Electrochemical water softening technology: From fundamental research to practical application.

In recent decades, the environmentally benign electrochemical softening process has been gaining widespread interest as an emerging alternative for water softening. But, in spite of decades of research, the fundamental advances in laboratory involving electrolytic cell design and treatment system development have not led to urgently needed improvements in industrially practicable electrochemical softening technique. In this review, we firstly provide the critical insights into the mechanism of the currently widely used cathode precipitation process and its inherent limitations, which seriously impede its wide implementation in industry. To relieve the above limitations, some cutting-edge electrochemically homogeneous crystallization systems have been developed, the effectiveness of which are also comprehensively summarized. In addition, the pros and cons between cathode precipitation and electrochemically homogeneous crystallization systems are systematically outlined in terms of performance and economic evaluation, potential application area, and electrolytic cell and system complexity. Finally, we discourse upon practical challenges impeding the industrial-scale deployment of electrochemical water softening technique and highlight the integration of strong engineering sense with fundamental research to realize industry-scale deployment. This review will inspire the researchers and engineers to break the bottlenecks in electrochemical water softening technology and harness this technology with the broadened industrial application area.

Centralized softening as a solution to chloride pollution: An empirical analysis based on Minnesota cities.

Chloride is a key component of salt, used in many activities such as alkali production, water treatment, and de-icing. Chloride entering surface and groundwater is a concern due to its toxicity to aquatic life and potential to degrade drinking water sources. Minnesota being a hard-water state, has a high demand for water softening. Recent research has found that home-based water softeners contribute significantly to chloride loading at municipal wastewater treatment plants (WWTPs). Because of this, many WWTPs would now require water quality based effluent limits (WQBELs) to comply with the state's chloride water quality standards (WQS), unless they install chloride treatment technologies, which are limited and cost-prohibitive to most communities. A potential solution to this problem, is shifting from home-based water softening to a system where water is softened at drinking water plants, before reaching homes, i.e. centralized softening, analyzed in this paper based on its ability to address both chloride pollution and water softening needs, at reasonable cost. We estimate lifetime costs of three alternative solutions: centralized softening, home-based softening, and a Business as Usual (BAU) or baseline alternative, using annualized 20-year loan payments and Net Present Value (NPV), applied to 84 Minnesota cities with matching data on drinking water plants and WWTPs. We find that centralized softening using either Reverse Osmosis (RO) or lime-softening technologies is the more cost-effective solution, compared to the alternative of home-based softening with end-of-pipe chloride treatment, with a cost ratio in the range 1:3-1:4. Between the two centralized softening options, we find RO-softening to be the lower cost option, only slightly more costly (1.1 cost ratio) than the BAU option. Considering additional environmental and public health benefits, and cost savings associated with removal of home-based softeners, our results provide helpful information to multiple stakeholders interested in an effective solution to chloride pollution.

Application of Chemical Crystallization Circulating Pellet Fluidized Beds for Softening and Saving Circulating Water in Thermal Power Plants.

The circulating pellet fluidized bed (CPFB) softening method is a highly efficient and environmentally friendly softening technology that can be used to reduce water hardness during the pretreatment process of circulating water in thermal power plants. The performance of chemical crystallization CPFB reactors was tested for increasing the concentration ratio and softening the circulating water in a thermal power plant in Dingzhou, Hebei. The results show that usage of CPFB reactors removed water hardness and Ca2+ ions with efficiencies exceeding 60% and 90%, respectively. The size of the particles discharged from the reactors was approximately 1-3 mm, and the content of CaO in these particles was found to be greater than 50%. All the discharged particles were reused in the desulfurization system in the power plant. The operational cost of the CPFB system is US$0.074 per cubic meter of water. After adopting the proposed CPFB softening method in the Dingzhou Power Plant, the concentration ratio of the circulation cooling water was increased from 4.5 to more than 9. In addition, the amount of replenished water and sewage discharge were both reduced by 150 m3/h, and the amount of scale inhibitor used in the system was reduced by more than 30%. These improvements contribute to approximately US$200,000 in annual savings in the power plant. In summary, the CPFB softening method demonstrated a high hardness removal rate, strong economic benefits, and remarkable environmental and social benefits. Therefore, this method seems ideal for softening replenished circulating cooling water, increasing the concentration ratio of the water and achieving zero liquid discharge (ZLD) in thermal power plants.

Synthesis and fabrication of antibacterial hydrogel beads based on modified-gum tragacanth/poly(vinyl alcohol)/Ag0 highly efficient sorbent for hard water softening.

