rate-determining step for W sorption on the resin,and the corresponding activation energy is calculated to be 21.976 k J/mol.

Purification of Lactic Acid by Heterogeneous Catalytic Distillation Using Ion-exchange Resins

The purification of lactic acid based on the esterification of raw lactic acid from fermentation broth and then the catalytic distillation hydrolysis of methyl lactate simultaneously to achieve pure lactic acid is reported. The esterification kinetics of lactic acid with methanol catalyzed by strong-acid cation-exchange resins (Amberlyst-15,D001, D002, NKC, 002) was studied under the condition that simulates the real catalytic environment. Experimental results were correlated by a Langmuir-Hinselwood model and the nonideality of the solution was taken into account by using activities calculated by the universal quasichemical functional group activity coefficient (UNIFAC) method.A good agreement between the model and the experimental data was achieved. Continuous purification experiments were conducted to find the optimum column configuration and operation condition for the system. The effects of various parameters, e.g. the length of different section of the column, feed rate and ratio of reactants, packing material and catalyst type, were studied. This novel system shows good separation results in lab scale, and is potential for industrial application.

Kinetic Study of Esterification of Lactic Acid with Isobutanol and n-Butanol Catalyzed by Ion-exchange Resins

The esterification reactions of lactic acid with isobutanol and n-butanol have been studied in the presence of acid ion-exchange resin Weblyst D009.The influences of catalyst loading,stirrer speed,catalyst particle size,initial reactant molar ratio and temperature on the reaction rate have been examined.Experimental kinetic data were correlated by using the Pseudo-homogeneous,Langmuir-Hinshelwood and Eley-Rideal models.Nonideality of the liquid phase was taken into account by using activities instead of molar fractions.The activity coefficients were calculated according to the group contribution method UNIFAC.Provided that the nonideality of the liquid is taken into account,the esterification kinetics of lactic acid with isobutanol and n-butanol catalyzed by the acid ion-exchange resin can be described using all three models with reasonable errors.

Adsorption properties of Ag(Ⅰ),Au(Ⅲ),Pd(Ⅱ)and Pt(Ⅳ)ions on commercial 717 anion-exchange resin

The adsorption properties of the four precious metal ions(Ag(Ⅰ),Au(Ⅲ),Pd(Ⅱ)and Pt(Ⅳ))on the commercial Cl--form 717 strongly basic anion-exchange resin were studied in detail.The effects of the contact time,solution acidity,and concentrations of Cl - and Pb 2+ ions on the adsorption properties were studied by the batch method.Then,the column method was conducted under the optimized adsorption conditions(pH=3.0).The effects of the sample loading flow rate and the length-to-diameter ratios of the columns were investigated.The precious metal ions adsorbed could not be eluted completely after the saturated adsorption because the precious metal ions were found to be reduced to their metallic states during the adsorption process.So,it is recommended that the commercial Cl--form 717 strongly basic anion-exchange resin should be decomposed directly to recovery the precious metals after the saturated adsorption.

The Desalting Property of Ion-Exchange Resins in Organic Solvent

The desalting property of ion-exchange resins in organic solvent is reported by using potassium acetateas a model compound. The experimental results show that the solvability of the solvent stirring speed, andtemperature are the factors which influence the ion-exchange rate. The increase of solvability, stirring speed andtemperature will speed up the ion-exchange process.

Study on Stability of Ion-exchange Resin Catalysts:Ⅱ. Desulfonation during Isobutylene Dimerization

The performance of ion-exchange resin catalysts during isobutene (IB) dimerization was investigated under different IB contents,temperatures and liquid-volume hourly space velocity (LHSV) using a plug flow reactor in the absence of any selectivity enhancing component.High IB content and temperature resulted in a high conversion and C12 selectivity bu low C8 selectivity.The influence of LHSV was related with the IB content:LHSV had great effect at high IB content,while the performance of ion-exchange resin changed little with LHSV if IB content was low.The effect of water on the stability of resins was also studied.Desulfonation was observed during the C4 dimerization reaction when water was added to the feed.Chlorinated resin was more stable than conventional polystyrene-based resins during the test.

