A study on stack configuration of continuous electrodeionization for removal of heavy metal ions from the primary coolant of a nuclear power plant

This study investigated the production of high-purity water in the primary coolant of a nuclear power plant via the continuous electrodeionization (CEDI) process, using ion exchange resins as ion-conducting media between ion exchange membranes. The effectiveness of this method was examined with respect to the removal of heavy metals. The study was carried out on a laboratory scale with an effective area of 20 cm(2). The CEDI system was operated with a layered bed of cation exchange resins, anion exchange resins, and mixed-bed ion exchange resins. The stack configuration was designed to prevent a reaction between metal ions and hydroxide ions. The CEDI operation with the layered bed removed more than 99% of the ions at 30% of the current efficiency. The results showed that, with an inlet conductivity of 40 microScm(-1), a linear velocity of 4.17 cms(-1), and an applied current density of 17 mAcm(-2), the CEDI process yielded an outlet conductivity of 0.5 microScm(-1), thereby preventing the precipitation of metal ions. This study therefore successfully demonstrated the feasibility of the CEDI operation for the removal of heavy metals at a very low concentration.     

Determination of the complexing properties of drinking waters toward copper(II) and aluminium(III) by ligand titration

The complexing capacity of some drinking waters for aluminium(III) and copper(II) is determined by a ligand titration with metal ions based on the use of complexing resins. The resins used in the titration are the iminodiacetic resin Chelex 100, the carboxylic resin Amberlite CG50 and the anionic exchange resin AG1X8. They allow the detection of ligands forming complexes of different stability with the metal ions used for the titration, since they have different sorbing properties. After equilibration with the resin, the concentration of the free metal ion in solution is evaluated from the concentration of sorbed metal ion and from the quantity K^*, which is the ratio of the concentration of the metal ion sorbed on the resin to the free metal ion in solution. It strongly depends on the conditions, but it can be evaluated, at the considered conditions, from the sorption equilibria of the metal ion on the resin. The concentration of the ligands in solution and the conditional stability constant are obtained from the Ruzik linearization procedure. Very strong ligands of copper(II) and aluminium(III) were detected in a tap water sample at concentrations ranging from 10⁻⁷ to 10⁻⁶ mol kg⁻¹, and forming complexes having conditional complexation constants K_cI=2.3×10¹⁷ (pH=6.77) and 4.5×10¹⁶ (pH=6.24), respectively, for copper(II) and aluminium(III). Weaker ligands were detected using the less strongly sorbing resins Amberlite CG50 and AG1X8, but at a concentration equal to that of the strong ligands. This was ascribed to the presence of competing metals in solution, not sorbed by the weak resins. Two other drinking waters had completely different complexing properties both towards copper(II) and aluminium(III), containing much weaker ligands.     

Performance of ion-exchanger grafted textiles for industrial water treatment in dynamic reactors

The performance of a special class of grafted textiles in removing metal cations from industrial wastewaters was examined in continuous reactors. The influence of various parameters on the ion exchange process (reactor geometry, inlet metal ion concentration, solution flow rate, concentration and type of reagent, etc.) was studied over the complete service cycle of the exchanger (saturation, desorption, regeneration, rinsing). Dynamic ion exchange characteristics were determined and compared with those of resins under identical operating conditions. Higher efficiency of fibrous ion exchangers compared to analogous resins, was shown at all stages of the service cycle. Results were expressed as a function of breakthrough capacity, exchanger utilisation efficiency, volume of solution treated, eluted metal concentration. The use of different reactor geometries showed two of the many possible applications of grafted textiles in water treatment processes.     

