Spherical Resorcinol‐Formaldehyde Resin Testing for Cesium Removal from Hanford Tank Waste Simulant

Abstract

A new spherical form of resorcinol‐formaldehyde (RF) resin was tested for efficacy of cesium removal from Hanford tank waste. Two spherical RF formulations, prepared by varying curing temperature, were tested. Both resins had a tight particle size distribution and a high degree of sphericity. Small‐scale column testing (on ～20‐mL resin beds) was conducted evaluating the cesium load profile with AZ‐102 simulated tank waste and the cesium elution profile using 0.5 M HNO₃ eluant. The load and elution profiles were compared in side‐by‐side testing with ground‐gel RF resin and SuperLig® 644, the Waste Treatment Plant baseline ion exchanger. Although breakthrough capacity was not as high as the other resins tested, the spherical RF resin met plant cesium loading requirements with the AZ‐102 simulant matrix. Excellent reproducibility of cesium load and elution was demonstrated over three process cycles with no evidence of degraded performance. Residual cesium on the resin beds after elution was nearly a factor of 10 lower than that of the ground‐gel RF and SuperLig^® 644.     

Hydraulic Testing of Ion Exchange Resins for Cesium Removal from Hanford Tank Waste

Abstract

The granular ion exchange resin SuperLig^® 644 is the ion exchange resin of choice for ¹³⁷Cs separation from Hanford tank wastes. Current testing activities are evaluating both ground gel and spherical resorcinol‐formaldehyde (RF) resins as alternatives to the sole‐source supplied SL‐644 while achieving comparable loading and elution performance. The purpose of this testing was then to compare the bed forces, resin particle breakage, and differential pressure across the resin bed during multiple load‐elute cycles. These tests were conducted in a small‐scale column with high flow rates to simulate the hydraulic conditions that would be experienced in a full‐scale column.     

Evaluation of Elution Parameters for Cesium Ion Exchange Resins

Abstract

Cesium ion exchange is one of the planned processes for treating and disposing of waste at the U.S. Department of Energy Hanford Site. Radioactive supernatant liquids from the waste tanks will undergo ultrafiltration, followed by cesium ion exchange using a regenerable organic ion exchange resin. Two resins, SuperLig^®644 and a resorcinol‐formaldehyde resin, are being evaluated for cesium removal and cesium elution characteristics. The main purpose of this study is to optimize the cesium elution to provide a resin that, after undergoing elution, would meet the U.S. Department of Energy/Office of River Protection Project‐Waste Treatment Plant processing and resin disposal criteria. Columns of each resin type were loaded to greater or equal to 90% breakthrough with a Hanford waste stimulant and eluted with nitric acid. The temperature, flow rate, and nitric acid concentration were varied to determine the optimal elution conditions. Temperature and eluant flow rate were the most important elution parameters. As would be predicted based upon kinetic consideration alone, decreasing the eluant flow rate and increasing the temperature provided the optimal elution conditions. Varying the nitric acid concentration did not have a significant effect on the elution completion; however, elutions performed using both high acid concentration (1 M) and elevated temperature (45°C) resulted in resin degradation, causing gas generation and resin bed disruption.     

Valeric acid extraction with tri‐n‐butyl phosphate impregnated in a macroporous resin: II. Studies in fixed bed columns

Extraction and back‐extraction of valeric acid in a fixed bed packed with Amberlite XAD‐4 resin impregnated with tri‐n‐butyl phosphate were experimentally studied at 25 °C. The effects of the feed flow rate, acid concentration in the feed solution and extractant concentration in the impregnated resin on the breakthrough curves, were investigated. The bed saturation capacity was larger under the conditions of higher extractant concentration in the resin phase and higher acid concentration in the feed solution. A dynamic model that considers intraparticle diffusion and external liquid film diffusion as limiting steps in mass transfer rates was successfully applied. The intraparticle effective diffusivities (10^?9 dm² s^?1) were from one to three orders of magnitude lower than the diffusivities in the external liquid film (10^?8–10^?6 dm² s^?1). A fast and complete back‐extraction of valeric acid from the saturated bed was carried out with sodium hydroxide solutions. The operational life of the impregnated resin was also studied. Copyright © 2005 Society of Chemical Industry     

