Fluoride Removal Research Articles

Treatment of fluoride-contaminated water in a prototype adsorption unit using zirconium-activated carbon nanocomposites

ABSTRACT Zirconium-activated carbon nanocomposites (ZANC) are found to have high fluoride removal capacity and thus used as an adsorbent to perform column studies. The adsorbent was characterised using SEM-EDS and FTIR before and after the adsorption of fluoride. A packed bed adsorber prototype of 1 m length was fabricated to carry out defluoridation studies. The effect of varying initial fluoride concentration (2.5–10 ppm) and bed height (6–14 cm) was studied. The maximum fluoride removal was found to be 29.4% and uptake capacity was 4.72 mg/g at an initial fluoride concentration of 10 ppm, flow rate of 2 LPM, and bed height of 14 cm for synthetic samples. The Thomas, Yoon–Nelson and Bed Depth Service Time (BDST) models were employed and their results confirmed the experimental findings. The maximum fluoride adsorption capacities obtained from the Thomas model are 1.9 mg/g and from the BDST model, the N value was 20.979 mg/cm3. Regeneration studies were performed and found that the adsorbent can be regenerated for three cycles. Column studies were also performed using real-field groundwater samples collected from Pavagada of Tumakuru district. All the tested parameters of the treated water were found to be within the permissible limit.

Development of modified MgO/biochar composite for chemical adsorption enhancement to cleanup fluoride-contaminated groundwater

Fluoride contamination in groundwater has become a global environmental issue. Magnesium oxide (MgO) has demonstrated effectiveness as an adsorbent in treating fluoride pollution in groundwater. However, its use in powder and fine granular form often results in losses during the adsorption process, posing challenges for post-treatment recovery and potentially causing secondary environmental pollution. In this study, two novel fluoride adsorbents [rice husk (RH) and spent coffee grounds (SCG)-based magnesium oxide (MgO) biochar composites (MgO/RH and MgO/SCG)] were developed to cleanup fluoride-polluted groundwater. During the adsorbent synthesis process, RH and SCG biochar were pyrolyzed at 500 °C and modified by calcination using MgO. Both MgO/RH and MgO/SCG surfaces exhibited abundant pore structures and formed MgO crystal phases. Batch experiments results show that when the MgO/RH and MgO/SCG material dosages were 1 g/L, fluoride removal rates reached 80% and 86% respectively. The isotherms and kinetics of fluoride adsorption with MgO/RH and MgO/SCG followed the Langmuir isotherm equation and pseudo-second-order kinetic model. The maximum fluoride adsorption capacities of MgO/RH and MgO/SCG were 63.47 mg/g and 141.98 mg/g, respectively, indicating these materials used mono-layer adsorption mechanism for fluoride adsorption. The addition of MgO into the pores of porous adsorbent materials effectively increased their reactive sites and enhanced the adsorption performance of carbon materials. Particularly, SCG biochar had a richer pore structure than RH biochar, providing a larger contact surface area, facilitating the effective dispersion and doping of MgO into the pores. Therefore, MgO/SCG composite exhibited excellent fluoride adsorption properties in water, indicating the potential for developing a new type of MgO-modified SCG adsorbent material with green prospects. This composite effectively mitigated fluoride contamination, reducing the fluoride concentration in groundwater. Both RH and SCG are agricultural and food waste by-products, thus offering the opportunity to significantly reduce production, operation, and maintenance costs.