Determination of copper complexing capacity of natural river water, well water and artificially reconstituted water

A cupric ion electrode and computerized chemical equilibrium model were used to determine the copper complexing capacity of several natural river waters, well water and two artificially reconstituted waters. After adding a series of copper spikes to each water, the cupric ion concentration was measured and a comparison was made with cupric ion concentrations predicted by a chemical equilibrium model. Plots of cupric ion concentration vs total copper concentration (complexing capacity curves) were nonlinear at the lower total copper concentrations for several of the natural river waters. The slope of the linear portion of the complexing capacity curves was a function of pH and total alkalinity. For the natural river waters investigated, measured cupric ion concentrations were nearly always less than the theoretically computed cupric ion concentrations, while for two different artificially reconstituted waters and well water, reasonably quantitative agreement resulted.     

Extraction of zinc from aqueous solutions by electrically polarized cation exchange fibers

The process of treating galvanizing bath rinsing water by electrodialysis method with dialysate chamber filled with Fiban-K cation exchange fiber was investigated. The relationship between electromigration of zinc ions and electric current density was shown to have a maximum value within a range of 8–12 mA/cm². Within this range the electromigration flow of zinc ions in the presence of ion exchange fiber increases by ～20%, transport of hydrogen ions reaches 11.3% of the total flow of cations, residual concentration of zinc ions in dialysate in quasi-stationary mode at a current density of >10 mA/cm² does not exceed 2–4 mg/dm³, and without chamber loaded—10–15 mg/dm³.     

Microbiological investigation of an industrial ultra pure supply water plant using cultivation-based and cultivation-independent methods

Ultra pure waters (UPW), characterized by extremely low salt and nutrient concentrations, can suffer from microbial contamination which causes biofouling and biocorrosion, possibly leading to reduced lifetime and increased operational costs. Samples were taken from an ultra pure supply water producing plant of a power plant. Scanning electron microscopic examination was carried out on the biofilms formed in the system. Biofilm, ion exchange resin, and water samples were characterized by culture-based methods and molecular fingerprinting (terminal restriction fragment length polymorphism [T-RFLP] analysis and molecular cloning). Identification of bacteria was based on 16S rDNA sequence comparison. A complex microbial community structure was revealed. Nearly 46% of the clones were related to as yet uncultured bacteria. The community profiles of the water samples were the most diverse and most of bacteria were recruited from bacterial communities of tube surface and ion exchange resin biofilms. Microbiota of different layers of the mixed bed ion exchange resin showed the highest similarity. Most of the identified taxa (dominated by β-Proteobacteria) could take part in microbially influenced corrosion.     

Desalination of glycerol-water solutions by electrodyalysis using the organo-inorganic membranes

The organo–inorganic ion exchange membranes based on heterogeneous membrane materials and inorganic ion exchangers (zirconium hydrophosphate and hydrated zirconium dioxide) have been developed for electrodialysis desalination of glycerol–water solutions. It was shown that the electrodialysis efficiency with pristine polymer membranes decreases with time due to formation of deposit directly in the membrane pores. In contrast, the organo–inorganic membranes exhibit resistance to poisoning by organic substances, and the current yield during the electromembrane treatment can reach 95–98%.     

Removal of bromide and natural organic matter by anion exchange

Bromide removal by anion exchange was explored for various water qualities, process configurations, and resin characteristics. Simulated natural waters containing different amounts of natural organic matter (NOM), bicarbonate, chloride, and bromide were treated with a polyacrylate-based magnetic ion exchange (MIEX) resin on a batch basis to evaluate the effectiveness of the resin for removal of bromide. While bromide removal was achieved to some degree, alkalinity (bicarbonate), dissolved organic carbon (DOC), and chloride were shown to inhibit bromide removal in waters with bromide concentrations of 100 and 300 μg/L. Water was also treated using a two-stage batch MIEX process. Two-stage treatment resulted in only a slight improvement in bromide removal compared to single-stage treatment, presumably due to competition with the high concentration of chloride which is present along with bromide in natural waters. In view of the relatively poor bromide removal results for the MIEX resin, a limited set of experiments was performed using polystyrene resins. DOC and bromide removal were compared by treating model waters with MIEX and two polystyrene resins, Ionac A-641 and Amberlite IRA910. The two polystyrene resins were seen to be more effective for bromide removal, while the MIEX resin was more effective at removing DOC.     