In the current study, hard water softening for the removal of Ca2+ and Mg2+ ions was performed using hydrogel beads based on Gum Tragacance (GT) modified by using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and poly(vinyl alcohol). The antibacterial spherical hydrogel beads were fabricated by instantaneous gelation of well dispersed mixture of poly(AMPS)-g-GT (1 g), poly(vinyl alcohol) (PVA, 1 g) flocculent, green-synthesized silver metal nanoparticles (AgNPs, 10 mg), and graphene oxide (GO, 10 mg) in the acetone solution of boric acid and then transferring into the different amounts (0.5-2.5 mL) of acidic solution of glutaraldehyde (GA) as cross-linker. The beads were fully characterized and their adsorption behavior matched well with the pseudo-second-order kinetic and the Langmuir isotherm models with the maximum adsorption of Ca2+(114.18 mg g-1) and Mg2+(162.46 mg g-1). The removal ability of the beads decreased by 6% after four adsorption/desorption cycles. The antibacterial performance of the hydrogel beads was also investigated against Gram-positive and Gram-negative bacteria.

Full-Scale Experimental Study of Groundwater Softening in a Circulating Pellet Fluidized Reactor.

The softening effect of a new type of circulating pellet fluidized bed (CPFB) reactor on groundwater was studied through a full-scale experiment. The operation of the CPFB reactor in the second water plant in Chang'an District in Xi'an China was monitored for one year, and the results were compared with those for the Amsterdam reactor in The Netherlands. The removal efficiency of Ca2+ in the CPFB reactor reached 90%; the removal rate of total hardness was higher than 60%; effluent pH was 9.5⁻9.8; the turbidity of the effluent and the turbidity after boiling were lower than 1.0 NTU; the unit cost was less than €0.064 per m³; and the softened effluent was stable. The pellets in the CPFB reactor were circulated, providing higher crystallization efficiency. The diameter of the discharged pellets reached between 3⁻5 mm, and the fluidized area height of the CPFB reactor was 4 m. The performance parameters of the CFPB reactor were optimized.

Production of demineralized water for use in thermal power stations by advanced treatment of secondary wastewater effluent.

The operation and efficiency of a modern, high-tech industrial full-scale water treatment plant was investigated in the present study. The treated water was used for the supply of the boilers, producing steam to feed the steam turbine of the power station. The inlet water was the effluent of municipal wastewater treatment plant of the city of Bari (Italy). The treatment stages comprised (1) coagulation, using ferric chloride, (2) lime softening, (3) powdered activated carbon, all dosed in a sedimentation tank. The treated water was thereafter subjected to dual-media filtration, followed by ultra-filtration (UF). The outlet of UF was subsequently treated by reverse osmosis (RO) and finally by ion exchange (IX). The inlet water had total organic carbon (TOC) concentration 10-12 mg/L, turbidity 10-15 NTU and conductivity 3500-4500 µS/cm. The final demineralized water had TOC less than 0.2 mg/L, turbidity less than 0.1 NTU and conductivity 0.055-0.070 µS/cm. Organic matter fractionation showed that most of the final DOC concentration consisted of low molecular weight neutral compounds, while other compounds such as humic acids or building blocks were completely removed. It is notable that this plant was operating under "Zero Liquid Discharge" conditions, implementing treatment of any generated liquid waste.

A sulphonated carbon dot-chitosan hybrid hydrogel nanocomposite as an efficient ion-exchange film for Ca2+ and Mg2+ removal.

We have developed a hybrid hydrogel nanocomposite film via conjugation of oxidised carbon dots synthesized from 11-mercaptoundecanoic acid with chitosan. The potential applicability of the film was then successfully tested for the removal of Ca2+ and Mg2+ ions from solution.

A clinoptilolite-PDMS mixed-matrix membrane for high temperature water softening.

A mixed-matrix membrane composed of polydimethylsiloxane (PDMS) as the continuous phase and clinoptilolite, a naturally occurring zeolite, as the active phase has been used to decrease the conductivity of water by more than 80% across the membrane. Testing was carried out using a cross-flow configuration at temperatures as high as 160 °C using a constant transmembrane pressure of 8 bar. The simple fabrication method for the membrane, the durability of the system under the test conditions, and a suitable flux rate make such membranes promising candidates for industrial wastewater treatment.

[Adsorption of calcium ion from aqueous solution using Na(+)-conditioned clinoptilolite for hot-water softening].