Evaluation of engineered binderless alumina – titania beads for fluoride removal from impaired water resources

Groundwater is often contaminated with various species, with fluoride concentrations being of particular concern. Numerous studies have used adsorbents for fluoride uptake, but most are tested only as powders and not commercially acceptable engineered shapes. Therefore, it was necessary to evaluate the performance of the newly developed Al2O3/TiO2 sorbents in their beaded form to assess their efficacy in comparison to activated alumina granules. Binderless sorbent beads were self-bound with the alumina and titania phases present. The fluoride exchange kinetics of Al2O3/TiO2 beads were comparable to the powdered form. Moreover, the Al2O3/TiO2 beads had higher fluoride loading than commercially available alumina (0.17 meq/g compared to 0.13 meq/g). The Al2O3/TiO2 beads also removed: barium, calcium, lithium, magnesium, manganese, potassium, silica, and strontium from groundwater. In fixed bed column tests, the beads-maintained fluoride within acceptable limits for 42 bed volumes, which substantially outperformed activated alumina (2.5 bed volumes). This study demonstrated that Al2O3/TiO2 beads outperformed commercially available activated alumina materials. Notably, transforming the materials into beaded forms significantly improved their suitability for fluoride removal in industrially relevant fixed-bed column environments. Future studies should focus on enhancing material binding properties to increase crush strength and attrition resistance. A deeper knowledge of regeneration strategies may also facilitate cost reduction.

Adsorption effect for removing fluoride with species of nitrogen by using La-BDC-NH2/C3N4: Experiments and mechanism

Fluoride contamination has emerged as a significant global environmental concern, with prolonged consumption of fluoride-rich groundwater being a primary contributor to fluorosis. Nitrogen sites play an important role in the process of fluoride removal, but the influence of different nitrogen species on fluoride adsorption has not been clearly clarified. In this study, a lanthanide organic framework adsorbent La-MOF-NH2 was prepared by solvothermal method, and a new adsorbent La-MOF-NH2@g-C3N4 was synthesized by adding g-C3N4 rich in various nitrogen sources. The effects of adsorbent dosage, pH, temperature and co-existing anions on the adsorption of fluorine were systematically studied. Optimal conditions were identified at a dosage of 2 g/L and a pH of 3, achieving theoretical maximum adsorption capacities of 219.4406 mg/g and 63.1401 mg/g, respectively. The results of five regeneration experiments shown that La-MOF-NH2 and La-MOF-NH2@g-C3N4 have strong recovery capacity. According to the adsorption isotherm and kinetic model, the adsorption mechanism of fluoride ions is mainly hydrogen bonding and chemisorption. In addition, through the experimental characterization and mechanism study, it was proved that amino group > pyridinic nitrogen > graphitic nitrogen. It provides a good guide for designing adsorbents containing nitrogen sites.

High-performance fluoride removal by Fe/N co-doped microporous carbon: Mechanism of capacitive deionization with FeNx sites

Fluoride pollution is becoming increasingly serious with industrial growth. Controlling fluoride pollution have become important environmental issues of global concern. Transition metal nitrides are excellent CDI electrode materials due to their excellent conductivity and electrochemical stability. In this study, FeNx/C was synthesized as an electrode material for using the capacitive deionization (CDI) technique to achieve the effective removal of fluoride ions from wastewater. Its high specific surface area (463.278 mg/g) and high capacitance (44.29 F/g) were demonstrated and it had a high adsorption capacity of 158.33 mg/g. FeN3 and FeN4 were used as the main sites as capacitive deionization for removing fluoride from the water by chemisorption and hydrogen bonding. The higher adsorption energy by density functional calculation also indicated that the existence of Fe-N coordination bond effectively improved its electrosorption capacity. This study is beneficial to provide references and research ideas for removing fluoride in the CDI field.

Sustainable fluoride removal with scrap aluminum: Co-producing cryolite and hydrogen

This study presents a novel continuous process for fluoride removal and re- source recovery as cryolite, using a scrap aluminum-packed column. Efficient aluminum dissolution in hydrofluoric acid (HF) generates hydrogen gas and provides cost-saving alkalinity. The process achieves high efficiency (Al/F molar ratio of 2/6) within short Empty Bed Contact Times (15 min) and at low HF concentrations (500 mg/L). Solution pH plays a crucial role, with Al/F ratios above 1 achievable at pH below 4. The exothermic reaction requires temperature control, with a strong correlation (R²=0.99) between HF concentration and heat generation. Hydrogen production matches theoretical predictions. Cryolite synthesis was confirmed at optimized pH (5–5.5) with a 1:1 bypass ratio, achieving 98 % fluoride removal. XRD and SEM- EDS analyses verified cryolite formation. This approach offers a promising solution for industrial fluoride management, resource recovery, and clean hydrogen production.