Removal of THM precursors by coagulation or ion exchange

The removal of natural organic matter (NOM) from drinking water supplies can be achieved by different processes, among them coagulation and adsorption. Synthetic waters made from concentrates of humic substances from reservoir and river waters were tested in the laboratory for ease of removal of NOM by coagulation with cationic organic polymers and with alum, and by adsorption on anion exchangers. For polymers such as high molecular weight polydiallyldimethylammonium chloride (polyDADMAC) and cationic polyacrylamides of high charge, performance was nearly as effective as alum, with colour removals 86–100% of those obtained for alum. Ion exchange using the best commercially available resins designed for this purpose, a gel polystyrene and a macroporous acrylic resin, was more effective than alum treatment for two of the natural waters studied, but inferior for a third. The resins were overall superior to cationic polymers.

The NOM was separated into four fractions based on hydrophobic and hydrophilic properties. Alum was not as effective as ion exchange for the elimination of individual ionic NOM fractions. It was better than cationic polymers for removal of humic and fulvic acids, although polyDADMAC was as good for one water. For the removal of charged compounds alum then polyDADMAC were the best performers for that water. Unequivocal evidence was obtained that coagulants remove material that is not adsorbed by resins, and vice versa. A combination of coagulation with a cationic polymer and adsorption by an anion exchanger removed essentially all of the NOM. The preference of the coagulants was for the larger, more hydrophobic molecules, and of resins for smaller highly charged hydrophilic molecules. Each fraction had trihalomethane formation potentials in the range 11–24 μg/mg, except for one water that was more reactive. Hence, the actual amount of each fraction in the original water becomes a crucial factor.     

基于热响应测试的分层土壤地埋管换热器数值模拟研究

结合热响应测试数据,建立了三维分层土壤地埋管换热器非稳态模型,并进行了验证。通过分析比较单层、分层土壤地埋管换热器模型,结果显示分层土壤地埋管模型误差较小;通过分层土壤地埋管模型分析了100 m、80 m、60 m深度埋管的换热性能,结果显示增加埋深时,单位延米换热量随着埋深的增加而减小,验证了热短路现象存在性。     

Impact of a magnetic ion exchange resin on ozone demand and bromate formation during drinking water treatment

The objective of this research was to examine the impact of a magnetic ion exchange resin (MIEX) on ozone demand and bromate formation in two different ozonated waters at bench scale. The first raw water had a high bromide ion concentration, a high ozone demand, and was highly colored. Based on experimental findings from the first water, the second water was selected as a model water in which more controlled experiments were performed. The waters were treated with the MIEX resin using jar test procedures to find the optimal MIEX dosage based upon the removal of ultraviolet (UV)-absorbing substances, dissolved organic carbon (DOC), and bromide. The optimal resin dosage was chosen for bulk MIEX treatment and subsequent ozonation in a semi-batch reactor. The ozone demand and formation of bromate were analyzed as a function of ozone dosage and dissolved ozone concentration for the MIEX pre-treated water, and compared to the results obtained by ozonating the water without MIEX pre-treatment. The results indicate that pre-treatment of the water with the MIEX resin significantly reduces total organic carbon, DOC, UV absorbance, color, and to some extent, bromide. MIEX pre-treatment of the water prior to ozonation substantially lowered the ozone demand and formation of bromate during subsequent ozonation.     

