Preparation of ion exchange resins from carbonaceous adsorbents

Carbonaceous adsorbents are obtained by thermolysis of sulfonated macroreticular polystyrene ion exchange resins at 300-500°C. The hard, spherical, carbonaceous particles react exothermally with elemental chlorine to form products containing up to 38% Cl. The chlorinated particles react readily with polyamines to form anion exchange resins with capacities of up to 2.2 meq/g dry resin. Less than 60% of the nitrogen atoms in the particles are utilized as ion exchange sites. The carbonaceous particles can also be chloromethylated with chloromethyl methyl ether or chlorinated with sulfuryl chloride and then aminated with polyamines to form anion exchange resins, sulfonated with sulfuric acid or chlorosulfonic acid to form strongly acidic cation exchange resins, or chlorosulfonated and then aminated with polyamines to form anion exchange resins. Model structures of the thermolyzed resins containing polycyclic aromatic hydrocarbon fragments are proposed to explain their chemical reactivities.     

Ion-exchange resins in non-aqueous solvents-III Solvent-uptake properties of ion-exchange resins and related adsorbents

Solvent-uptake properties for several synthetic resins and common adsorbents were determined by the centrifugation method. Data are reported for eighteen different solvents, which include water and the common polar and non-polar organic solvents. The cation-exchange resins are of two varieties: the microreticular or gel type and the macroreticular or porous type. The latter resin being rigid and porous takes up all types of solvents, whereas the former resin, which relies on swelling of the resin matrix, does not take up the nonpolar solvents. Data for the H(+) form and Na(+) form macroreticular resin are compared. Unsulphonated polystyrene-divinylbenzene polymers which possess similar micro- and macroreticular properties to the cation-exchange resins were also studied in the same solvents. The swelling properties of these non-polar resins are compared with each other and with the polar cation resins. Other adsorbents, which are frequently used as supports in chromatography were also examined in the same solvents. Several of these have large average pore diameters and surface areas like the macroreticular resin.     

Ion exchange studies of U(VI), Th(IV), Pu(IV) and Eu(III) on a macroreticular resin in TBP-Shell Sol-T solutions

Ion exchange studies of uranium(VI), thorium(IV), plutonium(IV) and europium(III) ions on a macroreticular cation exchange resin, Amberlyst A-15, from solutions of 30% and 5% TBP—Shell Sol-T have been carried out. The metal ions were extracted into TBP Shell Sol-T phase from 8M NH₄NO₃ at different nitric acid concentrations. Ion exchange distribution ratios as a function of organic phase acidity of 30% and 5% TBP have been computed. Separation factors computed from the observed Kd values are plotted as a function of organic phase acidity.     

弱碱性和强碱性阴离子交换树脂的离子交换平衡的比较SO2-4-Cl——NO-3体系

本文详细地比较了在弱碱性和强碱性阴离子交换树脂上, SO_4~(2-)-Cl~-、NO_3~--Cl~-及NO_3~--SO_4~(2-)二元交换的等温线和修正选择系数。实验测定及理论计算了上述三种二元交换反应的标准自由能的改变量。测得了在弱碱性树脂上的SO_4~(2-)-Cl~--NO_3~-三元交换的等温线。适用于强酸性和强碱性树脂的从二元交换平衡数据推算三元交换平衡数据的方法推广应用于弱碱性树脂。     

Some ion-exchange resins for anion-chromatography

The quaternary ammonium salts, n-butyltrimethylammonium iodide, 1,1,3,3-tetramethylbutyltrimethylammonium iodide, n-octadecyltrimethylammonium iodide and tri-n-dodecylmethylammonium iodide were synthesized from commercially available amines and together with n-hexadecyltrimethylammonium bromide tested for retention by a series of macroreticular resins (XAD-2, XAD-4, XAD-7, XAD-8 and XAD-11) for use as "surface" ion-exchangers in the chromatography of anions. Exchange-capacity studies of the coated resins showed that the non-polar XAD-2 and XAD-4 resins had retention characteristics superior to those of the polar resins and that pore size in the resin was more important than surface area per unit weight of resin. Tri-n-dodecylmethylammonium salts in XAD-2 gave the highest exchange capacity, with best retention under elution conditions. Columns prepared from this anion-exchanger were used to separate and analyse simple mixtures of anions (chloride, nitrate and sulphate) each within the 1-30 ppm range, by single-column operation with indirect photometric detection and also by conductivity detection with background-ion suppression. Though of use for the determination of anions in simple mixtures, the resolution and performance were generally poorer than those displayed by a commercial (Dionex) column. This is at least partly attributable to the inferior column-packing properties of the granular XAD-resin.     