Hydroxyapatite‐spent cathode carbon block modified asphalt and molecular dynamics simulation study

AbstractThe highly toxic substances contained in spent cathode carbon blocks (SCCB) pose a serious threat to human health and the ecological environment, and are difficult to recycle. To address this issue, we utilize H2O2 to oxidize cyanides and grow hydroxyapatite (HAP) on spent cathode carbon blocks to adsorb fluoride ions, achieving controlled removal of cyanides and fluorides. Subsequently, the hydroxyapatite‐spent cathode carbon block composite material (H‐SCCB) is applied to modified asphalt, and simulations of the interaction between hydroxyapatite interfaces and asphalt components are conducted. The results indicate that the total cyanide and fluoride ion concentrations in the experimental wastewater meet the discharge standards for industrial wastewater in China. Hydroxyapatite successfully grows on SCCB, presenting a rich porous structure and significantly increased surface area. Mechanical testing shows that 4% H‐SCCB exhibits optimal performance, with a 23.28% increase in complex modulus (G*) compared to the matrix asphalt. Creep recovery capability (R) increases by 54.32% and 7%, respectively. Additionally, molecular dynamics simulations reveal that the interface adsorption between hydroxyapatite and asphalt binder is primarily influenced by electrostatic forces. Under the influence of hydroxyapatite, the diffusion abilities of asphalt four components are as follows: resin > aromatic > saturate > asphaltene.

Highly enhanced fluoride removal from aqueous systems via solvent extraction utilizing trialkyl phosphine oxide as an efficient extractant

Solvent extraction (SX) has been recognized as an efficient approach for the large-scale removal of impurities, demonstrating considerable potential for fluoride extraction in industrial applications. However, existing fluoride extraction methods typically require the incorporation of additives to form complexes with fluoride for its removal. Due to the excessive additive requirements for efficient fluoride removal, these methods inevitably result in secondary contamination of feed solution, necessitating additional purification efforts to remove them. In this study, four extractants (trioctyl amine, tributyl phosphate, trioctyl phosphate, and trialkyl phosphine oxide (TRPO)) were investigated for fluoride removal via hydrogen bonding with hydrofluoric acid (HF). Various parameters, including the concentrations of extractants and stripping agents, pH values, extraction time, and temperature were initially optimized. It was found that TRPO exhibits the highest extraction efficiency for HF, with a single-stage extraction rate exceeding 70 %. Complete fluoride removal (> 99.9 %) was achieved through a consecutive four-stage extraction process. Further experiments, including maximum loading and slope analysis, combined with FT-IR and 19F NMR characterization, and DFT calculations elucidate the mechanism of the extraction. The transfer of HF into the organic phase is accomplished by the formation of a 1:1 hydrogen-bonded complex with TRPO. The loaded fluoride in the organic phase can be easily stripped by a base to get a fluoride salt. This study paves the way for the construction of novel SX systems to remove fluoride as HF.

Extraction of bio-hydroxyapatite from devilfish (Loricariidae) for the fluoride and cadmium adsorption from water and its feasible photocatalytic properties