Column Sorption of Citric Acid from Aqueous Solutions Using Tri-n-octylamine-Impregnated Macroporous Resins

Abstract

Column sorption of citric acid from aqueous solutions using tri-n-octylamine (TOA)-impregnated macroporous resins was studied at 298 K. The breakthrough curves were measured as a function of the feed flow rate, citric acid concentration in the feed solution, TOA concentration in the resin phase, and type of resin. It was found that the type of resin played a most important role in determining the saturated capacity under comparable conditions. The desorption of citric acid from loaded resins was also evaluated with various eluants, including HCl, HNO³, H²SO⁴, and Na²CO³     

Equilibrium data of the exchange of Cu2+, Cd2+ and Zn2+ ions for H+ on the cationic exchanger Lewatit TP‐207

Equilibrium ion exchange isotherms in aqueous medium of H⁺/Cu²⁺, H⁺/Zn²⁺ and H⁺/Cd²⁺ on a weak acid resin Lewatit TP‐207, at different pH values and at 298 K have been determined in order to assess the possibility of using ion exchange to eliminate heavy metal ions from industrial aqueous liquid streams. The experimental equilibrium data have been satisfactorily correlated using a Langmuir‐type empirical equation. It was found that the operating resin capacity with respect to each metal ion increased with increase in solution pH, in accordance with a second‐degree polynomial equation. Taking into account the variation of operating capacity with pH, each system exhibited a unique separation factor, namely all the experimental points can be described by a unique isotherm in a dimensionless form. Resin Lewatit TP‐207 exhibited the following selectivity order: Cu²⁺ > Zn²⁺ > Cd²⁺ at 298 K. Copyright © 2004 Society of Chemical Industry     

Hybrid Properties of Alginate‐PEI Adsorbent for Chromium (VI) Removal from Aqueous Solutions

Abstract

An adsorbent consisting of polyethyleneimine (PEI) immobilized in calcium alginate gel beads was synthesized and evaluated for Cr⁶⁺ removal. An evaluation of the synthesis process showed the importance of the PEI molecular weight on the immobilization efficiency. Polyethyleneimine of 70,000 Da molecular weight displayed the highest immobilization percentage at 52%. Batch kinetics and equilibrium tests showed that alginate‐PEI (APEI) resin displayed considerable affinity for negatively charged Cr⁶⁺ complexes at low pH conditions ranging from pH 1.5‐pH 3. The results also indicated the reduction of Cr⁶⁺ to less toxic Cr³⁺ species by the APEI adsorbent. The column adsorption experiments showed the ability of APEI resin to treat a 10 mg/L Cr⁶⁺ solution with pH influent adjustment from pH 1.5 to pH 3 to concentrations that satisfy effluent standards for Cr⁶⁺ (<0.1 mg/L) and total Cr (<0.5 mg/L). Finally, comparisons with a highly aminated commercial resin Chitopearl CS‐03 highlighted the unique ability of the hybrid APEI beads with its amine and carboxylic groups for the adsorption of Cr⁶⁺ as well as the retention of generated Cr³⁺ ions.     

Characterization of SuperLig® 639 Rhenium and Technetium Resin with Batch Contact and Column Tests

Two new (2013) lots of SuperLig^® 639 ion exchange resin (IBC Advanced Technologies, American Forks, UT) were tested for the first time above typical sodium concentrations (7.8 M sodium, along with typical 5 M concentration) in highly alkaline solutions. Batch contact and ion exchange column tests characterized rhenium (perrhenate) adsorption as a surrogate for pertechnetate. The work supports technetium removal options for Supplemental Low Activity Waste processing at the Hanford River Protection Project Waste Treatment Plant (WTP). The current work found that the resin performs well in the 7.8 M sodium simulant despite complete floating of the beads. A notable difference in performance between the two new resin lots was found. Resin loading overall versus temperature, potassium concentration, and rhenium/nitrate ratios is consistent with previous data and expectations despite the high sodium concentration and floating of the resin beads.     

Absence of Donnan Exclusion at High‐Concentration Ion Exchange for Macroporous Anionic Resin

Abstract

High‐concentration ion exchange has been studied for an anionic macroporous resin. The mechanism of interaction of Lewatit MP‐500 (strong base resin) with several high‐concentration inorganic salts was analyzed in order to determine the effect of the Donnan potential in the process.

