Removal of dark coloured and polyphenolic compounds of sugar beet vinasse by adsorption onto activated carbons: Application to a crosscurrent adsorption process

Sugar beet distillery vinasse is rich in betaine but the recovery of betaine by ionic exchange first requires removing ethanol‐insoluble compounds as well as dark coloured and polyphenolic compounds. The adsorption kinetics and isotherms of the latter compounds were studied on two commercial activated carbons. The results show that the pseudo‐second order kinetic model provided the best correlation, and the Langmuir model was selected for describing the isotherms. The data can be used to conduct experiments with a view to applying the crosscurrent process methodology to determine the number of stages necessary for the discolouration of the solution. © 2011 Canadian Society for Chemical Engineering     

甜菜糖蜜发酵废液中提取甜菜碱新工艺研究

研究了采用三段离子交换法从甜菜糖蜜发酵废液中提取甜菜碱的工艺条件和影响因素。三段交换分别使用D31 4、D0 0 1及 0 0 1× 7等苯乙烯型离子交换树脂。第一段交换使脱色、脱盐和除杂同时进行 ,免除了活性炭脱色过程。确定了第二段脱盐交换以pH =3为终点 ,使甜菜碱与金属离子彻底分离。第三段为吸附纯化甜菜碱 ,使用 c(HCl) =1 4mol/L为洗脱剂 ,直接制取了盐酸甜菜碱 ,并使洗脱与树脂再生同时进行 ,简化了工艺操作。所得产品纯度达 98%以上 ,收率(对甜菜 )达 90 %以上。     

Continuous removal of ammonium ion by ion exchange in the presence of organic compounds in packed columns

The removal of ammonia from wastewaters after secondary biological treatment can successfully be achieved by ion exchange. However, the presence of residual organic compounds can impart significant influence on the uptake and their presence may need to be considered during the design of a treatment system. The aim of this work was to determine the effect of the presence of certain organic compounds upon the uptake of ammonium ion and column breakthrough. Two organic contaminants were considered, including citric acid and protein (as whey protein isolate). Three cationic exchangers were used and included the natural zeolite clinoptilolite, the gel resin Dowex 50w‐x8, and a macronet resin, Purolite MN‐500. The influence of regeneration upon column breakthrough behaviour was also determined. The results showed that the presence of organic compounds had variable effects on ammonium ion uptake. In the case of clinoptilolite the presence of protein appeared to have very little effect upon breakthrough capacity. In the case of the clinoptilolite and the MN500 a substantial reduction of breakthrough capacity was observed in the presence of citric acid. In the case of clinoptilolite a very significant increase in column breakthrough performance was observed after cycles of exhaustion and regeneration. This was not observed in the case of the synthetic resins, which showed a more consistent performance from run to run. Overall the Dowex50w‐x8 gave the highest breakthrough capacity for ammonium ion removal of 700 bed volumes. Regenerated clinoptilolite showed a maximum breakthrough capacity of 450 bed volumes, and MN‐500 a consistent breakthrough capacity of 300 bed volumes. Copyright © 2006 Society of Chemical Industry     

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.     

处理高浓度氨氮废水的阳离子交换树脂筛选

目前树脂种类繁多,给处理高浓度氨氮废水的树脂选型带来困难。根据离子交换理论,利用001×7、D61和D001三种阳离子交换树脂,模拟研究了氮肥厂废水（氨氮浓度为915 mg·L^-1）氨氮的吸附等温式,在30～50 min内三种树脂对氨氮的吸附基本可达到平衡,吸附等温线均符合Freundlich吸附模式;进而研究了这三种树脂对废水中氨氮吸附的选择性系数、工作交换容量和离子交换速率。结果表明,用D61树脂处理含高浓度氨氮的废水效果较为理想,可以相对较少的用量,使处理后水质达到相关排放标准的要求。     