This work investigated adsorptive removal of calcium ion (Ca2+) by virtue of Na(+) -conditioned clinoptilolite simulating the process of softening for industrial hot-water system. Influential factors such as the activation/regeneration of sorbent and solution pH were tested. The kinetics/thermodynamics for adsorption of Ca2+ were analyzed and discussed. Results showed that: (1) The adsorption rate was in good agreement with the pseudo-second order kinetic models, and the process of adsorption better followed the Langmuir model; (2) Higher solution temperature allowed an enhanced efficiency on Ca2+ removal, albeit the maximum adsorption capacity of Na(+)-conditioned clinoptilolite was hardly affected; (3) The process of adsorption was dominated by chemisorption, and also characterized by entropy increase with spontaneous/endothermic nature; (4) Solution temperature was suggested to be controlled within the range of 6 to 10, and more than 9 times of sorbent regeneration could be ensured for an effective adsorption towards Ca2+ with initial concentration less than 20 mg x L(-1). It was demonstrated that the activated clinoptilolite should be a promising alternative adsorbent for industrial hot-water softening.

Natural clinoptilolite composite membranes on tubular stainless steel supports for water softening.

Disk membranes generated from high-purity natural clinoptilolite mineral rock have shown promising water desalination and de-oiling performance. In order to scale up production of these types of membranes for industrial wastewater treatment applications, a coating strategy was devised. A composite mixture of natural clinoptilolite from St. Cloud (Winston, NM, USA) and aluminum phosphate was deposited on the inner surface of porous stainless steel tubes by the slip casting technique. The commercial porous stainless steel tubes were pre-coated with a TiO2 layer of about 10 µm. Phase composition and morphology of the coating materials were investigated using X-ray diffraction and scanning electron microscopy. Water softening performance of the fabricated membranes was evaluated using Edmonton (Alberta, Canada) municipal tap water as feed source. Preliminary experimental results show a high water flux of 7.7 kg/(m(2) h) and 75% reduction of hardness and conductivity in a once-through membrane process at 95 °C and feed pressure of 780 kPa. These results show that natural zeolite coated, stainless steel tubular membranes have high potential for large-scale purification of oil sands steam-assisted gravity drainage water at high temperature and pressure requirements.

Effect of water treatment additives on lime softening residual trace chemical composition--implications for disposal and reuse.

Drinking water treatment residues (WTR) offer potential benefits when recycled through land application. The current guidance in Florida, US allows for unrestricted land application of lime softening WTR; alum and ferric WTR require additional evaluation of total and leachable concentrations of select trace metals prior to land application. In some cases a mixed WTR is produced when lime softening is accompanied by the addition of a coagulant or other treatment chemical; applicability of the current guidance is unclear. The objective of this research was to characterize the total and leachable chemical content of WTR from Florida facilities that utilize multiple treatment chemicals. Lime and mixed lime WTR samples were collected from 18 water treatment facilities in Florida. Total and leachable concentrations of the WTR were measured. To assess the potential for disposal of mixed WTR as clean fill below the water table, leaching tests were conducted at multiple liquid to solid ratios and under reducing conditions. The results were compared to risk-based soil and groundwater contamination thresholds. Total metal concentrations of WTR were found to be below Florida soil contaminant thresholds with Fe found in the highest abundance at a concentration of 3600 mg/kg-dry. Aluminum was the only element that exceeded the Florida groundwater contaminant thresholds using SPLP (95% UCL = 0.23 mg/L; risk threshold = 0.2 mg/L). Tests under reducing conditions showed elevated concentrations of Fe and Mn, ranging from 1 to 3 orders of magnitude higher than SPLP leachates. Mixed lime WTR concentrations (total and leachable) were lower than the ferric and alum WTR concentrations, supporting that mixed WTR are appropriately represented as lime WTR. Testing of WTR under reducing conditions demonstrated the potential for release of certain trace metals (Fe, Al, Mn) above applicable regulatory thresholds; additional evaluation is needed to assess management options where reducing conditions may develop.

A novel eco-friendly technique for efficient control of lime water softening process.

Lime softening is an established type of water treatment used for water softening. The performance of this process is highly dependent on lime dosage. Currently, lime dosage is adjusted manually based on chemical tests, aimed at maintaining the phenolphthalein (P) and total (M) alkalinities within a certain range (2 P - M > or = 5). In this paper, a critical study of the softening process has been presented. It has been shown that the current method is frequently incorrect. Furthermore, electrical conductivity (EC) has been introduced as a novel indicator for effectively characterizing the lime softening process.This novel technique has several advantages over the current alkalinities method. Because no chemical reagents are needed for titration, which is a simple test, there is a considerable reduction in test costs. Additionally, there is a reduction in the treated water hardness and generated sludge during the lime softening process. Therefore, it is highly eco-friendly, and is a very cost effective alternative technique for efficient control of the lime softening process.

