Fabrication and Characteristics of Poly(benzimidazole/fluoro/ether/siloxane/amide)/Sulfonated Polystyrene/Silica Nanoparticle-Based Proton Exchange Membranes Doped With Phosphoric Acid

Novel poly(benzimidazole/fluoro/ether/siloxane/amide) (PBFESA) was developed for the formation of hybrid proton exchange membrane. Afterward, phosphoric acid doped PBFESA/PS-S/SiNPs was prepared with PBFESA, sulfonated polystyrene (PS-S), and 0.1–2 wt% silica nanoparticles (SiNPs). Tensile strength of acid doped PBFESA/PS-S/SiNPs nanocomposites increased from 63.9 to 68.1 MPa with increasing SiNPs loading. They had higher ion exchange capacity (IEC) of 2.3–3.3 mmol/g and proton conductivity of 1.9–2.7 S/cm at 80°C (higher than perfluorinated Nafion 117 membrane 1.1 × 10^?1 S/cm). A H₂/O₂ fuel cell using PBFESA/PS-S/SiNPs 2 (IEC 3.3 mmol/g) showed better performance than Nafion 117 at 40°C (30% RH).     

Phosphorus Recovery from Urban Wastewater Treatment Plant Sludge Liquor by Ion Exchange

In this study phosphorus recovery from sludge liquor by ion exchange process was investigated. The efficiency of a commercially available anionic iron oxide resin was evaluated in batch and packed column tests using synthetic phosphorus solution and actual sludge liquor, taken from of an urban wastewater treatment plant (UWWTP). When phosphorus recovery from sludge liquor was investigated, experimental data fitted quite well Generalized Langmuir–Freundlich isotherm (R² = 0.92 for the new resin and R² = 0.96 for the regenerated resin); the maximum adsorption capacity being 14.2 and 14.4 mg P/g, respectively. The saturation of adsorption sites was not achieved also after 11.5 hours and 120 bed volumes, in column tests. When the reactor was operated with sludge liquor and the new resin, the saturation of packed bed was achieved after approximately 175 min and 31 bed volumes. The recovery efficiency of phosphorus during the regeneration step was as high as 95% (less than 13 bed volumes). According to the results achieved and the increasing cost of phosphorus production from conventional resources (yearly incremental cost 0.012 €/(kg · y)), its recovery from UWWTPs sludge liquor by the ion exchange process is expected to be really useful and beneficial for the following 10–15 years.     

Treatment of wastewater containing Pb and Fe using ion‐exchange techniques

Treatment of wastewater containing lead and iron was examined using two different ion‐exchange resins namely Duolite ES 467 (containing amino‐phosphonic functional groups) and a chelating ion‐exchange resin (containing hydroxamic acid functional groups). Initially different sorption parameters such as contact time, pH, concentrations of sorbent, sorbate and chloride ion were studied. The sorption kinetics was observed to be fast and equilibrium could be reached within 30 min. Lead sorption efficiency increased with increase in pH whereas the opposite trend was observed with iron. The presence of chloride ions greatly reduced the Pb sorption efficiency in the case of Duolite ES 467. Column studies were carried out to recover Pb and Fe individually using Duolite ES 467 resin. The maximum uptake of Pb at pH 2 and 3 was observed to be 11.63 and 33.96 g dm^?3 of resin respectively. Similarly, for Fe at pH 2 and 3 the uptake was observed to be 10.07 and 6.96 g dm^?3 of resin respectively. In the presence of chloride ions, column studies were carried out using Duolite ES 467 for iron and chelating ion‐exchange resin containing hydroxamic acid functional groups for lead sorption. Hydroxamic acid resin's loading capacity remains constant for at least up to 20 cycles. Copyright © 2005 Society of Chemical Industry     

Infra-red spectra of perfluorinated cation-exchanged membranes

Assignment of the i.r. spectrum of Nafion cation exchange membranes was made possible by use of i.r. absorption and reflectance (ATR) spectroscopy. Shifts in the water and sulphonic vibrations occurring upon exchange of various counterions were compared with those occurring in a polyethylene sulphonic acid and polystyrene sulphonic acid membrane. The type of binding of the cations and the possibility of cluster formation are discussed. A dimeric iron unit FeOFe was identified in the Nafion membrane.     