Study on the Stability of Ion-exchange Resin Catalysts:Ⅰ. TGA as a Rapid Evaluating Method

五商业离子交换树脂催化剂的热稳定性与不同的起始的水内容在 150 和 200 件树脂样品的范围在多达 600 的提高的温度和等温的温度借助于热 gravimetric 分析(TGA ) 被学习也被调查。学习显示了那 TGA，作为为塞子流动反应堆系统途径的一个补足的评估方法，能在离子交换树脂催化剂的热稳定性上为学习被用作一个快分析工具。等温地对待的树脂催化剂的 stoichiometric 计算基于 FTIR 分析和酸能力证实在 150 和 200 点的树脂的重量损失被 desulfonation 过程引起并且 desulfonation 主要在苯戒指的帕拉位置发生在树脂。H+ 离子和潮湿在 desulfonation 过程起了一个重要作用。

Environmentally benign chemical fixation of CO_(2) catalyzed by the functionalized ion-exchange resins

Basic ion-exchange resins,one kind of polystyryl-supported tertiary amine,were demonstrated to be highly efficient and recyclable catalysts for the fixation of carbon dioxide with aziridines under mild conditions,leading to the formation of 5-aryl-2-oxazolidinone with excellent regio-selectivities.Notably,neither solvents nor any additives were required,and the catalyst could be recovered by simple filtration and directly reused at least five times without significant loss of catalytic activity and selectivity.The present protocol has been applied to reactions of epoxides/propargyl amines with CO_(2)/CS2.This solvent-free process thus represents environmentally friendly catalytic conversion of CO_(2) into value-added chemicals and may have potential in various continuous flow reactors in industry.

Ultra-low concentration of total organic carbon in ultrapure water using ion-exchange resin embedding silanized magnetic nanoparticles

Regeneration of pure water is an important issue not only for the healthy life but also for the fine control of precise processes in various industries.One important issue in ultrahigh purified water is to reduce the amount of total organic carbon(TOC).Herein,we introduce a new approach to reduce the TOC using the surface silanized nanoparticles,in which the magnetic nanoparticles(mNPs)are silanized and then complexed with ion exchange resin(IER)beads.The Fe3O4 mNPs are surface modified by using high concentrated vinyltrimethoxysilane(VTMS)and then adhered on the surface of IER beads.The surface modified mNPs have a thick-shell of polysiloxane layer varying from 5 to 22 nm depending on the amount of VTMS used,which leads the significant increase of specific surface area.The IER beads embedding VTMS-silanized mNPs achieves about 7μg/L of the TOC level in ultrapure water system,which is two orders less than 228μg/L of the feeding water and one order less than 96μg/L from the system using pristine IER beads.This result is mainly attributed to the polysiloxane layer forming broccoli-like surface structure and some part by the vinyl group of VTMS exposed to the amines in the water.

Hole-growth phenomenon during pyrolysis of a cation-exchange resin particle

A novel central hole-expansion phenomenon is identified, in which the cation-exchange resin is pyrolyzed in a mixed atmosphere of nitrogen and oxygen at 400–500 ℃. In this reaction, the reaction path is predictable and always starts from the center of the resin particle to form a central hole, then continues and expands around the hole, finally forming a uniformly distributed hole group;the particle surface remains intact. Analysis shows that this formation mode is due to the different reaction paths of sulfonic groups between the surface and interior of the particle, caused by the temperature difference. On the surface, transformation reactions happen at high temperatures(410–500 ℃) to form stable organic sulfur structures, while decomposition occurs inside the particle at a relatively low temperature(<410 ℃) and promotes complete pyrolysis of the copolymer matrix to form holes.

Adsorption of three pharmaceuticals on two magnetic ion-exchange resins

The presence of pharmaceuticals in aquatic environments poses potential risks to the ecology and human health. This study investigated the removal of three widely detected and abundant pharmaceuticals, namely, ibuprofen（IBU）, diclofenac（DC）, and sulfadiazine（SDZ）, by two magnetic ion-exchange resins. The adsorption kinetics of the three adsorbates onto both resins was relatively fast and followed pseudo-second-order kinetics. Despite the different pore structures of the two resins, similar adsorption patterns of DC and SDZ were observed, implying the existence of an ion-exchange mechanism. IBU demonstrated a combination of interactions during the adsorption process. These interactions were dependent on the specific surface area and functional groups of the resin. The adsorption isotherm fittings verified the differences in the behavior of the three pharmaceuticals on the two magnetic ion-exchange resins. The presence of Cl-and SO2-4suppressed the adsorption amount, but with different inhibition levels for different adsorbates. This work facilitates the understanding of the adsorption behavior and mechanism of pharmaceuticals on magnetic ion-exchange resins.The results will expand the application of magnetic ion-exchange resins to the removal of pharmaceuticals in waters.