蛇笼树脂交换量的测定

本文介绍了蛇笼树脂的结构及其离子阻滞作用机理,提出了离子阻滞交换量的概念.研究了残余阴离子交换量、残余阳离子交换量、全阴离子交换量、离子阻滞交换量和全阳离子交换量的测定及计算方法,测定了美国的Retardion 11A-8及本文合成的9种蛇笼树脂的交换量.     

Uptake of alkanes and alcohols by ion-exchange resins in aqueous solution.

Uptake of alkane (C5-C9) and alcohol (C4-C7) solutes by both strong acid cation exchange resins and strong base anion exchange resins in aqueous medium has been studied. The amount of solute taken up by resins is directly proportional to the solute concentration equilibrium with resins. Hydrophobic interaction between the solute and the resin matrix appears to play an important role in the uptake phenomenon.     

Phenol removal from aqueous solution by adsorption and ion exchange mechanisms onto polymeric resins

The removal of phenol from aqueous solution was evaluated by using a nonfunctionalized hyper-cross-linked polymer Macronet MN200 and two ion exchange resins, Dowex XZ (strong anion exchange resin) and AuRIX 100 (weak anion exchange). Equilibrium experimental data were fitted to the Langmuir and Freundlich isotherms at different pHs. The Langmuir model describes successfully the phenol removal onto the three resins. The extent of the phenol adsorption was affected by the pH of the solution; thus, the nonfunctionalized resin reported the maximum loading adsorption under acidic conditions, where the molecular phenol form predominates. In contrast both ion exchange resins reported the maximum removal under alkaline conditions where the phenolate may be removed by a combined effect of both adsorption and ion exchange mechanisms. A theoretical model proposed in the literature was used to fit the experimental data and a double contribution was observed from the parameters obtained by the model. Kinetic experiments under different initial phenol concentrations and under the best pH conditions observed in the equilibrium experiments were performed. Two different models were used to define the controlling mechanism of the overall adsorption process: the homogeneous particle diffusion model and the shell progressive model fit the kinetic experimental data and determined the resin phase mechanism as the rate-limiting diffusion for the phenol removal. Resins charged after the kinetic experiments were further eluted by different methods. Desorption of nonfunctionalized resin was achieved by using the solution (50% v/v) of methanol/water with a recovery close to 90%. In the case of the ion exchange resins the desorption process was performed at different pHs and considering the effect of the competitive ion Cl⁻. The desorption processes were controlled by the ion exchange mechanism for Dowex XZ and AuRIX 100 resins; thus, no significant effect for the addition of Cl⁻ under acidic conditions was observed, while under alkaline conditions the total recovery increased, specially for Dowex XZ resin.     

Solid-state storage of Ag nanoparticles in anion exchange resin beads and their recovery

This paper reports the idea and describes a method of reversible storage and recovery of silver nanoparticles (NPs) in anion exchange resin beads based on the principle of ion exchange. We also report that similar exchange of NPs was not possible with cation exchange resins. The Ag NPs were stored by simple exchange of anions of the resins, which were activated with OH- and NO3- ions. FTIR spectroscopic measurements support that the Ag NPs were exchanged with NO3- ions in the resins. The so-stored NPs could be regenerated by addition of NaBH4 solution to the resins. These NPs were recovered and subsequently utilized for catalytic reduction of an organic dye (eosin). Powder X-ray diffraction (XRD) pattern indicated storage of the NPs in the form of various oxides of silver in the resin, with the peak value of intensity corresponding to XRD of the NPs not changing with time. Scanning electron microscopic measurements show that the NPs in the beads were stable for over a month without the formation of any apparent agglomeration.     

Ion-exchange resins in non-aqueous solvents-I Sorption rates of p-nitroaniline and the effects of small amounts of water

The rates of sorption of p-nitroaniline onto three hydrogenform resins in methanol, ethanol, n-propanol, isopropanol, n-butanol, acetonitrile, benzene, acetic acid and dioxan are reported. Two of the resins are typical gel-type, microreticular, sulphonated resins and the third is a new, highly porous and rigid, macroreticular, sulphonated resin, Amberlyst 15. There appears to be a correlation between viscosity or dielectric constant and the time for maximum sorption or maximum distribution coefficient when the alcohols are used, but no correlation for all the solvents is apparent. The macroreticular resin still functions when dry, even in the presence of non-polar solvents, but the microreticular resin does not. Small amounts of water present in the solvent or resin aid the sorption of the amine onto both types of resin. The effect of mesh size and cross-linkage are examined.     