CHITOSAN-BASED FUEL CELL MEMBRANES

Chitosan complex membranes are prepared and characterized at room temperature. They are expected to be used as proton exchange membranes. The studied membranes are cross-linked membranes with sulfuric acid; salt-complexed membranes with lithium nitrate; cross-linked and salt-complexed membranes; plasticized and salt-complexed membranes; cross-linked, plasticized, and salt-complexed membranes; and doped membranes with sulfuric acid. A fixed amount of ethylene carbonate is used as plasticizer. It is found that the ion exchange capacity and hydrogen gas permeability of all membranes is better than that of Nafion membranes. However, their proton conductivities are worse than Nafion membranes. It can be stated that ethylene carbonate does not improve conductivity. An optimum amount of lithium nitrate salt can enhance conductivity. The formation of a sulfate group in cross-linked membranes is necessary for proton conduction. The proton conductivities of 4%cross-linked and 50%LiNO₃ membrane before and after acid doping are (3.11±0.40) × 10^?2 and (6.64±0.11) × 10^?2 S cm^?1, respectively. That of Nafion is (8.02±1.19) × 10^?2 S cm^?1.     

Adsorption behavior of L-tryptophan on ion exchange resin

A batch method was applied to investigate the adsorption behavior and mechanisms of L-tryptophan (L-trp) on ion exchange resins. HZ-001 and JK006 were proved to be ideal adsorbents due to their large loading capacityand favorable selective adsorption for L-trp. Langmuir, Freundlich, and Dubinin-Radushkevich equations were appliedto simulate the experimental data to describe the adsorption process of L-trp onto HZ-001 and JK006. The maximumloading capacity (at pH 5.0, 30 °C), determined by the Langmuir and Dubinin-Radushkevich models, was close to eachother (833 mg/g vs. 874 mg/g) for HZ-001, while discrepant (833 mg/g vs. 935 mg/g) for JK006. Three diffusion-controlled kinetic models were utilized to analyze the results in order to identify the adsorption mechanism. The adsorptionkinetics of L-trp onto cation exchange resins was investigated under different experimental conditions, including initialsolution pH, temperature, initial L-trp concentration, and adsorbent dosage. Moreover, the diffusion process of L-trponto HZ-001 and JK006 was evaluated at different initial adsorbate concentrations. The thermodynamic parameters, obtained from the kinetic data, demonstrated that L-trp could be adsorbed spontaneously onto both resins.     

Preparation of poly(acrylic acid)/poly(vinyl alcohol) membrane for the facilitated transport of CO2

Poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) membrane was prepared for the facilitated transport of CO₂. The carrier of CO₂ was monoprotonated ethylenediamine and was introduced in the membrane by ion exchange. The ion‐exchange capacity of the membrane was 4.5 meq/g, which was much higher than that of the Nafion 117 membrane. The membrane was highly swollen by the aqueous solution. Much higher selectivity of CO₂ over N₂ and higher CO₂ permeability were obtained in the PAA/PVA membrane than in the Nafion membrane because of the higher ion‐exchange capacity and solvent content. The highest selectivity was more than 1900 when the CO₂ partial pressure in the feed gas was 0.061 atm. Effects of ion‐exchange capacity, membrane thickness, and annealing temperature in conditions of membrane preparation on membrane performance were investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 936–942, 2001     

Preparation Polyelectrolyte Complexes of Chitosan-Polyacrylic Acid-Modified Iron Sand Leachate for Proton Exchange Membranes

ABSTRACT

Polyelectrolyte complex (PEC) of chitosan (Chi) and poly (acrylic acid) (PAA)-modified iron sand leachate were prepared and considered for applicability as a proton exchange membrane in fuel cells. Chi-PAA-hematite blended in different weight ratios and the resulting membranes were treated to enable the formation of the polyelectrolyte. The membranes of Chi-PAA polyblend were treated using iron sand leachate and reveal high ion exchange capacity (IEC), proton conductivity, water uptake, and good mechanical stability. The result of research indicated that the membrane with 40 wt% of Chi and 60 wt% of PAA blend which its conductivity of 6.10 × 10^?2 S cm^?1 was potentially for a proton exchange membrane in fuel cell applications.     

Removal of Arsenic(III), Chromium(III) and Iron(III) Traces from Hydrofluoric Acid Solutions by Specialty Anion Exchangers

The removal of As(III), Fe(III), and Cr(III) at trace levels from HF solutions by means of specialty ion exchange resins has been investigated. These impurities are usually found in technical‐grade HF, and they need to be removed to prepare metal‐free HF for the semiconductor industry. It was assumed that Fe(III) and As(III) species in dilute HF were present in anionic form, while Cr(III) was probably in neutral form, CrF₃. First, a selection of specialty ion exchangers was performed. Then, fixed‐bed experiments were carried out to check the ability of selected resins to reach the impurity levels required in SEMI C29 for 5 wt.% HF (5 ppb of As, and 10 ppb of Cr and Fe). The effect of the flow rate and the HF concentration on the metal removal was studied with Purolite D‐3777 and Fuji PEI‐CS‐07 resins respectively. Fuji PEI‐CS‐07 showed the best performance for Fe(III) removal, even at high HF concentration (25 wt.%). A strong decrease in the Cr(III) and As(III) removal capacity with increasing concentration of HF was observed.     