The systems under study were Cl^?, SO₄ ^2? as counter‐ions and K⁺, Na⁺ as co‐ions in different combinations as single electrolytes. These salts were chosen because of their interest as raw materials in the fertilizer industry. The study focuses mainly on the behavior of high‐concentration (over 1 M) counter‐ and co‐ions in the anionic resin. The results showed that Donnan exclusion does not take place completely and that electrolyte penetration inside the resin is observed. Furthermore, a certain amount of ion exchange was observed for the co‐ions (K⁺ and Na⁺) when the resin was presaturated with sulphate and chlorides that were present in the solution. Equilibrium and kinetics data were obtained under these special experimental conditions. Equilibrium constants were obtained for counter‐ions and adsorption constants for co‐ions using a constant separation factor isotherm, while diffusion coefficients were obtained using a pore diffusion model.     

Separation and Recovery of Silver(I) Ions from Base Metal Ions by Melamine‐formaldehyde‐thiourea (MFT) Chelating Resin

Abstract

Melamine‐formaldehyde‐thiourea (MFT) chelating resin were prepared using melamine (2,4,6‐triamino‐1,3,5‐triazine), formaldehyde, and thiourea and this resin has been used for separation and recovery of silver(I) ions from copper(II) and zinc(II) base metals and calcium(II) alkaline‐earth metal in aqueous solution. The MFT chelating resin was characterized by elemental analysis and FT‐IR spectra. The effect of pH, adsorption capacity, and equilibrium time by batch method and adsorption, elution, flow rate, column capacity, and recovery by column method were studied. The maximum uptake values of MFT resin were found as 60.05 mg Ag⁺/g by batch method and 11.08 mg Ag⁺/g, 0.052 mg Zn²⁺/g, 0.083 mg Cu²⁺/g and 0.020 mg Ca²⁺/g by column method. It was seen that MFT resin showed higher uptake behavior for silver(I) ions than base and earth metals due to chelation.     

SOLVENT EXTRACTION CHEMISTRY: A FEW THOUGHTS ABOUT ITS INTERDISCIPLINARY NATURE,CHALLENGES AND OPPORTUNITIES

Abstract

In this article, the results of the application of a boron removal treatment based on a process of chemosorption on liquid waste of urban, agricultural, or industrial origin is presented. The isotherms of the process have been established and a study of the influence of the different variables in the tests in columns has been carried out. The results obtained indicate that the process of chemosorption shows strongly favorable isotherms, and moreover it is notably influenced by the variable “flow rate,” making the breakthrough point appear earlier and the curves move towards the left. However, important differences in the curves for the variable “dimensions of the bed” have not been observed. Furthermore, a pH‐dependent mechanism for the treatment process of boronated effluents by means of chemosorption with the specific Amberlite IRA-743 resin was developed. According to breakthrough point data, experimentally achieved in elution tests for the maximum value allowed by environmental legislation, of 3 mg B L^?1, a double mechanism is proposed. It can be suggested that for basic pH the mechanism corresponds to stereospecific reactivity between the borate ion and hydroxide groups of the N‐methylglucamine active site of the resin in cis‐position, a maximum appearing between pH 8.5 and 9.5, corresponding to borate ion predominance. On the other hand, a mechanism based on the hydrogen bridge bond formation reaction between the ionized amino group of the resin and boric acid is suggested for neutral and slightly acid pH. This last reaction differentiates this resin from the other absorbents used for boron removal in industrial wastes, such as metallic oxides, clays, humic acids, and so on.     

Laboratory‐Scale Column Testing Using Crystalline Silicotitanate (IONSIV™ IE‐911) for Removing Cesium from Acidic Tank Waste Simulant. 1: Cesium Exchange Capacity of a 15‐cm3 Column and Dynamic Stability of the Exchange Media*

Abstract

Bench‐scale column tests were performed using a commercial form of crystalline silicotitanate (CST) for removing radio‐cesium from a surrogate acidic tank solution representative of liquid waste stored at the Idaho National Engineering and Environmental Laboratory (INEEL). An engineered form of CST ion exchanger, known as IONSIV? IE‐911 (UOP, Mt. Laurel, NJ, USA), was tested in 15 cm³ columns at a flow rate of 5 bed volumes per hour. These experiments showed the ion exchange material to have reasonable selectivity and capacity for removing cesium from the complex chemical matrix of the solution. However, previous testing indicated that partial neutralization of the feed stream was necessary to increase the stability of the ion exchange media. Thus, in these studies, CST degradation was determined as a function of throughput in order to better assess the stability characteristics of the exchanger for potential future waste treatment applications. Results of these tests indicate that the degradation of the CST reaches a maximum very soon after the acidic feed is introduced to the column and then rapidly declines. Total dissolution of bed material did not exceed 3% under the experimental regime used.     