Enzyme catalyzed electricity-driven water softening system.

Hardness in water, which is caused by divalent cations such as calcium and magnesium ions, presents a major water quality problem. Because hard water must be softened before use in residential applications, there is great interest in the saltless water softening process because, unlike ion exchange softeners, it does not introduce additional ions into water. In this study, a saltless hardness removal driven by bioelectrochemical energy produced through enzymatic oxidation of glucose was proposed and investigated. Glucose dehydrogenase was coated on a carbon electrode to catalyze glucose oxidation in the presence of NAD⁺ as a cofactor/mediator and methylene green as an electrocatalyst. The results showed that electricity generation stimulated hardness removal compared with non-electricity conditions. The enzymatic water softener worked upon a 6h batch operation per day for eight days, and achieved an average hardness removal of 46% at a high initial concentration of 800 mg/L as CaCO3. More hardness was removed at a lower initial concentration. For instance, at 200mg/L as CaCO3 the enzymatic water softener removed 76.4±4.6% of total hardness. The presence of magnesium ions decreased hardness removal because of its larger hydrated radius than calcium ions. The enzymatic water softener removed 70-80% of total hardness from three actual hard water samples. These results demonstrated a proof-of-concept that enzyme catalyzed electricity generation can be used to soften hard water.

Predicting the settling velocity of flocs formed in water treatment using multiple fractal dimensions.

Here we introduce a distribution of floc fractal dimensions as opposed to a single fractal dimension value into the floc settling velocity model developed in earlier studies. The distribution of fractal dimensions for a single floc size was assumed to cover a range from 1.9 to 3.0. This range was selected based on the theoretically determined fractal dimensions for diffusion-limited and cluster-cluster aggregation. These two aggregation mechanisms are involved in the formation of the lime softening flocs analyzed in this study. Fractal dimensions were generated under the assumption that a floc can have any value of normally distributed fractal dimensions ranging from 1.9-3.0. A range of settling velocities for a single floc size was calculated based on the distribution of fractal dimensions. The assumption of multiple fractal dimensions for a single floc size resulted in a non-unique relationship between the floc size and the floc settling velocity, i.e., several different settling velocities were calculated for one floc size. The settling velocities calculated according to the model ranged from 0 to 10 mm/s (average 2.22 mm/s) for the majority of flocs in the size range of 1-250 µm (average 125 µm). The experimentally measured settling velocities of flocs ranged from 0.1 to 7.1 mm/s (average 2.37 mm/s) for the flocs with equivalent diameters from 10 µm to 260 µm (average 124 µm). Experimentally determined floc settling velocities were predicted well by the floc settling model incorporating distributions of floc fractal dimensions calculated based on the knowledge of the mechanisms of aggregation, i.e., cluster-cluster aggregation and diffusion-limited aggregation.

Optimisation of Lime-Soda process parameters for reduction of hardness in aqua-hatchery practices using Taguchi methods.

This paper presents the optimisation of Lime-Soda process parameters for the reduction of hardness in aqua-hatchery practices in the context of M. rosenbergii. The fresh water in the development of fisheries needs to be of suitable quality. Lack of desirable quality in available fresh water is generally the confronting restraint. On the Indian subcontinent, groundwater is the only source of raw water, having varying degree of hardness and thus is unsuitable for the fresh water prawn hatchery practices (M. rosenbergii). In order to make use of hard water in the context of aqua-hatchery, Lime-Soda process has been recommended. The efficacy of the various process parameters like lime, soda ash and detention time, on the reduction of hardness needs to be examined. This paper proposes to determine the parameter settings for the CIFE well water, which is pretty hard by using Taguchi experimental design method. Orthogonal Arrays of Taguchi, Signal-to-Noise Ratio, the analysis of variance (ANOVA) have been applied to determine their dosage and analysed for their effect on hardness reduction. The tests carried out with optimal levels of Lime-Soda process parameters confirmed the efficacy of the Taguchi optimisation method. Emphasis has been placed on optimisation of chemical doses required to reduce the total hardness using Taguchi method and ANOVA, to suit the available raw water quality for aqua-hatchery practices, especially for fresh water prawn M. rosenbergii.

Application of fractal dimensions to study the structure of flocs formed in lime softening process.

