A micro-electrolysis material (MEM) was successfully prepared from carbothermal reduction of blast furnace dust (BFD) and coke as raw materials in a nitrogen atmosphere. The MEM prepared from BFD had strong ability in removing methyl orange, methylene blue, and rose bengal (the removal rates of methyl orange and methylene blue were close to 100%). X-ray diffraction showed that the iron mineral in BFD was ferric oxide, which was converted to zero-valent iron after being reduced by calcination. Scanning electron microscopy showed that nano-scale zero-valent iron particles were formed in the MEM. In short, the MEM prepared from BFD can effectively degrade organic pollutants.
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Blast furnace dust (BFD) is discharged with blast furnace flue gas during the iron and steel smelting process, and is collected by dry bag dust removal. The BFD has fine and uneven particle size, and is composed mainly of iron oxide and carbon, as well as harmful impurities such as lead, zinc, and alkali metal oxides [1]. This solid waste will cause serious harm to the environment [2,3]. According to statistics, the annual output of BFD in China alone will exceed 20 million tons in [2], which contains a lot of valuable metals such as zinc and iron [4]. However, since the accumulation of lead, zinc, and other alkali metals will affect blast furnace smelting, it is difficult to recover the valuable metals in BFD [5]. Therefore, BFD cannot be recycled in large quantities. In addition, due to the small particle size of BFD, it is easy to be transported by wind, causing environmental pollution and damage to the ecological environment [6]. Therefore, it is very important to study the rational utilization of BFD.
In recent years, much research has been conducted on the application of BFD [7], including the recovery of valuable metals such as zinc, iron, and lead [8,9,10]. Other applications of BFD have also been studied, including the use of blast furnace slag and glass waste to prepare foamed glass-ceramics [11], and the use as a raw material to prepare geopolymers [12], black iron oxide pigment [13], catalysts [14], and catalytic ceramic fillers [4]. Therefore, it is of great significance to develop a suitable treatment process for efficient use of BFD.
Iron-carbon micro-electrolysis developed in Europe in the s is a low-cost, efficient, and environmentally-friendly method, and a promising wastewater treatment technology [15]. Its principle is to use the metal corrosion method to form a galvanic cell to treat wastewater. Iron-carbon micro-electrolysis is now used in many fields of wastewater treatment, including constructed wetland [16,17], pharmaceutical wastewater [18,19,20], petroleum wastewater, landfill leachate [21], ionic liquid wastewater [22], chemical wastewater [23,24], dye wastewater [25,26], and electroplating wastewater [27,28,29]. During the preparation of iron-carbon micro-electrolysis materials (MEMs), Fe0 and activated carbon are first uniformly mixed in a particular proportion and then immersed in wastewater to form a large number of microscopic primary cells [24,30]. The electrode reaction can be represented as follows [31,32,33]:
When the wastewater contacts with iron and carbon, the following electrochemical reactions occur:
anode: Fe 2e Fe2+, Eθ(Fe2+/Fe) = 0.44V
cathode: 2H+ + 2e 2[H]H2, Eθ(H+/H2) = 0V
When oxygen is present, the cathodic reaction is as follows:
O2 + 4H++ 4e 2H2O, Eθ(O2/H2O) = +1.23V
O2 + 2H2O + 4e 4OH, Eθ(O2/OH) = +0.40V
The above reactions show that the nascent Fe2+ produced by the anode and the [H] generated by the cathode have high chemical activity and can effectively destroy the carbon chains of organic pollutants [34], eventually forming CO2, H2O, and inorganic ions [35]. Fe3+ generated by Fe oxidation is gradually hydrolyzed to Fe(OH)3 colloidal flocculant, which can effectively adsorb and condense pollutants in water, enhancing the purification effect of wastewater [36,37,38]. Because the Fe-C micro-electrolysis system does not require additional power, it can effectively treat organic pollutant wastewater. Therefore, the Fe-C micro-electrolysis system has attracted growing attention in the treatment of organic pollutants.
In this work, we used BFD as the iron source and coke as the carbon source to prepare MEM from carbothermic reduction. This work is aimed to determine whether the waste generated in the smelting industry can be used to prepare MEM, and to evaluate the effect of the MEM on the dye degradation. Results show that the MEM prepared from BFD can rapidly degrades azo dyes, and is a treatment process with great prospects and good treatment effect on wastewater decolorization. Then, the structure and morphology of the material were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the possible decolorization mechanism was discussed by ultraviolet spectroscopy.
The application of ironcarbon microbial cell activated sludge (ICMC-AS) was carried out in a membrane bioreactor (MBR) processor to treat wastewater from an integrated railway station. Results showed that the chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) removal efficiencies of the original MBR processor increased from 80%, 30%, and 10% to 92%, 93.5%, and 92%, respectively. Further research showed that the combined sewage treatment system also had a strong impact resistance ability. The combined sewage treatment system ran stably when the COD, TN, and TP concentrations changed greatly. The in-depth analysis of the reaction process and reaction rate of the combined sewage treatment system revealed that the combined system is dominated by COD removal with high nitrogen removal efficiency. The removal rate constants of various pollutants were in the order: K COD (0.647 ± 0.017) > K N O 3 N (0.416 ± 0.044) > K N H 4 + N (0.275 ± 0.014) > K TN (0.258 ± 0.083). Calculations of the energy saving and carbon emission reduction of the combined system showed that the systems annual carbon emission reduction could reach more than 388,203.55 kg CO 2 e, which remarkably improves the carbon emission reduction effect and obtains a good green effect. The results indicate that adding ICMC-AS to the MBR processor for combined wastewater treatment can substantially improve the efficiency of wastewater treatment and obtain better energy-saving and emission-reducing effects. This combined application provides an effective way for the transformation and upgrading of small- and medium-scale water treatment systems.