In this study, the adsorption capacity of bio-hydroxyapatite (Bio-HAp) from devilfish for the removal of F- and Cd(II) from aqueous solutions was investigated. This material was synthesized according to a 2FI factorial experimental design by varying the extraction conditions for Bio-HAp, including the type of pretreatment (alkaline and peroxide), the calcination temperature from 550 to 850 °C, and the sonication process. The maximum adsorption capacities were 8.48 and 83.56 mg g-1 for F- and Cd(II), respectively. Statistical analysis showed the importance of the type of pretreatment, temperature, and sonication for adsorption. The predicted optimal conditions were Bio-HAp extracted from bone with peroxide pretreatment, calcination at 550 °C and sonication. The surface of the Bio-HAp was found to be mesoporous and basic in character. TGA, FT-IR and SEM-EDS characterizations confirmed the presence of F- and Cd(II) on the Bio-HAp surface and confirmed the adsorption mechanisms by electrostatic forces, ion exchange, and chemisorption. The Praunitz-Rake model of adsorption isotherm showed better agreement with the equilibrium adsorption data of F- and Cd(II) at pH 7. Furthermore, photodegradation experiments showed 100% degradation methylene blue (MB) under natural sunlight. This study indicates an effective photodegradation process, suggesting high adsorption capacity of the samples. The use of devilfish as an adsorbent promises to be a viable and sustainable option for the removal of fluoride and cadmium from water, and for use in photodegradation experiments.

Synthesis and characterization of a crosslinked deacetylated chitin modified chicken bone waste-derived hydroxyapatite and TiO2 biocomposite for defluoridation of drinking water

This work represents an innovative approach to the synthesis and characterization of a chitosan-based biocomposite for fluoride adsorption. The work involved the development of a biocomposite based on modified chicken bone waste-derived hydroxyapatite and TiO2. The composite was characterized using scanning electron microscopy with Energy Dispersive X-ray analysis (SEM-EDX), X-ray diffraction (XRD), Fourier-transform infrared analysis (FTIR), thermal-gravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The optimum parameters for fluoride removal were determined, and the kinetic data was better fitted to the pseudo-first-order model. The Liu equations provided a better description of the experimental adsorption isotherm data. The adsorption mechanism and the interaction of the composite with fluoride were better understood using Density Functional Theory (DFT) calculations and Non-Covalent Interactions (NCI) analyses, paving the way for more effective and efficient defluoridation methods.

Synthesis of Copper-Doped Metal Nanoferrites for Efficient Removal of Pharmaceutical Wastewater Pollutants in Membrane Bioreactor System

Pharmaceuticals present in the aquatic environment can poison aquatic species and humans through drinking water and cause harmful bacteria to become resistant. The role of transition metal doped metal nanoferrites for the enhanced efficiency of degradation process is widely achieved. In this work, copper doped magnesium ferrite (Cu-MgFe2O4) and copper doped zinc ferrite (Cu-ZnFe2O4) nanoparticles were synthesized using a sol-gel method. X-ray diffraction (XRD) analysis confirmed the formation of the spinel structure for both samples, with crystal sizes of 16.72 nm and 59.05 nm, respectively. The magnetic properties of the samples were studied using a vibrating sample magnetometer (VSM), which revealed that the addition of Cu2+ ions has a significant impact on the magnetic properties of the nanoparticles. The saturation magnetisation (Ms), retentivity (Mr) and coercivity value (Hc) for the Cu-MgFe2O4 sample were found to be 0.18453 emu, 39.584 × 10-3 emu and 139.61 Oe, respectively, while for the Cu-ZnFe2O4 sample, the values were 0.21271 emu, 71.022 × 10-3 emu and 285.91 Oe, respectively. The impact of copper doped nanoferrites on pollutant removal from pharmaceutical wastewater using the membrane Bioreactor (MBR) system has also been accomplished. The results demonstrated the effectiveness of ferrites in reducing concentrations of heavy metals, including lead and cadmium, within acceptable ranges for inland surface water and public sewers. Furthermore, the MBR system with ferrites exhibited efficient removal of fluoride, sulphide and radioactivity, ensuring compliance with the specified standards. Although the study exhibited the potential of ferrites in pollutants removal, further optimization is necessary to achieve complete compliance with water quality standards.