固定床动力学模型在离子交换过程中的应用

为了掌握所选的Thomas模型,Yoon-Nelson模型和Adams-Bohart模型在固定床米格列醇离子交换过程中的应用情况,实验借助对不同质量浓度的米格列醇溶液在定量树脂和固定流速下研究其在固定床中离子交换过程,并通过对透过曲线实验数据分析来验证相关固定床动力学模型在此过程中的有效性。结果表明:固定床上样液质量浓度增大,达到平衡饱和点的时间将缩短,传质区长度增大,吸附率变小,上样液质量浓度在8 mg/mL时吸附量达到最大;用动力学模型拟合透过曲线的过程参数,结果表明Thomas模型和Yoon-Nelson模型具有较好的相关系数,Thomas模型的速率常数和最大吸附量值随着上样液质量浓度的降低而增大,Yoon-Nelson模型的速率常数随着上样液质量浓度的降低而减小,且在Yoon-Nelson模型中计算得到的透过曲线中出口质量浓度与上样质量浓度比值为1/2时所对应的计算值和实验值相差很小,Thomas模型和Yoon-Nelson模型可用于该过程的离子交换性研究。     

Kinetic of copper ion exchange onto iminodiacetic resin

The internal porosity and swelling/shrinking of a chelating iminodiacetic type ion exchange resin have been experimentally studied during the uptake of copper onto it. The swelling of the particle could be analyzed with a modified model on th basis of the unreacted core model (UCM), including the influence of chemical equilibrium. The ion exchange kinetic results in batch experiments are used with the UCM to calculate the effect of pH on the internal diffusion coefficients. Results from shallow bed experiments with mixed internal and external diffusion controls have shown the applicability of the above model to analyze ion exchange with low external velocities.     

Purification of glycerol/water solutions from biodiesel synthesis by ion exchange: sodium and chloride removal. Part II

BACKGROUND: Equilibrium studies were carried out with the aim of finding the basic design parameters for ion exchange plants using a glycerol phase obtained from biodiesel production. The uptake of sodium and potassium ions on a strongly acidic ion exchanger, Amberlite IR‐120, in the proton form from glycerol/water mixtures has been studied. The effect on the selectivity towards sodium of the percentage of water in glycerine/water mixtures on the macroporous resin Amberlite 252 has been analyzed. Finally, chloride removal by a strongly basic anionic‐exchange resin Amberlite IRA‐420 at three different temperatures has been studied. RESULTS: The strongly acidic ion exchanger Amberlite IR‐120 exhibits higher selectivity for potassium versus sodium ions. The ideal mass action law model was able to fit the experimental equilibrium data. The equilibrium data obtained at different percentages of water in the glycerine/water mixture indicate that as the water content increased the resin selectivity for sodium uptake is reduced. The selectivity of the anion exchange resin Amberlite IRA‐420 for chloride ions decreases with temperature. The ideal mass action law was accurate enough to fit the equilibrium data of the three systems and allowed the equilibrium thermodynamic properties to be obtained. CONCLUSIONS: These results confirm that macroporous resin Amberlite 252 could be a good choice to remove sodium ions from glycerol/water solutions with a high salt concentration and also that a strongly basic anionic‐exchange resin could be used for chloride removal. Copyright © 2009 Society of Chemical Industry     

Adsorption of Cr(III) ions by Turkish brown coals

The equilibrium and kinetic properties of Cr(III) ion adsorption by two brown coals from Anatolia, Turkey, have been investigated in batch stirred-tank experiments. The effects of adsorbent dose, initial sorbate concentration and contact time on the adsorption of Cr(III) by Isparta-Yalvaç-Yarikkaya (YK) and Kasikara (KK) brown coals were evaluated. The Cr(III) ions are able to form complex compounds with carboxylic and phenolic groups of brown coals and they were also bounded with phenolic groups even at low pH reaction of the solution (<3). Mechanisms including ion exchange, complexation and adsorption to the surface are possible in the sorption process. Our batch adsorption studies show the equilibrium adsorption data fit the linear Langmuir adsorption isotherm. Adsorption equilibrium was achieved in about 15–20 min for chromium(III). The Langmuir adsorption isotherm was used to describe the observed sorption phenomena. The maximum equilibrium uptake was 0.05 mmol of Cr(III)/g for KK, and 0.26 mmol of Cr(III)/g for YK, respectively, at a pH of 4.5. More than 90% of chromium(III) was removed by KK and YK from an aqueous solution after 60 min. In every experiment, the maximum Cr(III) was sequestered from the solution within 60 min. It is proposed that KK and YK brown coals can be used as potential sorbents for Cr(III) removal from aqueous solutions.     