丙烯酸在强碱阴离子交换树脂中的聚合

研究了以水为介质，丙烯酸在强碱阴离子交换树脂中聚合时羧基分配系数随浸泡时间和反应时间的变化，以及树脂残阴交换量随反应时间的变化，结果是羧基分配系数在浸泡一小时后达到平衡，聚合反应开始后分配系数又迅速增大，三小时后达到最大值。残阴交换量随反应进行而减小，三小时后达到最小值。经分析认为丙烯酸的主要聚合场所是在树脂相，聚合过程中单体不断向树脂相扩散，基本不在液相聚合。     

The sorption of polymetaphosphate on anion exchange resins

From a solution of sodium polymetaphosphate, strongly basic anion exchange resins can retain a greater amount of polymetaphosphate than that corresponding to the exchange capacity. Sodium ions are held by the polymetaphosphate form of the resin and these sodium ions can be exchanged for other ions.     

INTERACTION OF AMINO ACID WITH ION EXCHANGE RESIN Ⅲ.FURTHER INVESTIGA TION OF SUPEREQUIVALENT ADSORPTION MECHANISM OF AMINO ACID ON ION EXCHANGE RESIN

The adsorption isotherms of glycine,alanine and oxidized glutathion on strong acid cation and strong base anion exchange resins from aqueous solutions were measured and the superequivalent adsorptions of glycine and alanine observed.The infrared spectra of glycine adsorbed on the cation and the anion exchange resins,001×7 and 201×7,were measured.From these results,it is concluded that the amino acid adsorption on the ion exchange resin proceeds not only through ion exchange and proton transfer mechanisms,but also through aminecarboxylate interaction between the adsorbed amino acid molecules,and the formation of second layer of amino acid molecules is the mechanism of superequivalent adsorption of amino acid,the carboxylate or amine groups of the first layer of amino acid molecules on the ion exchange resin act as the exchange sites for the second layer of amino acid molecules.     

Recovery and purification of plutonium in lean plutonium product stream obtained during reprocessing of fast reactor spent fuels

A method has been developed for final purification of plutonium from uranium and fission products of high beta gamma activity. This method involves selection of a suitable ion exchange resin for the purification of plutonium in order to deliver a quality PuO₂ product. The effect of the concentration of uranium and plutonium, effect of increased loading of uranium and number of bed volumes for effective washing, which are some of the parameters that generally affect the recovery and purification of plutonium were investigated. An excellent decontamination factor for fission products has been achieved by this anion exchange process which in turn delivered an excellent PuO₂ product quality in terms of purity and associated beta gamma activity with low personnel radiation exposure.     

大孔树脂分离纯化丹酚酸的研究

比较了D301R、D392、D380大孔阴离子交换树脂和X-5.AB-8、NKA-9、SP825大孔吸附树脂对丹参水溶性成分的吸附和解吸能力,筛选出效果较好的SP825进行分离纯化丹酚酸的研究.实验表明,大孔吸附树脂SP825能分离出纯度为95.32%的丹参素,在梯度洗脱条件下可得到以丹参素(水洗脱)和丹酚酸B(乙醇洗脱)为主的产品.在最佳吸附与解吸工艺参数下,丹参素、紫草酸、迷迭香酸、丹酚酸A和丹酚酸B的收率分别为:36.92%、80.39%、82.45%、43.07%和41.03%.     

Ion-isotopic exchange reaction kinetics using organic base anion exchange resins Indion-102 and Indion GS-400

The present study deals with the kinetic study of iodide and bromide ion-isotopic exchange reactions in organic based anion exchange resins Indion-102 (nuclear grade) and Indion GS-400 (non-nuclear grade) using radiotracer isotopes. The resins in iodide and bromide form were equilibrated respectively with iodide and bromide ion solutions which were previously spiked with ¹³¹I and ⁸²Br radiotracer isotopes. For both bromide and iodide ion-isotopic exchange reactions, it was observed that the values of specific reaction rate increase with increase in ion concentration from 0.001 to 0.004 M at a constant temperature of 40.0°C. However, at constant ion concentration of 0.003 M, the specific reaction rate was observed to decrease with rise in temperature from 30.0 to 45.0°C. Also it was observed that for iodide ion-isotopic exchange reaction by using Indion-102 resin, the values of specific reaction rate, amount of iodide ion exchanged, initial rate of iodide ion exchange and logK _d were 0.258 min^?1, 0.492 mmol, 0.127 mmol/min and 19.2, respectively, which were higher than 0.208 min^?1, 0.416 mmol, 0.087 mmol/min and 17.6, respectively, obtained by using Indion GS-400 resin under identical experimental conditions of 40.0°C, 1.000 g of ion exchange resin and 0.003M labeled iodide ion solution. The same trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate that, under identical experimental conditions, Indion-102 resin shows higher performance than Indion GS-400 resin.     