Effective removal of fluoride ions from contaminated water using electrochemical techniques: A critical review on recent developments and environmental perspective

Worldwide, water pollution poses significant threats to human health, with fluoride contamination emerging as a critical hazard. High fluoride concentrations in water cause severe health impacts, including dental and skeletal fluorosis, neurological damage, and harm to the parathyroid gland, cardiovascular, and reproductive systems. Electrochemical technique is one of the most widely used treatment technologies that has been extensively studied and provides a very effective, low-cost method of removing fluoride from contaminated water. The review reports the comprehensive electrochemical strategies for fluoride ions removal. The sources, toxicity, and impacts of fluoride pollution on health are discussed in this review. A comprehensive analysis of current electrochemical methods, including electrolysis, electrocoagulation, and the electro-fenton process, was provided in the context to facilitate the efficient removal of fluoride ions from wastewater. These methods exhibit high removal efficiencies, reaching up to 95 %, and offer scalability and operational flexibility, making them suitable for both centralized and decentralized water treatment systems. Furthermore, the recent advancements in the development of electrochemical technique for fluoride removal are critically reviewed. This study has prospected the recent developments, recommendations and future outlooks on electrochemical technique for fluoride removal.

Utilization of organic waste from Chinar leaves as sustainable and eco-friendly adsorbent for fluoride removal.

Due to concerns about high water fluoride concentrations and their detrimental consequences on health, particularly dental and skeletal fluorosis, dependable and cost-effective defluoridation techniques are needed. Chinar leaves (Platanus orientalis), a common waste, might be utilized for the production of activated carbon. For Chinar leaf activated carbon (CLAC) manufacturing, two pre-pyrolysis chemical modification procedures were used: acidic HCl (H-activation) and alkaline NaOH (OH-activation). The success of fluoride removal suggests further research and implementation in locations with fluoride-related water quality issues. This study examines how CLAC dosage, fluoride concentration, temperature, pH, and contact exposure effect defluoridation efficiency. The pseudo-second-order non-linear kinetic model and Freundlich non-linear isotherm model with R2 = 0.99 fit the data, resulting in a peak adsorption capacity of 30.3mg/g for 0.3g CLAC. In the present work, the adsorption mechanism was regulated by more than intraparticle diffusion. Adsorption occurred spontaneously as exothermic monolayer chemisorption, according to thermodynamic studies. Adsorbent activated with HCl (H-activated) showed promising results, with 73% F- removal efficiency for OH-activated and 91% for H-activated CLAC.

Recycling of Waste Oyster Shells for Fluoride Removal from Hydrofluoric Acid Wastewater

Recycling of Waste Oyster Shells for Fluoride Removal from Hydrofluoric Acid Wastewater

Simultaneous precipitation removal of fluoride ion and chloride ion from smelting waste acid using renewable remover

Purification and reuse is a potential method of smelting waste acid disposal. High concentrations of fluoride and chloride in waste acid are harmful impurity and must be removed. Previous studies have shown that fluoride removal with rare earth and chloride removal with bismuth have similar cyclic process of "precipitation removal-agent regeneration" and similar reaction conditions. In this paper, a method of simultaneous precipitation removal of F− and Cl− from waste acid using La(OH)3 and Bi2O3 as a mixed remover was proposed, and the mixed remover is regenerated by sodium hydroxide solution for the recycling of the remover. Thermodynamic analysis of La3+-Bi3+-F−-Cl−-H2O system verified the feasibility of simultaneous removal. The experimental results showed that under the optimum reaction conditions, the removal efficiencies of F− and Cl− were 93.67 % and 96.47 %, respectively, and the concentrations of F− and Cl− in the solution after removal were 66.70 mg/L and 71.10 mg/L, respectively. Under the optimum conditions, the regeneration efficiencies of La(OH)3 and Bi2O3 were 96.80 % and 96.95 %, respectively. The proposed process has the advantages of no waste output, short process, and low energy consumption and provides an environmentally friendly method of removing fluoride and chloride from waste acid.