TUNGSTEN TRIOXIDE HYDRATE INCORPORATED NAFION COMPOSITE MEMBRANE FOR PROTON EXCHANGE MEMBRANE FUEL CELLS OPERATED ABOVE 100°C

A new composite membrane is fabricated by incorporating tungsten trioxide hydrate into Nafion to be employed as a candidate electrolyte for proton exchange membrane fuel cells (PEMFCs) operated above 100°C. Thermal behavior and proton conductivity of the composite membrane are studied by means of thermogravimetric/differential thermal analyis (TG/DTA) and AC impedance measurements, respectively. These results demonstrate that the thermal stability of the composite membrane has no appreciable change when compared with the native Nafion membrane. The proton conductivity of the composite membrane is found to be better than that of the native Nafion membrane at high temperature and lower relative humidity. When the composite membrane is used as an electrolyte in H₂/O₂ PEMFC under the operating conditions of 110°C, 1.36 atm gas pressure, and 70% relative humidity, the observed current density value at 0.4 V is 1.5 times higher than that of the cell employing native Nafion membrane as an electrolyte.     

甘氨酸在离子交换树脂中扩散过程的控制步骤

研究了甘氨酸在001 ×7,001 ×4和D061 3种阳离子树脂上离子交换动力学过程,对甘氨酸在3种离子交换树脂上的扩散过程控制步骤进行分析.使用间歇式搅拌槽法分别测定了不同温度下甘氨酸在001 ×7,001 ×4和D061树脂上的吸附曲线,估算了颗粒扩散系数和相间传质系数,并比较了3种阳离子交换树脂吸附甘氨酸的特性...     

Preparation of highly efficient and stable Fe,Zn,Al-pillared montmorillonite as heterogeneous catalyst for catalytic wet peroxide oxidation of Orange II

Fe,Zn,Al-pillared montmorillonite (Mt) were prepared by ion exchange reaction. Effect of the Fe/Zn molar ratio in Fe,Zn,Al-pillaring solution on the structural properties of Fe,Zn,Al-Mt was examined. Characterization studies were performed by N₂-adsorption/desorption, ICP, FTIR, DR UV–Vis spectroscopy and XRD. The interlayer space, specific surface and volume of micropores of pillared-Mt was 18.8 Å, 157 m² g^?1 and 0.114 cm³ g^?1 respectively. Besides, the catalytic performance of Fe,Zn,Al-Mt was analyzed through wet peroxide oxidation of Orange II under mild experimental condition. The results indicated that the catalytic performance of Fe,Zn,Al-Mt was affected by the Fe/Zn molar ratio as following pattern: the obtained pillared solids with lower Fe/Zn molar ratios exhibited better catalytic performance and less iron leaching during the reaction. Moreover, the introduction of zinc into Mt shortened the induction time of reaction and improved the catalytic behaviour. Throughout this work, the chemical oxygen demand removal of OII was 77.1 % after the solution treated by Fe,Zn,Al(3/7)-Mt (defined as the Fe/Zn molar ratio of 3/7 in the pillaring solution) catalyst at temperature of 60 °C and atmospheric pressure of 1 atm.     

Batch adsorptive removal of copper ions in aqueous solutions by ion exchange resins: 1200H and IRN97H

The removal of copper from aqueous solution by ion exchange resins, such as 1200H and IRN97H, is described. Effect of initial metal ion concentration, agitation time and pH on adsorption capacities of ion exchange resins was investigated in a batch mode. The adsorption process, which is pH dependent, shows maximum removal of copper in the pH range 2–7 for an initial copper concentration of 10 mg/L. The experimental data have been analyzed by using the Freundlich, Langmuir, Redlich-Peterson, Temkin and Dubinin-Radushkevich isotherm models. The batch sorption kinetics have been tested for a first-order, pseudo-first order and pseudo-second order kinetic reaction models. The rate constants of adsorption for all these kinetic models have been calculated. Results showed that the intraparticle diffusion and initial sorption into resins of Cu(II) in the ion exchange resins was the main rate limiting step. The uptake of copper by the ion exchange resins was reversible and thus has good potential for the removal/recovery of copper from aqueous solutions. We conclude that such ion exchange resins can be used for the efficient removal of copper from water and wastewater. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Influence of Resin Molecular Weight on Curing and Thermal Degradation of Plywood Made From Phenolic Prepreg Palm Veneers

