Process optimization to enhance utilization efficiency of precipitants for chloride removal from flue gas desulfurization wastewater via Friedel's salt precipitation.

The treatment cost for Cl- removal by Friedel's salt precipitation depended significantly on utilization rate of the precipitant aluminate. In this study, effects of Ca/Al molar ratio, reaction time, temperature and Al/Cl molar ratio were investigated to maximize Al utilization rate for Cl- removal from flue gas desulfurization wastewater. Batch results showed that the maximum Al utilization rate of 55.8-60.3% was obtained at Ca/Al ratio of 3.00, reaction time of 90 min, temperature of 35 °C and Al/Cl ratio of 0.50 regardless of the initial Cl- concentration. The precipitate obtained at the highest Al utilization rate had the highest interlayer spacing, the best crystal integrity, and the strongest binding energy of the Al-OH bond. The optimized condition made ion exchange between Cl- and OH- easier, and obtained more stable Friedel's salt structure to adsorb Cl-. Pilot-scale results showed that maximizing Al utilization rate with low dosages of precipitants had insignificant effects on the removal of Mg2+, Ca2+ and sulfate compared to the strategy to maximize Cl-, but enhanced Al utilization rate from 38.2% to 56.4%. Economic analysis showed that enhancing Al utilization rate greatly reduced treatment cost of the Friedel's salt precipitation method by 30.5%, and made the two-stage desalination process more feasible and worth popularizing.

Sulfate removal from wastewater using ettringite precipitation: Magnesium ion inhibition and process optimization.

One of the main challenges in industrial wastewater treatment and recovery is the removal of sulfate, which usually coexists with Ca2+ and Mg2+. The effect of Mg2+ on sulfate removal by ettringite precipitation was investigated, and the process was optimized in the absence and presence of Mg2+. In the absence of Mg2+, the optimum conditions with sulfate removal of 99.7% were obtained at calcium-to-sulfate ratio of 3.20, aluminum-to-sulfate ratio of 1.25 and pH of 11.3 using response surface methodology. In the presence of Mg2+, sulfate removal efficiency decreased with increasing Mg2+ concentration, and the inhibitory effect of Mg2+ matched the competitive inhibition Monod model with half maximum inhibition concentration of 57.4 mmol/L. X-ray diffraction and Fourier transform infrared spectroscopy analyses of precipitates revealed that ettringite was converted to hydrotalcite-type (HT) compound in the presence of Mg2+. The morphology of precipitates was transformed from prismatic crystals to stacked layered crystals, which confirmed that Mg2+ competes with Ca2+ for Al3+ to form HT compound. A two-stage process was designed with Mg2+ removal before ettringite precipitation to eliminate the inhibitory effect, and is potential to realize sludge recovery at the same time of effective removal of sulfate and hardness.

Application of disk tube reverse osmosis in wastewater treatment: A review.

Disk tube reverse osmosis (DTRO), a modified module RO, has received growing attention in wastewater treatment. However, there is no comprehensive review of DTRO applications for wastewater treatment. In this study, China was found to be a major contributor to DTRO investigations. Specifically, 46 full- and 17 pilot-scale DTRO applications in China from the literature are summarized. The cumulative reported DTRO application scale in wastewater treatment amounted to ~16,500 m3/d by 2020 in China. Leachate and flue gas desulfurization (FGD) wastewater had the highest reported frequencies. Two-stage DTRO and "biological treatment + DTRO/two-stage DTRO" were the most reported processes in leachate treatment. Chemical oxygen demand (COD) and NH4+-N were removed at 99.00-99.95% and 98.00-99.98%, respectively, in full scales in leachate treatment. DTRO was primarily utilized in the concentration unit in hypersaline wastewater treatment (e.g., FGD wastewater). Total dissolved solids (TDS) were removed at 94.69-96.87% and 85.95-96.5% in the full- and pilot-scales, respectively. The overall operating costs were 17.50-60.61 CNY/m3 and 0.69-8.75 CNY/kgCOD for leachate treatment and 26.94-52.28 CNY/m3 and 0.71-3.61 CNY/kgTDS for FGD wastewater treatment. The major components of operating costs were chemical costs (13.09 CNY/m3, 1.63 CNY/kgCOD) for two-stage DTRO and electricity costs (19.73 CNY/m3, 1.67 CNY/kgCOD) for the "biological treatment + DTRO/two-stage DTRO" process. DTRO has shown promising prospects for wastewater treatment.