The Separation of Beryllium from Selected Elements Using the Dipex® Extraction Chromatographic Resin

Abstract

An extraction chromatographic resin containing the acidic chelating organophosphorus extractant, Dipex^®, sorbed onto an inert polymeric substrate has been evaluated for the separation of beryllium from a wide range of elements. The elements selected comprise those which can interfere with the determination of beryllium by inductively coupled plasma‐atomic emission spectroscopy (ICP‐AES) and matrix elements which commonly occur in environmental and industrial samples. Based on batch uptake measurements, a method that separates beryllium from all potential ICP‐AES spectral interfering elements using a single extraction chromatographic column is outlined. The chromatographic parameters of the separation method have been optimized using simulated samples generated using the digestion process employed in beryllium analyses by the Y‐12 National Security Complex and simulated ground water samples.     

Charged Membrane Ultrafiltration of Toxic Metal Oxyanions and Cations from Single- and Multisalt Aqueous Solutions

Abstract

With application to the treatment of nonferrous metals production streams, the toxic metals As(V), Se(IV), As(III), and Cd(II) are separated from single-and multisalt aqueous solutions by continuous-flow, membrane ultrafiltration with charged, noncellulosic membranes. The single-salt aqueous solutions of As(V), Se(IV), As(III), or Cd(II) are investigated over pH 5 to 10, metal concentrations in the range 0.5 to 20.0 mM, and transmembrane pressure differences from 2.8 × 10⁵ to 5.6 × 10⁵ N/m², with the effects of these three independent variables established on the metal rejections. The rejections of the monovalent oxyanions H₂AsO₄ ^?, HSeO₃ ^?, and H₂AsO₃ ^? (with sodium as the counterion) are of the order 0.85, and those of the divalent HAsO₄ ^2?, SeO₃ ^2? (and SO₄ ^2?), and of Cd²⁺ are of the order 0.95 for 6.0 mM feed streams. Comparisons are made with the halides, NO₃ ^?, and ClO₄ ^?. The rejection behavior of multisalt solutions of H₂AsO₄ ^? and HSeO₃ ^? is not influenced by the presence of sulfate, but Cd²⁺ produces a decrease in the rejection of Se(IV). For feed streams 2.0 mM each in H₂AsO₄ ^?, HSeO₃ ^?, Cd²⁺, and Zn²⁺ at pH 5, the presence of a high sulfate concentration does not affect the metal rejections, except at greater than 14.0 mM where the Se(IV) rejection begins to decline sharply     

REILLEX™-HPQ ANION EXCHANGE COLUMN CHROMATOGRAPHY: REMOVAL OF PERTECHNETATE FROM DSSF-5 SIMULANT AT VARIOUS FLOW RATES

ABSTRACT

The 1% breakthrough volumes (BTV) for TcO₄^on Reillex^?-HPQ anion exchange resin columns have been measured as a function of flow rate. The 1% BTV is defined as that point in the column loading when an aliquot of eluent contains 1% of the activity of an equivalent aliquot of column feed solution. The 2.54 × 50 cm     

Preparation of Chelating Resins Containing a Pair of Neighboring Carboxylic Acid Groups and the Adsorption Characteristics for Heavy Metal Ions