Recovery of 1,4‐Dimethyl Piperazine from Aqueous Solutions Using Polymeric Adsorbent and Ion‐Exchange Resins

Abstract

Strong and weakly acidic ion exchange resins and polymeric adsorbents are used for recovery of 1,4‐dimethyl piperazine (DMP) from aqueous solutions. Sorption of the amine in undissociated form is the primary mechanism of uptake of DMP on the ion‐exchange resins. Equilibrium adsorption data for DMP on the resins, at various temperatures, are fitted in Langmuir adsorption isotherm. Kinetic studies show that intraparticle diffusional resistance controls the sorption of DMP into the resin matrix. A mathematical model based on intraparticle diffusion and external mass transfer is used for simulating breakthrough profiles and compared with the experimental results for a fixed bed of weakly acidic Indion‐652 resin. The DMP loaded bed of the resin was effectively regenerated with methanol.     

Ion exchange properties of sulfonated polycarbonate and polyimide track etch membranes

Heterogeneous sulfonation was successfully utilized to convert the surfaces of PC and PI track etched membranes with 20 nm pores into ion exchange membranes. Short sulfonation times of 1-5 min using gaseous sulfuric trioxide were sufficient to achieve good coverage of ion exchange sites on the membrane surface yet minimal structural damage to the bulk material. Consequently, the ion exchange capacities were relatively low, up to 0.015 meq/g, compared to literature. Electroselectivity typical of ion exchange materials was observed for these membranes and metal uptake of higher valences was preferred Eu³⁺ > Co²⁺ > Cs⁺. Clear differences in metal uptake properties were measured between the sulfonated PC and PI membranes with different ions. As a consequence of relatively high metal uptake and certain experiment set up also Donnan exclusion was determined to play a role in the overall ion exchange process.     

Dissolution-precipitation behaviour of ettringite, monosulfate, and calcium silicate hydrate

The stability of the cement minerals ettringite, monosulfate, and calcium silicate hydrate (C-S-H) was investigated to better understand the uptake of contaminants in waste-cement mixes. Suspensions were spiked with radioisotopes of components (⁴⁵Ca and ³⁵SO₄ for ettringite and monosulfate and ⁴⁵Ca and ³²Si for C-S-H) to observe their uptake behaviour within 0-70 days. A physical model was applied to determine dissolution-precipitation rates. An initial fast uptake was observed to occur in most systems, so the data obtained between 7 and 70 days were chosen for analysis. Dissolution-precipitation rates were in the range of 10^−11.5 to 10^−12.2 mol m⁻² s⁻¹ for all minerals. The whole solids would be dissolved and reprecipitated within 1-4 years. The measured dissolution-precipitation rates of pure cement minerals give the maximum rate for ion substitution processes with contaminants and are distinguishable from faster processes such as surface complexation and ion exchange processes.     

Sorption of cobalt to bone char: Kinetics, competitive sorption and mechanism

Swine bone char is the combustion residues of swine bone. Cobalt adsorption to swine bone char was studied. Batch kinetics studies showed that a rapid uptake occurred during the first 5 min and was followed with a very slow intraparticle diffusion process. The sorption kinetics was ideally conformed to pseudo-second equation, indicating several mechanisms involved in the adsorption process. Equilibrium sorption isotherm studies showed that the Freundlich isotherm model satisfactorily described the sorption data. The presence of co-ions had appreciable inhibiting effects on cobalt uptake by bone char because copper and zinc had higher affinity for the bone char surface than cobalt. Calcium concentration in solution and XRD analysis showed that ion exchange was involved in the removal of Co from solution over a certain initial cobalt concentration range.     

