Optimization of Calcium Fluoride Crystallization Process for Treatment of High-Concentration Fluoride-Containing Semiconductor Industry Wastewater.

This study utilized a fluidized bed reactor (FBR) for fluoride removal from high-concentration fluoride-ion-containing simulated semiconductor industry wastewater and recovered high-purity CaF2 crystals. The effects of hydraulic retention time (HRT), pH, Ca2+ to F- ratio, upflow velocity, seed size and seed bed height were investigated by performing lab-scale batch experiments. Considering fluoride removal and CaF2 crystallization efficiency, 5 h HRT, pH 6, seed height of 50 cm and [Ca2+]/[F-] ratio of 0.55 (mol/mol) were found to be optimum. The effect of the interaction between the important process parameters on fluoride removal was further analyzed using response surface methodology (RSM) experimental design. The results showed that all the individual parameters have a significant impact (p = 0.0001) on fluoride removal. SEM-EDX and FTIR analysis showed the composition of the crystals formed inside FBR. HR-XRD analysis confirmed that the crystalline structure of samples was mainly CaF2. The results clearly demonstrated the feasibility of silica seed material containing FBR for efficient removal and recovery of fluoride as high-purity calcium fluoride crystals.

Simultaneous removal of fluoride and phosphate from semiconductor wastewater via chemical precipitation of calcium fluoride and hydroxyapatite using byproduct of recycled aggregate.

Semiconductor wastewater with high concentrations of fluoride and phosphate is an environmental issue that cannot be ignored. Moreover, the byproduct of recycled aggregates, concrete fines, cannot be reused in concrete manufacturing, which is a key issue to address for the sustainable development of the concrete industry. The objective of this study was to tackle the crucial environmental issues of these two industries by developing concrete fines as an alternative material to treat semiconductor wastewater. The chemical precipitation of calcium fluoride and hydroxyapatite in the presence of concrete fines was determined as the mechanism underpinning the removal of fluoride and phosphate in wastewater. Owing to the wide range of contaminant concentration and solution pH and the possibility of multi-stage treatment, the effects of the initial contaminant concentration (F: 100-1000 mg/L; P: 20-200 mg/L) and solution pH (pH: 2-7) on the removal reactions were determined. The highest F and P removal percentages were more than 99%, and the final F and P concentrations met the effluent standard (F: 15 mg/L, P: 1.3 mg/L). The removal reactions of F and P are generally in competition, and the removal of F has priority over the removal of P. The pseudo-second-order model can describe the kinetics of the removal reactions well. The formation of fluorapatite can reduce the F concentration below the concentration achievable by CaF2 precipitation alone. Furthermore, using the byproduct of recycled aggregates instead of conventional chemicals to treat semiconductor wastewater is promising in terms of reducing CO2 emissions, and prospective applications are discussed. This study can lead to the development of a sustainable and clean process for semiconductor wastewater treatment using byproducts from the concrete industry.

Treatment of Semiconductor Wastewater Containing Tetramethylammonium Hydroxide (TMAH) Using Nanofiltration, Reverse Osmosis, and Membrane Capacitive Deionization.

As the semiconductor industry has grown tremendously over the last decades, its environmental impact has become a growing concern, including the withdrawal of fresh water and the generation of harmful wastewater. Tetramethylammonium hydroxide (TMAH), one of the toxic compounds inevitably found in semiconductor wastewater, should be removed before the wastewater is discharged. However, there are few affordable technologies available to remove TMAH from semiconductor wastewater. Therefore, the objective of this study was to compare different treatment options, such as Membrane Capacitive Deionization (MCDI), Reverse Osmosis (RO), and Nanofiltration (NF), for the treatment of semiconductor wastewater containing TMAH. A series of bench-scale experimental setups were conducted to investigate the removal efficiencies of TMAH, TDS, and TOC. The results confirmed that the MCDI process showed its great ability as well as RO to remove them, while the NF could not make a sufficient removal under identical recovery conditions. MCDI showed higher removals of monovalent ions, including TMA+, than divalent ions. Moreover, the removal of TMA+ by MCDI was higher under the basic solution than under both neutral and acidic conditions. These results were the first to demonstrate that MCDI has significant potential for treating semiconductor wastewater that contains TMAH.

Investigating the potential of ammonium retention by graphene oxide ceramic nanofiltration membranes for the treatment of semiconductor wastewater.