Development of polymer-based nanosized hydrated ferric oxides (HFOs) for enhanced phosphate removal from waste effluents

Phosphate originated from industrial effluents is one of the key factors responsible for eutrophication of the receiving waterways especially in the developing countries such as China. In the current study we proposed a novel process to immobilize nanoparticulate hydrated ferric oxide (HFO) within a macroporous anion exchange resin D-201, and obtained a hybrid adsorbent (HFO-201) for enhanced phosphate removal from aqueous system. The resulting HFO-201 possesses two types of adsorption sites for phosphate removal, the ammonium groups bound to the D-201 matrix and the loaded HFO nanoparticles. The coexisting sulfate anion strongly competes for ammonium groups, which bind phosphate through electrostatic interaction. However, it does not pose any noticeable effect on phosphate adsorption by the loaded HFO nanoparticles, which is driven by the formation of the inner-sphere complexes. Batch adsorption experiments also indicated that HFO-201 exhibits a little higher capacity for phosphate than the commercially available phosphate-specific adsorbent ArsenX^np, which possesses similar structure of HFO-201 and is produced by another patented technique. Fixed-bed column tests indicate that phosphate retention by HFO-201 from the synthetic waters results in the significant decrease of P from 2 mg/L to less than 0.01 mg/L, with the treatment capacity of ∼700 bed volume (BV) per run, while that for D-201 was less than 200 BV under otherwise identical conditions. Such satisfactory performance of the hybrid adsorbent is mainly attributed to the specific affinity of HFO toward phosphate as well as the Donnan membrane effect exerted by the anion exchanger support D-201. Moreover, the exhausted HFO-201 was amenable to efficient in situ regeneration with a binary NaOH-NaCl solution for repeated use without any significant capacity loss. Similar satisfactory results were also observed by using a phosphate-containing industrial effluent as the feeding solution.     

Fabrication of polymer-supported nanosized hydrous manganese dioxide (HMO) for enhanced lead removal from waters

In the current study, a new hybrid adsorbent HMO-001 was fabricated by impregnating nanosized hydrous manganese dioxide (HMO) onto a porous polystyrene cation exchanger resin (D-001) for enhanced lead removal from aqueous media. D-001 was selected as a support material mainly because of the potential Donnan membrane effect exerted by the immobilized negatively charged sulfonic acid groups bound to the polymeric matrix, which would result in preconcentration and permeation enhancement of lead ions prior to their effective sequestration by the impregnated HMO. HMO-001 was characterized by scanning electron micrograph (SEM), transmission electron micrograph (TEM), and X-ray diffraction (XRD). Lead adsorption onto HMO-001 was dependent upon solution pH due to the ion-exchange nature, and it can be represented by the Freundlich isotherm model and pseudo-first order kinetic model well. The maximum capacity of HMO-001 toward lead ion was about 395 mg/g. As compared to D-001, HMO-001 exhibited highly selective lead retention from waters in the presence of competing Ca²⁺, Mg²⁺, and Na⁺ at much greater levels than the target toxic metal. Fixed-bed column adsorption of a simulated water indicated that lead retention on HMO-001 resulted in a conspicuous decrease of this toxic metal from 1 mg/L to below 0.01 mg/L (the drinking water standard recommended by WHO). The exhausted adsorbent particles are amenable to efficient regeneration by the binary NaAc-HAc solution for repeated use without any significant capacity loss. All the results validated the feasibility of HMO-001 for highly effective removal of lead from contaminated waters.     

Organic arsenic removal from drinking water

Arsenic occurs in both inorganic and organic forms in water. Although various methods have been adopted to remove inorganic species of arsenic from drinking water, not much emphasis has been given to the removal of organic species of arsenic. In the present study column studies were conducted using manganese greensand (MGS), iron oxide-coated sand (IOCS-1 and IOCS-2) and ion exchange resin in Fe³⁺ form, to examine the removal of organic arsenic (dimethylarsinate) spiked to required concentrations in tap water. Batch studies were conducted with IOCS-2, and the results showed that the organic arsenic adsorption capacity was 8 μg/g IOCS-2. Higher bed volumes (585 BV) and high arsenic removal capacity (5.7 μg/cm³) were achieved by the ion exchange resin among all the media studied. Poor performance was observed with MGS and IOCS-1.     