Abstract

For the functional enhancement of chelating resins containing carboxylic acids, copolymer beads were prepared by suspension polymerization of styrene (St), methyl methacrylate (MMA), and divinylbenzene (DVB) in the presence of toluene as diluent. The phenyl rings of the beads were directly chloromethylated, and the carboxylic ester groups of the beads were converted into hydroxymethyl groups by reduction followed by chlorination to give chloromethyl groups, respectively. The chelating resins containing a pair of neighboring carboxylic acid groups (NCAGs) were obtained by the alkylation of chloromethyl groups in copolymer beads with diethyl malonate in the presence of sodium hydride followed by hydrolysis using aqueous alkali solution. Accordingly, the structural effects of the resins on the adsorption of heavy metal ions were investigated. Poly(St‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, and Cu²⁺, whereas poly(MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Cu²⁺, Cd²⁺, and Co²⁺. On the other hand, poly(St‐co‐MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, Co²⁺, and Cu²⁺: a synergistic effect on the adsorption of heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, and Co²⁺ was observed. The adsorption ability of poly(St‐co‐MMA‐co‐DVB)‐based chelating resin among three kinds of chelating resins was relatively good.     

Determination of formaldehyde/urea molar ratio in amino resins by near‐infrared spectroscopy

New processes for synthesis of urea‐formaldehyde (UF) and melamine‐fortified urea‐formaldehyde (mUF) resins have been developed in the last years, motivated by the current concerns about the effects of formaldehyde on human health. All these formulations are quite susceptible to possible operation error, which can significantly influence the characteristics of the final product. The main objective of this work was to implement chemometric techniques for off‐line monitoring of the product's formaldehyde/urea (F/U) molar ratio using near infrared (NIR) spectroscopy. This allows the timely implementation of the necessary corrections in case the product is off‐specification. Calibration models for F/U molar ratio were developed taking into account the most relevant spectral regions for these resins, individually or in combination (7502–6098 cm^?1 and 5000–4246 cm^?1) and using different preprocessing methods. When the appropriate spectral range and preprocessing methods are selected, it is possible to obtain calibration models with high correlation values for these resins. The best preprocessing methods were identified for three cases: UF resin (produced by strongly‐acid process), mUF resin (alkaline‐acid process), and a combined model that involves both UF and mUF resins. It was concluded that significantly better accuracy is obtained when a new model is developed for each particular resin system. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Note: Two-Enthalpy Feed for Distillation with Vapor Feed and Refrigerated Condenser

Abstract

The use of two-enthalpy feed, which involves splitting the feed, condensing part of it, and sending both the liquid and vapor streams to the distillation column, is explored for columns that have a vapor feed and require refrigeration in the column condenser. The use of two-enthalpy feed can reduce both capital and operating costs compared to condensing all the feed. Compared to use of partial cooling and use of a two-phase feed, two-enthalpy feed reduces the condenser heat duty, but the feed cooling occurs at a lower temperature.     

Mass Transfer Mechanisms in the Fixed‐Bed Ion‐exchange Process for Dilute Colloidal Silica Manufacture

The ion exchange behavior of the H⁺ form C‐100 Purolite resin for the production of colloidal silica from dilute sodium silicate solutions has been investigated. The exchange isotherm has been found to be almost irreversible. The effective resin diffusion coefficient has been found to be 2.84 × 10^–10 m² s^–1 using a shrinking core model for the batch uptake experiments. Fixed bed experiments for different column heights and feed flow rates were performed. Numerical solution of the governing equations showed that the process is initially controlled by film diffusion and consequently by resin diffusion. Axial dispersion had to be taken into account. A simple power law correlation has been determined that relates the fluid Peclet number to the Reynolds number. It is presumed that some sort of resin ‘deactivation’ due to intraparticle microgel formation is responsible for the sluggish end part of the breakthrough curves.     

Separation of Nitrogen Isotopes by Displacement Band Chromatography

Abstract

A study of the separation of ¹⁴N and ¹⁵N isotopes via displacement band chronatography was conducted using sulfonated styrene-divinylbenzene resins. Starting with a feed solution of 0.5 N NH₄OH (containing 51% ¹⁵N), a band was developed that generated a concentration profile ranging from 11 to 85 % ¹⁵N. The separative power and HETP (height equivalent to a theoretical plate) were found to be dependent on the resin characteristics (size, crosslinkage) and operating parameters (superficial velocity, concentration). The use of a 7/10-microneter-size, high performance resin increased the separative power by a factor of 17 and decreased the HETP by a factor of 10, when compared to a 100/200 mesh Dowex 50W-X12 resin under similar process conditions. The HETP could further be reduced by lowering the superficial velocity and/or eluant concentration.