The use of fractal dimensions to study the internal structure and settling of flocs formed in lime softening process was investigated. Fractal dimensions of flocs were measured directly on floc images and indirectly from their settling velocity. An optical microscope with a motorized stage was used to measure the fractal dimensions of lime softening flocs directly on their images in 2 and 3D space. The directly determined fractal dimensions of the lime softening flocs were 1.11-1.25 for floc boundary, 1.82-1.99 for cross-sectional area and 2.6-2.99 for floc volume. The fractal dimension determined indirectly from the flocs settling rates was 1.87 that was different from the 3D fractal dimension determined directly on floc images. This discrepancy is due to the following incorrect assumptions used for fractal dimensions determined from floc settling rates: linear relationship between square settling velocity and floc size (Stokes' Law), Euclidean relationship between floc size and volume, constant fractal dimensions and one primary particle size describing entire population of flocs. Floc settling model incorporating variable floc fractal dimensions as well as variable primary particle size was found to describe the settling velocity of large (>50 µm) lime softening flocs better than Stokes' Law. Settling velocities of smaller flocs (<50 µm) could still be quite well predicted by Stokes' Law. The variation of fractal dimensions with lime floc size in this study indicated that two mechanisms are involved in the formation of these flocs: cluster-cluster aggregation for small flocs (<50 µm) and diffusion-limited aggregation for large flocs (>50 µm). Therefore, the relationship between the floc fractal dimension and floc size appears to be determined by floc formation mechanisms.

Bacterial colonization of pellet softening reactors used during drinking water treatment.

Pellet softening reactors are used in centralized and decentralized drinking water treatment plants for the removal of calcium (hardness) through chemically induced precipitation of calcite. This is accomplished in fluidized pellet reactors, where a strong base is added to the influent to increase the pH and facilitate the process of precipitation on an added seeding material. Here we describe for the first time the opportunistic bacterial colonization of the calcite pellets in a full-scale pellet softening reactor and the functional contribution of these colonizing bacteria to the overall drinking water treatment process. ATP analysis, advanced microscopy, and community fingerprinting with denaturing gradient gel electrophoretic (DGGE) analysis were used to characterize the biomass on the pellets, while assimilable organic carbon (AOC), dissolved organic carbon, and flow cytometric analysis were used to characterize the impact of the biological processes on drinking water quality. The data revealed pellet colonization at concentrations in excess of 500 ng of ATP/g of pellet and reactor biomass concentrations as high as 220 mg of ATP/m(3) of reactor, comprising a wide variety of different microorganisms. These organisms removed as much as 60% of AOC from the water during treatment, thus contributing toward the biological stabilization of the drinking water. Notably, only a small fraction (about 60,000 cells/ml) of the bacteria in the reactors was released into the effluent under normal conditions, while the majority of the bacteria colonizing the pellets were captured in the calcite structures of the pellets and were removed as a reusable product.

Investigation on removal of hardness ions by capacitive deionization (CDI) for water softening applications.

Capacitive deionization (CDI) for removal of water hardness was investigated for water softening applications. In order to examine the wettability and pore structure of the activated carbon cloth and composites electrodes, surface morphological and electrochemical characteristics were observed. The highly wettable electrode surface exhibited faster adsorption/desorption of ions in a continuous treatment system. In addition, the stack as well as unit cell operations were performed to investigate preferential removal of the hardness ions, showing higher selectivity of divalent ions rather than that of the monovalent ion. Interestingly, competitive substitution was observed in which the adsorbed Na ions were replaced by more strongly adsorptive Ca and Mg ions. The preferential removal of divalent ions was explained in terms of ion selectivity and pore characteristics in electrodes. Finally, optimal pore size and structure of carbon electrodes for efficient removal of divalent ions were extensively discussed.

Dechlorination by ultraviolet radiation: a suitable alternative to activated carbon in dialysis water systems?

Chlorine-based products are widely used in the water supply industry, and the potential for adverse effects in the haemodialysis setting is well documented. To date, the most commonly used method of chlorine removal has been granular activated carbon filters. An increasingly popular method of dechlorination is the use of high intensity, broad-spectrum UV systems to reduce both free chlorine and combined chlorine compounds (chloramines) into easily removed by-products. UV radiation has been successfully used in the pharmaceutical and food industries to destroy free chlorine and/or chloramines present in water, and kill all known spoilage microorganisms including bacteria, viruses, yeasts and moulds (and their spores). This nonchemical method can offer significant advantages and benefits compared to conventional dechlorination technologies currently employed in dialysis water systems. Whilst UV treatment at 254 nm wavelength has been routinely used for disinfection purposes in dialysis water systems, this paper considers whether UV radiation can be used as an alternative to more traditional methods of chlorine removal.

The soft option. Interview by Louise Hunt.

A study is recruiting 310 children in hard water areas of England to test anecdotal evidence that water softeners reduce the symptoms of eczema.