Use of polymeric sub-micron ion-exchange resins for removal of lead,copper,zinc,and nickel from natural waters

This research investigated the removal capacity of polymeric sub-micron ion-exchange resins(SMR) for removal of lead, copper, zinc, and nickel from natural waters in competition with natural organic matter(NOM). Polymeric SMR particles were created and tested to ensure that they were adequately dispersed in the solution. They removed little NOM(10%or less) from river water and wastewater, indicating that competition from NOM was not a major concern. SMR were able to remove 82% ± 0.2% of lead, 46% ± 0.6% of copper, 55% ±20% of zinc, and 17% ± 2% of nickel from river water spiked with 500 μg/L of each. Similarly,in wastewater, they were able to remove 86% ± 0.1% of lead, 38% ± 0.8% of copper, 28% ± 1%of zinc, and 11% ± 1% of nickel.

Adsorption of Zinc and Cyanide from Cyanide Effluents on Anionic Ion-exchange Resin

The adsorption of zinc and cyanide from cyanide effluents onto strong and weak basic anion exchange re sins was studied in a batch adsorption system. Factors influencing the adsorption rates such as resin selection, resin amounts, contact time and temperature were studied and scanning electron microscopyenergy disperse spectrosco py（SEMEDS） was used in the analysis. The present study shows that the adsorption capacity of resin 201 x7 is better than that of resin 301. The adsorption process was relatively fast and came to equilibrium after 60 min. The kinetic data were analyzed with three models and the pseudosecondorder kinetic model was found to agree with the expe rimental data well. The equilibrium data could also be described well by Langmuir isotherm model. Thermodynamic parameters such as enthalpy change（AH0）, free energy change（AG0） and entropy change（AS0） were calculated and the adsorption process was spontaneous and endothermic.

Effects of ion-exchange on the pervaporation performance and microstructure of NaY zeolite membrane

Pervaporation performance of NaY zeolite membranes is improved by ion-exchange with di-valent nitrate salt.Different nitrate salts,including Co(NO_(3))_(2),Mg(NO_(3))_(2),Zn(NO_(3))_(2),Ca(NO_(3))_(2),Cu(NO_(3))_(2),KNO_(3),and AgNO_(3),have great effects on the channel structure and water affinity of the NaY zeolite membrane.When the concentration of nitrate salt,ion-exchange temperature and time are 0.1 mol·L^(-1),50℃and 2 h,the ion-exchange degree order of NaY zeolites is Ag^(+)>K^(+)>Ca^(2+)>Zn^(2+)>>Co^(2+)>Mg^(2+).Especially,Ag^(+)and K^(+)cation exchange degree of NaY zeolites are achieved to 96.54% and 82.77% in this work.BET surface,total pore capacity,pore size distribution and water contact angle of the ion-exchanged NaY zeolites are all disordered by mono-and di-valent cations.Di-valent nitrate salt is favor for increasing the dehydration performance of NaY zeolite membranes by ion-exchange.When the ion-exchange solution is Zn(NO_(3))_(2),the total flux variation and separation factor variation of the NaY membrane(M-5)are -45% and 230% for separation of 10%(mass)H_(2)O/EtOH mixture by pervaporation,and the ion-exchanged membranes showed good reproducibility.

SIMULTANEOUS ION-EXCHANGE AND ADSORPTION OF LACTIC ACID ON D354 RESIN

From a number of ion-exchange resins and adsorbents,a macro-pore weak-base type anionion-exchange resin,D354,was selected for the separation of lactic acid.Experimental data showedthat simultaneous ion-exchange and physical adsorption existed in the lactic acid-D354 system.Amathematical model was suggested to simulate the experimental data.Also,the effects of inorganicsalts on the ion-exchange.equilibrium were studied.The difference in ion-exchange equilibrium be-tween DL-and L-lactic acid was observed.

B-COPNA resin formation from ethylene tar light fractions:Process development and mechanical exploration by molecular simulation

An efficient utilization strategy of ethylene tar(ET),the main by-product of the ethylene cracking unit,is urgently required to meet demands for modern petrochemical industry.On the other hand,condensed polynuclear aromatic resin of moderate condensation degree(B-COPNA)is a widely used carbon material due to its superb processability,the production of which is,however,seriously limited by the high cost of raw materials.Under such context,an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar(ETLF,boiling point<260℃)facilitated by molecular simulation.1,4-Benzenedimethanol(PXG)was first selected as the crosslinking agent according to the findings of molecular simulation.The effects of operating conditions,including reactions temperature,crosslinking agent,and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process.The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents.It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents.In addition to the highest yield and greatest heat properties,PXG-prepared resin contained the most condensed aromatics.The corresponding optimized conditions of resin preparation were 180℃,1:1.9(PXG:ETLF),and 3%(mass)of catalyst content with a resin yield of 78.57%.It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation,according to the experimental characterization and molecular simulation.Hence,it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation,bringing huge economic value to the current petrochemical industry.