Fluoride Removal in Water Using Kaolin and Eggshell Powder Blend Adsorbents

Fluoride contamination in water has emerged as a significant global concern due to its adverse health effects when consumed in excess. This study is focused on developing an eco-friendly, cost-effective adsorbent for fluoride removal using eggshells and kaolin. Adsorbent blends were prepared by mixing kaolin and eggshell powder in six different ratios, namely; 100:0, 80:20, 65:35, 50:50, 35:65, and 20:80. Cylindrical-shaped pellets were produced from each of the blends and subjected to the thermal treatment at 950 ◦C. Fluoride adsorption capacities of the pellets were investigated at different pH conditions (from pH 2 to pH 10) for a 5 mg/L fluoride solution with 1 g of adsorbent dosage and 60 min of contact time. Pellets with a 50:50 ratio (CKE3) were found to be the most effective adsorbent considering the adsorption capacity and stability at all the studied pH conditions. At pH 6, CKE3 showed an adsorption capacity of 0.06 mg/g compared to 0.02 mg/g of kaolin-only pellets. XRD, TGA-DSC, EDX and SEM analysis were used to characterize the adsorbent. XRD analysis showed that the raw adsorbent contained phases of CaCO3 and kaolinite, whereas the calcined material comprised Ca(OH)2 and metakaolinite. Batch experiments were carried out with CKE3 for adsorbent dosage, pH, contact time, and initial fluoride concentration. An adsorbent dosage of 4 g was capable of resulting in a 53% removal of fluoride for a 5 mg/L solution after 60 min of contact time. Pseudo-first-order and pseudo-second-order kinetic models were applied in the study, and pseudo-second-order exhibited the best fit. The isotherm data were studied for Langmuir and Freundlich models, and the results were satisfactorily fitted with Langmuir isotherm.

Fluoride removal using a rotating anode electro-coagulation reactor: Parametric optimization using response surface methodology, isotherms and kinetic studies, economic analysis and sludge characterization

The presence of fluoride in drinking water can cause various diseases, such as dental fluorosis and skeletal fluorosis. The present study aims to intensify the fluoride removal using a rotating anode electro-coagulation (EC) reactor with providing the proper hydrodynamics conditions. This fluoride removal is modeled and optimized using Response Surface Methodology (RSM) and central composite design (CCD) with varying operational parameters (rotation speed: 20–80 RPM, current: 0.2–1.0 A, initial fluoride concentration: 8–40 mg/L and time: 15–75 min). The maximum fluoride removal is obtained as 96.87% (predicted) and 95.40% (experimental) for the optimized process parameters, initial concentration of 32 mg/L, 0.8 A current, 60 min, and 60 RPM of rotating speed. Kinetic analysis reveals that the removal process adheres to a second-order kinetic model, suggesting that the rate of fluoride removal is dependent on the concentration of fluoride ions present. Isothermal studies indicate that the effective sorption of fluoride onto the generated flocs follows a sips isotherm. The optimal cost analysis is carried out to determine the operational cost as 0.256 USD/m3 for F removal of 93.49% at initial concentration 24 mg/L, time 50 min, current 0.7 A, and rotation 70 rpm and presenting a cost-effective solution for fluoride mitigation. Further, characterizations of the resultant sludge through X-Ray Diffraction (XRD), Fourier-Transform Infrared Spectroscopy (FTIR), and the Toxicity Characteristic Leaching Procedure (TCLP) confirmed the safe disposal potential of the sludge. The findings show a promising approach for fluoride removal, combining high efficiency, economic viability, and environmental safety.