Selective removal of arsenate from drinking water using a polymeric ligand exchanger

The new maximum contaminant level (MCL) of 10 μg/L for arsenic in the US drinking water will take effect on January 22, 2006. The compliance cost is estimated to be $ 600 million per year using current treatment technologies. This research aims to develop an innovative ion exchange process that may help water utilities comply with the new MCL in a more cost-effective manner. A polymeric ligand exchanger (PLE) was prepared by loading Cu²⁺ to a commercially available chelating ion exchange resin. Results from batch and column experiments indicated that the PLE offered unusually high selectivity for arsenate over other ubiquitous anions such as sulfate, bicarbonate and chloride. The average binary arsenate/sulfate separation factor for the PLE was determined to be 12, which were over two orders of magnitude greater than that (0.1–0.2) for commercial strong-base anion (SBA) exchangers. Because of the enhanced arsenate selectivity, the PLE was able to treat 10 times more bed volumes (BVs) of water than commonly used SBA resins. The PLE can operate optimally in the neutral pH range (6.0–8.0). The exhausted PLE can be regenerated highly efficiently. More than 95% arsenate capacity can be recovered using 22 BVs of 4% (w/w) NaCl at pH 9.1, and the regenerated PLE can be reused without any capacity drop. Upon treatment using FeCl₃, the spent brine was recovered and reused for regeneration, which may cut down the regenerant need and reduces the volume of process waste residuals. The PLE can be used as a highly selective and reusable sorbent for removal of arsenate from drinking water.     

Recovery of ammonium sulfate from fermentation waste by electrodialysis

Electrodialysis experiments of the lysine fermentation waste were performed to generate demineralized feed and ammonium sulfate, which can be utilized as a fertilizer and an animal feed, respectively. The electrodialysis performances were compared for different ion exchange membranes in terms of ammonium sulfate removal rate, resistance and conductivity change. Analysis of fouling phenomena revealed that organics fouled ion exchange membranes reversibly in electrodialysis of the fermentation waste. In this study, mitigation of membrane fouling with the pulsed electric field was examined for the electrodialysis of the fermentation waste containing strong foulants. The half-wave power reduced membrane fouling significantly. For a quantitative measure of the membrane fouling tendency, a membrane fouling index for electrodialysis was used. This study showed the potential use of pulsed power as an effective fouling mitigation method for the electrodialysis of fermentation waste.     

Bench-scale testing of a magnetic ion exchange resin for removal of disinfection by-product precursors

The objective of this research was to compare enhanced coagulation with anion exchange for removal of disinfection by-product (DBP) precursors (i.e. natural organic matter (NOM) and bromide). Treatment with a magnetic ion exchange resin (MIEX((R))) was the primary focus of this study. Raw waters from four utilities in California were evaluated. The waters had low turbidity, low to moderate organic carbon concentrations, a wide range of alkalinities, and moderate to high bromide ion concentrations. The treated waters were compared based on removal of ultraviolet (UV) absorbance, dissolved organic carbon (DOC), trihalomethane formation potential (THMFP), and haloacetic acid formation potential (HAAFP). The results indicated that treatment with MIEX is more effective than coagulation at removing UV-absorbing substances and DOC. Treatment with MIEX and treatment with MIEX followed by coagulation yielded similar results, suggesting that coagulation of MIEX-treated water does not provide additional removal of organic carbon. MIEX treatment reduced the THMFP and HAAFP in all waters, and did so to a greater extent than coagulation. Treatment with MIEX was most effective in raw waters having a high specific UV absorbance and a low anionic strength. Following MIEX treatment, subsequent chlorination resulted in a shift to the more brominated THM and HAA species as compared to chlorination of the raw water. MIEX also removed bromide to varying degrees, depending on the raw water alkalinity and initial bromide ion concentration.     