钯-高分子载体催化剂对糠醛加氢液相反应的研究

以弱碱性苯乙烯系阴离子交换树脂[D392,-NH₂,D382,-NHCH₃,D301R,-NH(CH₃)₂],强碱性苯乙烯系阴离子交换树脂[201×7DVB,-NH⁺(CH₃)₃]和弱碱性环氧系阴离子交换树脂(701,-NH₂)为载体制备了3种钯-高分子载体催化剂.考察了反应条件、高分子载体的种类、钯含量和催化剂用量对糠醛催化加氢生成四氢糠醇反应及催化性能的影响.在体积分数为50%的乙醇-水溶液和水中对糠醛常压液相加氢反应,钯-高分子载体(阴离子交换树脂D392,-NH₂,D382,-NHCH₃)催化剂均可使糠醛的加氢反应转化率达100%,生成四氢糠醇的选择性达98%以上,而用金属钯为催化剂的转化率达70%以上,选择性达97%以上.同时用XPS分析了高分子载体催化剂的结构与催化加氢反应性能的关系.     

Adsorption Behavior of Metal Ions by Amidoxime Chelating Resins

In this work, the acrylonitrile (AN) – divinylbenzene (DVB) –methylacrylate (MA) resin was synthesized via suspension polymerization in the presence of toluene as diluent, and benzoylperoxide (BPO) as initiator. The effect of MA, toluene and alkaline treatment on the exchange capacity of the resin were investigated. The results showed that the anion exchange capacity decreased with an increase in the amount of MA, while alkaline treatment had no significant effect. Also, the cation exchange capacity increased with an increase in the amount of hydrophilic agent and reached a maximum point. The sorption equilibrium was achieved relatively fast within 40 mins, and the resin exhibited affinity towards lead (II), copper (II) and in particular uranium (VI). The adsorption of uranium was directly depended up on the pH value. Furthermore, the macroreticular chelating resin, containing amidoxime group had higher adsorption of uranium (VI) in comparison to other metal ions studied. Finally, the alkaline treatment enhanced the potential for much faster adsorption characteristics and the highly porous chelating resin provided a more favorable pore structure for the rapid rate of diffusion of metal ions.     

含长碳链间隔臂结构的强碱性阴离子交换树脂的合成及热稳定性

研究了一种含长碳链间隔臂结构的强碱性阴离子交换树脂的新合成方法.评价了该树脂在水中的热稳定性.结果表明,以苯乙烯-二乙烯基苯共聚白球和1,3-噁嗪-2-酮为原料,季铵型离子液体为催化剂,得到带有胺丙基的苯乙烯-二乙烯基苯共聚珠体,再用甲酸和甲醛N-甲基化,溴乙烷季铵化,可以生成强碱交换量为1.86mmol/g强碱阴离子交换树脂.含长碳链间隔臂结构的OH~-型阴离子交换树脂在100℃去离子水中保持720h交换量仅下降11.83%,好于商业通用的强碱阴离子交换树脂.     

Plutonium and americium in sediment samples along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of²³⁸Pu,^239,240Pu and²⁴¹Am were determined in eight sediment samples, collected from the bed of the Romanian sector of the Danube river and the Black Sea coast during 1994 and 1995. Fusion with potassium carbonate was used to achieve complete dissolution of the samples. Tracers,²⁴²Pu and²⁴³Am, were added and the separation of plutonium from americium, uranium and thorium was performed by anion exchange. Americium was separated from uranium in two steps, using a conventional anion exchange resin and an extraction chromatographic resin for transuranics. After electrodeposition on stainless steel discs the nuclides were counted with -spectrometry with -PIPS detectors. The total plutonium concentrations obtained by this method were compared with the acid leachable plutonium concentrations reported for the same samples in a previous paper.