Fate and distribution of phosphorus in coking wastewater treatment: From sludge to its derived biochar.

Due to the phosphorus (P) deficiency in coking wastewater, sufficient P needs to be provided in the treatment process to maintain biotic activity. However, most of the dosed P sources are transferred to the sludge phase out of the chemical equilibrium. After an in-depth investigation of P morphology changes in coking wastewater treatment, it is found that above 71.6 % P applied to the full-scale O/H/H/O (oxic-hydrolytic & denitrification-hydrolytic & denitrification-oxic) process for coking wastewater treatment is ended up in the sludge phase of the aerobic reactors in the forms of non-apatite inorganic phosphorus (NAIP). Theoretical simulations suggest that the P forms precipitates such as FePO4·2H2O, AlPO4·2H2O, MnHPO4 at pH < 7, and Ca5(PO4)3OH at pH > 7. Microbial utilization of P in coking wastewater treatment is swayed by precipitation, pH and sludge retention time (SRT). By pyrolysis treatment of the waste sludge at 700 °C, phosphoric substances in coking sludge are enriched and converted into Ca5(PO4)3OH, Ca5(PO4)3Cl, Ca3(PO4)2, etc. with apatite phosphorus (AP) accounting for 65.7 % of total phosphorus. Moreover, the heavy metals in biochar were below the national standard limits for discharge. This study shows that hazardous waste (coking sludge) can be transformed into bioavailable products (P-rich biochar) through comprehensive management of the fate of P. Combined with the O/H/H/O process, the mechanisms of phosphorus consumption in coking wastewater treatment are revealed for the first time, which will facilitate a reduced consumption of phosphorus and provide a demonstration for other phosphorus-deficient industrial wastewater treatment.

Evolution of biochemical processes in coking wastewater treatment: A combined evaluation of material and energy efficiencies and secondary pollution.

The application of advanced biological treatment technology results in improved coking wastewater (CW) effluent quality at lower material and energy input practiced by wastewater treatment plants. In wastewater treatment, the diversity of biological processes combinations affects the variety of microorganisms and biochemical reactions resulting in effluent quality. Four full-scale CW processes, anaerobic-anoxic-oxic (A/A/O), anoxic-oxic-hydrolytic-oxic (A/O/H/O), anoxic-oxic-oxic (A/O/O), and oxic-hydrolytic-oxic (O/H/O) were compared for their consumption of chemicals and energy, emissions of greenhouse gases, and excess sludge production. A new performance indicator combining the above mentioned parameters was proposed to comprehensively evaluate processes in capacity to CW. The O/H/O process showed stable and reliable operation with minimum chemicals cost and the average energy consumption, whereas A/A/O at its good performance in TN removal required a large amount of alkaline chemicals to maintain stability. Besides, a substantial addition of chemicals in A/A/O results in larger average amounts of inorganic sludge. Also, the A/A/O process with a single aerobic unit appeared to be incapable of energy saving when dealing with CW rich in nitrogen and poor in phosphorus. The process with dual aerobic units can achieve more complete carbon and nitrogen removal, which is related to the sequence of biochemical reactions. Diverse sequence combinations can create variation in HRT and DO, whereby contaminants proceed through distinct channels of degradation. In the comparative analysis of CWPIs, it could be seen that O/H/O is the biological treatment process with the least equivalent energy consumption input at present thus exhibiting promising application in CW treatment. The A/O/O and A/O/H/O combinations are good attempts of development; however, more energy-efficient operation modes have to be further investigated.

[Behavior and Degradation of Polycyclic Aromatic Hydrocarbons (PAHs) in Coking Wastewater of A/O2 and A/O/H/O Processes].

Polycyclic aromatic hydrocarbons (PAHs) are typical organic pollutants found in coking wastewater, and their behavior and reduction can be affected by different treatment processes. Based on these considerations, this study investigated the behaviors of PAHs in coking wastewater under A/O2 and A/O/H/O treatment processes, respectively. In order to evaluate variations in PAH removal under two different treatment processes, samples were taken from different treatment units for quantification of PAHs using gas chromatography-mass spectrometry. Results showed that PAHs were barely degraded in anaerobic tanks of either treatment process and accumulated much higher concentrations than in aerobic and hydrolytic tanks. While low molecular weight PAHs (LMW PAHs) in aqueous phase from anaerobic tanks were degraded effectively in aerobic tanks, high molecular weight PAHs (HMW PAHs) mostly accumulated in the sludge phase; these potentially pose a higher environmental risk and therefore need to be treated separately. Moreover, the A/O/H/O process showed higher degradation of PAHs bioavailability and higher removal effectiveness for PAHs with four or more benzene rings than the A/O2 process; this is attributed to the hydrolytic tank's ability to promote hydrolysis of macromolecular organic compounds and therefore improve biodegradability of PAHs. Comprehensive results from the study indicated that the A/O/H/O process is more advantageous for degradation of PAHs than the A/O2 process.

[Characteristic of Benzo[a]pyrene Anaerobic Degradation by Phenol Co-substrate and Microbial Communities from Two Types of Sludge].

Benzo[a]pyrene (BaP) is a typical representative of PAHs in coking wastewater and priority-controlled pollutants in the coking industry; its response characteristics with microorganisms and the methods to promote its degradation are worth studying. On the other hand, because the inoculated sludge for the adjustment and operation of newly-constructed coking wastewater treatment plants comes from municipal sludge or other coking plants, currently, the study of the microbial properties of different sludges', sludge availability, and the conditions that influence these properties are lacking. On account of the above perspectives, an experiment to study and compare the durability of municipal sludge and coking sludge, and their ability to degrade BaP was carried out. An anaerobic reactor was selected for the experiment and anaerobic-activated sludges were collected from a coking wastewater processing unit and a municipal wastewater plant. Then, 10 mg·L-1 of BaP alone and BaP with phenol as a co-metabolic carbon source was added to the coking and municipal sludge samples, respectively, for comparison experiments to study the microbial degradation of BaP and its dynamics. Moreover, high-throughput sequencing technology was also used to analyze the changes in the microbial community structure before and after the degradation experiment. The results showed that:① Both sludges were capable of degrading BaP, but municipal sludge showed a higher degradation efficiency than coking sludge; ② Adding phenol as co-substrate promoted the biodegradation of BaP in both sludges. When BaP was the sole carbon source, the half-life of BaP in the two sludges was 155.41 d and 116.3 d respectively. After the addition of phenol, the half-life was reduced to 81.25 d and 38.44 d, respectively; ③ According to the analysis of the microbial community structure, the community composition in both sludges changed markedly. Moreover, the microbial community in the municipal sludge showed a more evident change than that of the coking sludge. In the coking sludge, the dominant bacteria community changed a little after acclimation, most of the observed bacteria were previously reported common PAH-degrading strains. In contrast, the dominant bacteria community in the municipal sludge varied greatly after acclimation, and the most abundant bacteria were not common PAH-degrading strains. In addition, some frequently reported PAHs-degrading bacteria such as Bacillus sp., Pseudomonas, Achromobacter, and Sphingomonas sp., were identified in both the sludges and were present in high abundance. The results indicated that municipal sludge utilized BaP more actively than coking sludge; this phenomenon can be explained by the fact that municipal sludge contained a higher diversity of microbes that were involved in the degradation of BaP. Furthermore, the presence of phenol promoted the degradation of PAHs like BaP. Therefore, we proposed that the PAHs in coking sludge discharge might be reduced by the addition phenol and municipal wastewater.