Application of a three-component competitive adsorption model to evaluate and optimize granular activated carbon systems

A recently developed kinetic model for granular activated carbon (GAC) adsorbers (COMPSORB-GAC) that quantitatively describes the adsorption of trace organic contaminant in the presence of competing natural organic matter (NOM) was applied to evaluate the performance of different GAC system configurations: conventional fixed-bed adsorbers, layered upflow carbon adsorbers (LUCA), and moving-bed adsorbers (with few or many bed sections). COMPSORB-GAC separately tracks the adsorption of three components: a trace compound, a strongly competing NOM fraction that reduces trace compound equilibrium capacity, and a pore-blocking NOM fraction that reduces kinetics. Performance was simulated for various design criteria and with model parameters derived for two natural waters with significantly different NOM concentrations. For the range of simulated conditions and with baseline performance defined by a fixed-bed adsorber, LUCA generally reduced carbon usage rates (CURs) by 15-35%. A 2-section and a 16-section moving-bed reactor reduced baseline CURs by 20-30% and 45-55%, respectively. Projected CURs for the water source with a relatively high NOM concentration were 2-3 times higher for all reactor configurations and indicated that NOM preloading would cause performance deterioration in deep GAC beds, which highlights the importance of source water quality. These results show how COMPSORB-GAC can be used in a comprehensive, site-specific optimization of GAC systems to ensure robust system performance and to balance capital and operating costs.     

Bicarbonate-form anion exchange: affinity, regeneration, and stoichiometry

Magnetic ion exchange (MIEX) is an effective process for removing dissolved organic carbon (DOC) from natural waters, but its implementation has been limited due to production of waste sodium chloride solution (i.e., brine) from the regeneration process. Chloride is of concern because elevated concentrations can have adverse effects on engineered and natural systems. The goal of this research was to explore the efficacy of using anion exchange resin with bicarbonate as the mobile counter ion, which would produce a non-chloride regeneration solution. It was found that bicarbonate-form MIEX resin had a similar affinity as chloride-form MIEX resin for sulfate, nitrate, DOC, and ultraviolet-absorbing substances. Both bicarbonate-form and chloride-form MIEX resins showed the greatest removal efficiencies as fresh resin, and removal efficiency decreased with multiple regeneration cycles. Nevertheless, sodium bicarbonate solution was as effective as sodium chloride solution at regenerating MIEX resin. Regeneration of the bicarbonate-form MIEX resin was illustrated by sparging carbon dioxide gas in a water/resin slurry. This regeneration process would eliminate the need for the addition of salts such as sodium chloride or sodium bicarbonate. The stoichiometry of the bicarbonate-form resin revealed that the bicarbonate was deprotonating within the resin matrix leading to a mixture of both carbonate and bicarbonate mobile counter ions. This work makes an important contribution to ion exchange applications for water treatment by evaluating the affinity, regeneration, and stoichiometry of bicarbonate-form anion exchange.     

Enhanced coagulation using a magnetic ion exchange resin

The objective of this investigation was to examine the effectiveness of a magnetic ion exchange resin (MIEX) to enhance the coagulation of disinfection by-product precursors in nine surface waters, each representing a different element of the USEPA's 3 x 3 enhanced coagulation matrix. The effect of MIEX-pretreatment on the requisite alum dose needed for subsequent coagulation of turbidity was also evaluated. Enhanced coagulation with MIEX was found to be very effective for removing trihalomethane (THM) and haloacetic acid (HAA) precursors from the nine waters examined. THM and HAA formation potential was reduced by more than 60% in all of the waters studied; reductions approaching 90% were seen in the waters with the highest specific ultraviolet absorbance values. The residual total organic carbon concentration, ultraviolet absorbance, and THM and HAA formation potential were all substantially lower as a result of MIEX and alum treatment compared to alum coagulation alone. MIEX pre-treatment also lowered the coagulant demand of each of the waters substantially.