Ceramic membranes with high chemical and fouling resistance can play a critical role in treating industrial wastewater. In the present study, we demonstrate the fabrication of graphene oxide (GO) assembled ceramic nanofiltration (NF) membranes that provide effective ammonium retention and excellent fouling resistance for treating semiconductor wastewater. The GO-ceramic NF membranes were prepared via a layer-by-layer (LbL) assembly of GO and polyethyleneimine (PEI) on a ceramic ultrafiltration (UF) substrate. The successful fabrication of the GO-ceramic NF membranes was verified through surface characterization and pore size evaluation. We also investigated the performance of GO-ceramic NF membranes assembled with different numbers of bilayers for the rejection of ammonium ions. GO-ceramic NF membranes with three GO-PEI bilayers exhibited 8.4- and 3.2-times higher ammonium removal with simulated and real semiconductor wastewater, respectively, compared to the pristine ceramic UF substrate. We also assessed flux recovery after filtration using real semiconductor wastewater samples to validate the lower fouling potential of the GO-ceramic NF membranes. Results indicate that flux recovery increases from 39.1 % in the pristine UF substrate to 71.0 % and 90.8 % for the three- and ten-bilayers GO-ceramic NF membranes, respectively. The low-fouling GO-ceramic NF membranes developed in this study are effective and promising options for the removal of ammonium ions from semiconductor wastewater.

Removal of tetramethylammonium hydroxide (TMAH) in semiconductor wastewater using the nano-ozone H2O2 process.

In this study, we used a nano-ozone bubble to enhance the efficiency of the ozone/H2O2 process for the degradation of tetramethylammonium hydroxide (TMAH) found in semiconductor wastewater at high levels. The nano-ozone bubble significantly increased ozone mass transfer rate compared to that of the macro-ozone bubble. The half-life of nano-ozone bubbles was 23 times longer than that of the nano-ozone bubbles. Due to the high ozone mass transfer rate and its durability, the nano-ozone bubble increased the TMAH degradation rate compared to that of the macro-ozone. The addition of H2O2 significantly increased the TMAH degradation rate constant by OH production during the nano-ozone bubbles/H2O2 process. The optimum conditions for TMAH removal was 25 °C and pH 10. Within 90 min of the nano-ozone/H2O2 process, TOC removal was 65 % while 80 % of nitrogen was converted into nitrate (NO3-) with 95 % of TMAM removal. Decreases in acute (40-fold) and chronic (2-fold) toxicity were achieved after applying the nano-ozone/H2O2 process to TMAH containing wastewater. However, there was no significant chronic toxicity decrease during the nano-ozone/H2O2 process of TMAH.

Degradation of EDTA in H2O2 -containing wastewater by photo-electrochemical peroxidation.

Semiconductor wastewater currently contains H2O2 which is an important reagent in wafers cleaning. Recalcitrant organic pollutant such as EDTA are always present in this type of wastewater and may represent a threat for the environment. In this work, a new photoelectrochemical reactor is proposed to remove EDTA from H2O2 contaning wastewater. First, photolysis, electrochemical peroxidation and photo-electrochemical peroxidation were compared. The results showed that the removal efficiency decreases in the sequence: UV/H2O2 «EC/H2O2

Removal of fluoride, SDS, ammonia and turbidity from semiconductor wastewater by combined electrocoagulation-electroflotation.

Semiconductor industry effluents contain organic and inorganic pollutants, such as sodium dodecyl sulfate (SDS), fluoride and ammonia, at high levels which consists a major environmental issue. A combined EC-EF process is proposed as a post-treatment after precipitation for simultaneous clarification and removal of pollutants. In EC step, a hybrid Fe-Al was used as the soluble anode in order to avoid supplementary EC step. EC-Fe is more suitable for SDS removal; EC-Al is more suitable for fluoride removal, while EC with hybrid Al-Fe makes a good compromise. Clarification and ammonia oxidation were achieved in the EF step. Effects of anodic material, initial pH, current, anion nature, chloride concentration and initial pollutant concentration were studied. The final concentrations may reach 0.27, 6.23 and 0.22 mg L-1 for SDS, fluoride and ammonia respectively. These concentrations are far lower than the correspondent discharge limits. Similarly, the final turbidity was found 4.35 NTU which is lower than 5NTU and the treated water does not need further filtration before discharge. Furthermore, the EC-EF process proves to be sufficiently energy-efficient with less soluble electrode consumption.

Toxicity of tetramethylammonium hydroxide to aquatic organisms and its synergistic action with potassium iodide.

The aquatic ecotoxicity of chemicals involved in the manufacturing process of thin film transistor liquid crystal displays was assessed with a battery of four selected acute toxicity bioassays. We focused on tetramethylammonium hydroxide (TMAH, CAS No. 75-59-2), a widely utilized etchant. The toxicity of TMAH was low when tested in the 72 h-algal growth inhibition test (Pseudokirchneriellia subcapitata, EC50=360 mg L(-1)) and the Microtox® test (Vibrio fischeri, IC50=6.4 g L(-1)). In contrast, the 24h-microcrustacean immobilization and the 96 h-fish mortality tests showed relatively higher toxicity (Daphnia magna, EC50=32 mg L(-1) and Oryzias latipes, LC50=154 mg L(-1)). Isobologram and mixture toxicity index analyses revealed apparent synergism of the mixture of TMAH and potassium iodide when examined with the D. magna immobilization test. The synergistic action was unique to iodide over other halide salts i.e. fluoride, chloride and bromide. Quaternary ammonium ions with longer alkyl chains such as tetraethylammonium and tetrabutylammonium were more toxic than TMAH in the D. magna immobilization test.