从甜菜糖蜜发酵废液中提取色素及甘油的工艺研究

研究了用离子交换法从甜菜糖蜜发酵废液中提取焦糖色素和甘油的新工艺 ,探讨了工艺条件及影响因素。结果表明 ,色素的产率 (对废液 )达 1 %～ 1 .5 % ,得到的精制甘油 ,其纯度可达 98%以上。通过实验找出了色素在吸附和洗脱过程中的体积、p H值及相应的色素含量之间的变化关系。与前文制取甜菜碱工艺相结合并与糖蜜发酵工业相配套 ,将形成一套彻底综合利用糖蜜生产多种产品的新工艺方案     

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     

3种离子交换相平衡模型在Tau/OH~-体系中的比较

在牛磺酸/氢氧根相平衡体系下,对计量置换模型、异质作用模型和改进的Langmuir模型的计算精度等特性进行了比较。采用静态法进行牛磺酸/氢氧根体系的离子交换平衡实验,测定30℃下的离子交换等温线;分别使用计量置换模型、异质作用模型和改进的Langmuir模型方程对相平衡数据进行拟合得到相关模型参数。结果表明:改进的Langmuir模型在一定牛磺酸浓度范围内可以正确地描述Tau/OH-体系的相平衡,拟合结果优于计量置换模型和异质作用模型。     

影响CeY分子筛吸附脱硫性能因素的研究

通过液相离子交换法对NaY分子筛进行改性制得CeY分子筛,采用静态法考察了改性CeY分子筛中铈离子的负载量、焙烧温度、铈的价态、吸附水和分子筛骨架的结构对CeY分子筛吸附脱硫性能的影响。采用XRD和ICP分别对不同CeY分子筛的骨架结构及阳离子负载量进行了分析。结果表明,二次交换后,离子交换度达到88.9%,分子筛已达到交换平衡;最佳焙烧温度为500 ℃,温度过高会破坏分子筛的骨架结构;Ce(Ⅳ)Y的脱硫性能明显好于Ce(Ⅲ)Y;分子筛上的吸附水对硫化物的吸附能力也有较大的影响。     

Comparison of Ion Exchange Performance of Polystyrene Nanofiber Cation Exchanger and Glass Fibers Coated with Poly(styrene‐co‐divinylbenzene)

Polystyrene nanofiber ion exchangers (PSNIE) were prepared by electrospinning from solutions of dissolved polystyrene followed by sulfonation processes. Coating and sulfonation have been used to modify glass fiber surfaces with polystyrene to produce cation exchange fibers (CEF). In this paper, new experimental results investigating the performance of PSNIE and CEF are presented in relation to the relevant parameters (ion exchange capacity (IEC), water uptake, and surface morphology). The IEC and water uptake of the PSNIE and CEF is depended upon the sulfonation time. The PSNIE sample with 30 min sulfonation time showed the maximum IEC of 3.74 mmol/g‐dry‐PSNIE and water uptake of 0.77 g H₂O/g‐dry‐PSNIE. The IEC and water uptake of CEF reached up to 3.61 mmol/g‐CEF and 0.25 g H₂O/g‐dry‐CEF.     

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.     

Modeling of Reactive Diffusion in Glass‐Ceramics

A model of reactive ion‐exchange diffusion in glassy materials (glasses and glass‐ceramics) has been developed. The model can be used to simulate the processes of ion‐exchange‐induced decrystallization of glass‐ceramics and ion‐exchange‐induced glass crystallization. Analysis of the model in dimensionless form resulted in determining a set of dimensionless complexes comprising dimensional parameters of the ion exchange system (diffusivity, rate constant of grain dissolution, initial size and composition of the crystalline grains, etc.). Numerical values of the complexes enable one, not solving the problem, to predict the composition and structure of glass‐ceramic subsurface layers produced in a certain glassy material and under given ion‐exchange conditions. It was shown that the developed model correctly describes experimental data on ion‐exchange‐induced glass‐ceramics decrystallization. It appears that the model can be used in developing a new technology of optical glass‐ceramics for photonic applications.