Search

The Fenton process is used as a tertiary treatment to remove organic pollutants from the effluent of bio-treated pharmaceutical wastewater (EBPW). The optimal and most appropriate Fenton conditions were determined by an orthogonal array test and single-factor experiments. The removal of chemical oxygen demand (COD) was influenced by the following factors in a descending order: H2O2/Fe(II) molar ratio > H2O2 dosage > reaction time. Under the most appropriate Fenton conditions (H2O2/Fe(II) molar ratio of 1:1, H2O2 dosage of 120 mg L−1 and reaction time of 10 min), the COD and dissolved organic carbon (DOC) were removed with efficiencies of 62 and 53%, respectively, which met the national discharge standard (GB 21903-2008) for the Lake Tai Basin, China. However, the Fenton treatment was inadequate for removal of N compounds, and the removal of organic nitrogen led to an increment in N-NH3 from 3.28 to 19.71 mg L−1. Proteins and polysaccharides were completely removed, and humic acids (HAs) were partly removed with an efficiency of 55%. Three-dimensional excitation/emission matrix spectra (3DEEMs) indicated complete removal of fulvic acid-like substances and 90% reduction in the florescence intensity of humic acid-like substances. Organic pollutants with molecular weights (MW) > 10 kDa were completely removed, MW 5–10 kDa were degraded into smaller MW ones, and some low molecular weight acids (MW 0.1–1 kDa) were mineralized during the Fenton process. Some species, including pharmaceutical intermediates and solvents were detected by gas chromatography-mass spectrometry (GC-MS). The operational costs of the Fenton’s treatment were estimated to be 0.58 yuan RMB/m3 EBPW based on reagent usage and iron sludge treatment and disposal.

A rapid Fenton treatment at second-scale intervals was investigated for further removal of organic compounds in the effluent of bio-treated dyeing and finishing wastewater (BDFW). The decolorization kinetics was studied using a stopped-flow spectrophotometer (SFS) at second-scale intervals. A combined first-order model was found to fit well for the decrease of both methylene blue and rhodamine B in SFS as well as SCOD (soluble chemical oxygen demand) and DOC (dissolved organic carbon) in real BDFW in batch test during Fenton oxidation. A full-scale plant with treatment capacity of 400,000 m3·d−1 was designed and has been run continuously based on the results of the stopped-flow study to treat the effluent of BDFW using Fenton oxidation in 16 pipeline reactors, each with a volume of 6.9 m3 and 24 s of reaction time since 2014. The COD, SCOD and DOC decreased from 140, 110 and 35 mg·L−1 to 77, 71 and 26 mg·L−1 respectively, which can meet the latest strict discharge limitations. The natural fluorescent substances detected in the BDFW were completely removed. The main organic pollutants in the BDFW can be significantly reduced using both gas chromatography-mass spectrometry and ultrahigh-performance liquid chromatography-hybrid quadrupole time-of-flight mass spectrometry. The rapid Fenton reaction applied in pipeline reactors at second intervals has several advantages over the conventional Fenton’s process such as much shorter reaction time at second scale intervals, no need to build extra pH adjustment or reaction tanks, simple operation, low capital cost, etc.

Catalytic ozonation of organic pollutants from actual bio-treated dyeing and finishing wastewater (BDFW) with iron shavings was investigated. Catalytic ozonation effectively removed organic pollutants at initial pH values of 7.18–7.52, and the chemical oxygen demand (COD) level decreased from 142 to 70 mg·L −1 with a discharge limitation of 80 mg·L −1 . A total of 100% and 42% of the proteins and polysaccharides, respectively, were removed with a decrease in their contribution to the soluble COD from 76% to 41%. Among the 218 organic species detected by liquid chromatography-mass spectrometry, 58, 77, 79 and 4 species were completely removed, partially removed, increased and newly generated, respectively. Species including textile auxiliaries and dye intermediates were detected by gas chromatography-mass spectrometry. The inhibitory effect decreased from 51% to 33%, suggesting a reduction in the acute toxicity. The enhanced effect was due to hydroxyl radical ( OH) oxidation, co-precipitation and oxidation by other oxidants. The proteins were removed by OH oxidation (6%), by direct ozonation, co-precipitation and oxidation by other oxidants (94%). The corresponding values for polysaccharides were 21% and 21%, respectively. In addition, the iron shavings behaved well in successive runs. These results indicated that the process was favorable for engineering applications for removal of organic pollutants from BDFW.