The present work evaluates curing and the thermal behavior of different molecular weight phenol formaldehyde (PF) resins used to prepare PF prepreg oil palm stem veneers. The physical properties (solid contents, gelation time, pH, and viscosity) of PF resins were determined. The molecular weight of resins was characterized by gel permeation chromatography, whilst thermal properties were determined by differential scanning calorimetry and thermogravimetric analyses. The average molecular weight of PF resins were 526 g/mole (low), 1889 g/mole (medium), and 5178 g/mole (control - commercial). Among the resins, medium (MMwPF) gives better thermal stability with a retained weight of 48.9% at 300°C. High (Commercial PF) had a low decomposition temperature (109.3°C) which occurred within 11 min. Both low (LMwPF) and MMwPF started to melt at ≥120°C. Based on strength and shear values, phenolic prepreg palm veneers can be prepared using either low or medium molecular weight PF but with varying results. In all cases, the mechanical properties of palm plywood made from PF prepreg veneers were superior to those made from PF-bonded plywood using the commercial process.     

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.     

Use of deep eutectic solvent as extractant for separation of Fe (III) and Mn (II) from aqueous solution

In this work, we used deep eutectic solvent (DES) composed of decanoic acid and lidocaine, which is characterized as a green solvent, for separation of Fe (III), which is the most-used metal in the world, and Mn (II), which is currently being used in many industries. We found that the pH of the initial metal solution strongly influenced the extraction mechanism. Fe (III) can be extracted at pH 1.0–2.0 due to the ion pair reaction between Fe³⁺ and decanoic anion, while at higher pH, the extraction mechanism cannot be evaluated due to formation of precipitation at the aqueous phase. In the case of Mn (II), the ion pair reaction occurred at pH of lower than 2.2 and higher than 3.5, while from pH 2.2 to 3.5, the cation exchange between Mn²⁺ and lidocaine cation probably dominated the extraction process. The DES concentration needed to reach the complete separation of Fe (III) was about 25 g/L, while Mn (II) was completely extracted using about 300 g/L of DES. The selectivity of this method was very high when was applied in the separation of Fe (III) from Mn (II).     

Synthesis of organic-inorganic composite membrane by sol-gel process

Silica was succesfully incorporated into cation exchange polymer membranes, CL-25T and Nafion 417, utilizing sol-gel process. As dipping time increased, increase in silica uptake in membrane was observed. In Nafion 417 membrane, no relationship was found between the silica uptake and the change in ion exchange capacity. But CL-25T which has larger pores than Nafion 417 shows proportional decrease in ion exchange capacity with increasing silica uptake. It suggests that the pore structure of membrane and the size control of silica sol are important to modify the structure of composite membranes. In CL-25T membranes modified by silica, the transport rate of IPA (isopropyl alcohol) increased with increasing OH^- concentration on the pore surface.     

载铁(Fe~(2+))螯合树脂的制备及其去除水中余氯的研究

用D401氨基羧酸螯合树脂吸附Fe2+,获得了具有还原性能的载铁改性树脂,利用水中余氯与Fe2+的氧化还原作用,实现了对水中微量余氯的去除。实验结果表明,树脂改性的最佳条件为:Fe2+溶液浓度4 045.44 mg/L,pH在3~5,改性时间2 h。可得到载铁量为39.648 mg/g。当树脂交换铁量达到平衡时,其吸附除氯率可高达98%以上,溶液中余氯残留量低于0.5 mg/L。全过程无其他离子引入水中。获得了一种新的从饮用水中去除有害余氯的方法。     

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.     

Highly methanol resistant and selective ternary blend membrane composed of sulfonated PVdF‐co‐HFP,sulfonated polyaniline and nafion

Partially sulfonated poly(vinylidene fluoride‐co‐hexafluoro propylene)/partially sulfonated polyaniline (SPVdF‐co‐HFP/SPAni) binary blend membranes have shown promising results in terms of low methanol permeability and high membrane selectivity compared to Nafion‐117 membrane. However, the proton conductivity and IEC of this binary blend membrane was much lower than Nafion‐117. It was found that incorporation of minimal quantity of Nafion within SPVdF‐co‐HFP/SPAni blend membrane at a constituent weight % ratio of SPVdF‐co‐HFP:SPAni:Nafion = 50:40:10 induced significant improvements in ion‐exchange capacity (IEC), proton conductivity and tensile strength over that of the binary blend membrane. In addition, the SPVdF‐co‐HFP/SPAni/Nafion ternary blend membrane exhibited much lower methanol permeability, higher membrane and relative selectivities and comparable IEC to Nafion‐117. In effect, presence of minimal quantity of Nafion induced significant positive attributes to the ternary blend membrane; and assisted in reaching a balance between material cost and properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43294.