Insight into the magnetic lime coagulation-membrane distillation process for desulfurization wastewater treatment: From pollutant removal feature to membrane fouling.

The high suspended solid (SS) and salts were main issues for flue gas desulfurization wastewater (FGDW). A magnetic lime coagulation (MLC)-membrane distillation (MD) integrated process was firstly applied with a self-made poly (vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) membrane and the pollutants remove feature and membrane fouling were discussed. The SS was nearly 100 % removed and magnetic seed significantly accelerate the settleability. The flux was 43.00 kg/m2 h with a salt rejection >99 %. It was higher than 13 kg/m2 h in the first 125 h during the 18d continuous test, and the rejection for all cations, anions, total organic carbon (TOC) and total inorganic carbon (TIC) were higher than 99.95 %, 99.00 %, 98.81 %, and 99.65 %, respectively. Humic substances and tryptophan with 100-5000 Da were main dissolved organic matter (DOM), which were significantly removed. However, membrane fouling and wetting happened after 150 h. Scaling was the main foulants, while the organic fouling and biofouling were also detected. A new "bricklaying model" was induced to depict the formation of foulant layer, the colloids, organic matters (OMs) and microbe communities act as the "concrete", while the inorganic crystals (magnesium and calcium oxysulphides) were the "bricks". This contribution offers a new method for FGDW treatment and the membrane fouling mechanism of MD process.

A two-stage desalination process for zero liquid discharge of flue gas desulfurization wastewater by chloride precipitation.

A two-stage desalination process was developed to achieve zero liquid discharge (ZLD) of flue gas desulfurization (FGD) wastewater by precipitating chloride as Friedel's salt. Influential factors for Friedel's salt precipitation, including dosage, reaction time, concentration of sulfate, were investigate by batch tests. Batch results showed that at calcium to aluminum molar ratio of 3.0, the optimal chloride removal and the highest crystallinity of Friedel's salt were obtained. Sulfate impeded Friedel's salt precipitation by competitive inhibition mechanism, and thus calcium sulfate removal was designed in advance of chloride removal. Batch results and long-term results of bench-scale experiments showed that magnesium and part of sulfate were effectively removed by lime addition in Stage I of the proposed process, and then the remaining sulfate and 48.1 % of chloride were precipitated as ettringite and Friedel's salt in Stage II. The effluent of the two-stage process was alkaline with low turbidity, and had considerable desulfurization capacity. Techno-economic evaluation showed that the two-stage process is technically feasible, economically viable and environmentally friendly technology for ZLD of FGD wastewater.

The efficient removal of thallium from sintering flue gas desulfurization wastewater in ferrous metallurgy using emulsion liquid membrane.

The removal of thallium ions in flue gas desulfurization wastewater from ferrous metallurgic industry was studied by emulsion liquid membrane (ELM) method using 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (P507) as carrier, aviation kerosene (AK) as organic solvent, polyisobutylene succinimide (T154) as surfactant, polyisobutylene (PIB) as additive, and sulfuric acid as internal reagent. Some important influence parameters such as concentrations of carrier, surfactant and stripping agent, agitation speed, extraction time, volume ratios of feed solution to emulsion phase and internal phase to membrane phase, and their effects on the removal efficiency of Tl in the ELM process were investigated and optimized. Under the optimum operating conditions of 2% of carrier, 5% of surfactant, 0.5 M of stripping agent, 350 rpm of agitation speed, 12.5:1 of volume ratio of feed solution to emulsion phase, and 3:1 volume ratio of membrane to internal phase, the maximum extraction efficiency of thallium reached 99.76% within 15-min reaction time. The ICP-MS analysis indicated that the thallium concentration in treated wastewater was below 5 µg/L and could meet the emission standard demand for industrial wastewater enacted by the local government of Hunan province of China. Meanwhile, the extraction of impurity ions calcium and magnesium in the ELM system was investigated. The result showed that an acidic environment would be in favor of the removal of Tl from calcium and magnesium contained in wastewater. Graphical abstract ᅟ.