Fluoride Removal from Aqueous Solutions by Using Super-Adsorbents of Chitosan/Orange Peels/Activated Carbon@MgO: Synthesis, Characterization, and Adsorption Evaluation

Exposure to excessive concentrations of fluoride in potable water is harmful to human health; therefore, its limitation is deemed necessary. Among the commonly applied technologies, adsorption is selected, as it is a highly effective, simple, and economically efficient treatment. In the present study, several combinations of chitosan (CS), orange peels (OP), activated carbon (AC), and MgO were synthesized and tested as adsorbents in order to find the most effective derivative for fluoride extraction. The impact of the adsorbent dosage, pH level, contact time, and initial concentration was investigated to assess the feasibility of the chitosan/orange peels/activated carbon@MgO composite. According to the results, the modification of chitosan with AC, OP, and MgO in a unique adsorbent (CS/OP/AC@MgO), especially in acidic conditions (pH 3.0 ± 0.1) by using 1.0 g/L of the adsorbent, demonstrated the highest efficiency in F removal, up to 97%. The pseudo-second (PSO) order model and Langmuir isotherm model fit better to the experimental results, especially for CS/OP/AC@MgO, providing a Qm = 26.92 mg/g. Thermodynamic analysis confirmed the spontaneous nature of the adsorption process. The structure and morphology of the modified OP/CS@AC-Mg were extensively characterized using BET, XRD, FTIR, and SEM techniques.

Double cross-linked chitosan sponge encapsulated with ZrO2/soy protein isolate amyloid fibrils nanoparticles for the fluoride ion removal from water

Fluoride ion pollution in water has become a serious threat to the water environment and human health. Adsorption is a promising means of fluoride removal, but it also faces challenges such as the difficult separation and recovery of powdered particles, the leaching of modified coatings from adsorbents, and the structural disintegration of macroscopic adsorbents. For addressing the above challenges, glutaraldehyde/polyvinyl alcohol co-crosslinked ZrSAF/chitosan spongy composites (ZrS/GPCS) were prepared by utilizing encapsulation strategies and cross-linking. ZrS/GPCS-1, ZrS/GPCS-3 and ZrS/GPCS-4 were prepared due to the different amounts of cross-linking agents. The results showed that their fluoride ion adsorption capacities were 42.02, 44.44 and 39.84 mg/g, respectively. The removal of fluoride ions by ZrS/GPCS was maintained at >80 % in the pH range of 4–10. The addition of glutaraldehyde and polyvinyl alcohol affected the contact efficiency of fluoride ions with chitosan and ZrSAF, influencing the adsorption rate and adsorption effect. Glutaraldehyde, polyvinyl alcohol and ZrSAF improved the thermal stability, mechanical properties and structural integrity of chitosan matrix. Both the chitosan matrix and the internal ZrSAF played an important role in fluoride removal, and the removal mechanisms included electrostatic interaction, hydrogen bonding, and complexation.

Insights into the crucial role of pH to achieve the dual goals of efficient fluoride removal and resource recovery from the photovoltaic manufacturing wastewater

Fluoride-containing wastewater arose from the rapid development of photovoltaic manufacturing, and caused many environmental and health concerns. Chemical precipitation is commonly applied for fluoride removal, in which pH plays a crucial role while lacking systematic and in-depth research. In this study, the effect of pH on fluoride removal was investigated from both theoretical and experimental views, and the recovered precipitates with pH control were characterized. Theoretical analysis illustrated the quantitative relationship between reaction rate and pH, which indicated an optimal pH of about 8 for fluoride removal. This result was further validated by the batch and continuous experiments. In the batch experiments, the highest fluoride removal efficiency of 99.00 ± 0.01 % and lowest fluoride residual of 19.93 ± 0.16 mg/L were achieved at pH 8.00. In the continuous experiments, the fluoride residual was controlled under 10 mg/L with a fluoride removal rate of 2298.3 ± 0.5 kg F/(m3·d) in the optimal pH range of 6.95 to 8.47. The precipitate characteristics in terms of morphology, elements composition, and crystallization property showed a close correlation with reaction pH. Furthermore, a multidimensional system involving CaF2 content, precipitant saving, particle size, crystallinity, and fluoride residual was established to assess the fluoride removal and precipitate recovery with pH control. A neutral condition was recommended to achieve the above dual goals. This work provided systematical and deep insights into the pH role in fluoride removal and precipitates recovery, and could offer guidelines for the development of industrial fluoride-containing wastewater treatment.