The basic principle of wastewater treatment by activated sludge is based on a series of electrochemical and microbial reactions, such as microelectrolysis and electronic exchange (between different microorganisms, between microorganisms and various organic or inorganic substances, and between various substances) in the water formed by ironcarbon galvanic cells. A large number of studies have shown that microelectrolysis has a remarkable degradation effect on refractory substances in sewage treatment (Deng et al., a). However, the application mechanism and removal efficiency of biochemical water treatment under the action of microelectrolysis are not clear because of the complexity of the microelectrolysis process. Current research on microelectrolysis wastewater treatment focuses on iron and carbon microelectric decontamination technologies. For example, Deng et al. developed a microelectrolytic process coupled with microbial nitrogen removal, which is a contact oxidation process based on the loading of microelectrolytic biological carrier formed by mixing Fe0 and activated carbon. The process removes nitrogen under micro-oxygen condition. The NH4+-N and TN removal efficiencies of this process were 92.6% and 95.3%, respectively (Deng et al., a). Hu et al. developed an iron-rich substrate (IRS) based on ironcarbon microelectrolysis that can be used for sediment and overlying water remediation. NH4+-N, PO43-P, organo-N, organo-P, TN, and total phosphorus (TP) in the overlying water were reduced by 48.6%, 97.9%, 34.2%, 67.1%, 53.2%, and 90.4%, respectively, by IRS during the 90 day long-term restoration. Moreover, NO3-N, NH4+-N, and organic N in sediments were reduced by 98.5%, 26.5%, and 6.3%, respectively (Hu et al., ).
Engineering applications are mostly carried out by iron and carbon microelectrolysis combined with biochemical decontamination technology. For example, Qi et al. applied microelectrolysis combined with sequencing batch reactor process to treat oxytetracycline production wastewater. When the influent chemical oxygen demand (COD) was 500 mg/L, the average COD removal rate increased from 76.1% to 94.4% (Qi et al., ). Microelectrolysis combined with expanded granular sludge bed and anaerobic/oxic system was used to treat oxytetracycline production wastewater. The oxytetracycline removal rate in the microelectrolysis reaction cell reached more than 95% (Wu et al., ).
In this study, ironcarbon microbial cell activated sludge (ICMC-AS) was formed by implanting ironcarbon-based materials into activated sludge microbial mass. ICMC-AS + membrane bioreactor (MBR) process was used for wastewater treatment in an integrated railway station. In order to solve the pollution problem of low nitrogen, phosphorus and other refractory elements in the original MBR reactor. The reaction principle of ICMC-AS is shown in Equations 14. The operation law of the combined processing system was obtained by studying its operation efficiency and parameters. The application mechanism of biochemical water treatment under the action of microelectrolysis was clarified through in-depth analysis of the reaction process and mechanism of the ironcarbon-based microelectrolysis wastewater treatment system. This study provides an effective way for the transformation and upgrading of small- and medium-scale water treatment systems. It also provides technical support and research data basis for the application of microelectrolysis in sewage treatment technology.
FeFe2++2e;E0Fe2+/Fe=0.44V(1)Fe2+Fe3++e;E0Fe3+/Fe2+=0.77V(2)H2O+eH+OH,E0H+/H=0.00V(3)2H2O+2eH2+2OH,E0H+/H=0.00V(4)The main body of the sewage treatment equipment is an integrated MBR reactor. Raw sewage was used to discharge wastewater from a comprehensive railway station, which consists of a railway passenger station, a large warehouse area, and related supporting facilities. The water quality indexes were COD levels of 100400 mg/L, NH4+-N concentrations of 15 45 mg/L, TN concentrations of 2060 mg/L, and TP concentrations of 26 mg/L.
As shown in Figure 1 1) sewage from the integrated railway station was collected through the pipeline to the grid pool of the sewage treatment plant. Inorganic suspended matter in the sewage was removed through a thick and fine grid to reduce the wear on the subsequent pipelines and equipment. The effluent enters the catchment pool. As shown in Figure 1 2) A large number of facultative aerobic bacteria are contained in the facultative MBR system and can degrade organic matter in sewage by the dual action of microelectrolysis and facultative bacteria metabolism to degrade macromolecular organic pollutants into small molecular organic matter, which are eventually oxidized and decomposed into stable inorganic substances. Such as carbon dioxide and water. Moreover, power consumption is reduced, because the generation of facultative bacteria does not need the guarantee of dissolved oxygen (DO). The main function of aeration in a sewage treatment system is to scour and shock membrane filaments, and the DO produced can be used to oxidize a part of the small molecular organic matter and maintain the DO value of the effluent to ensure the normal microbial metabolism in the combined MBR system with concurrent oxygen microelectrolysis.
FIGURE 1
FIGURE 1. ICMC-AS combined MBR device schematic diagram and process flow chart. 1) Flow chart of FeC microelectrolysis combined with MBR process. 2) Schematic diagram of ICMC-AS combined MBR device.
The design scale of the combined treatment system is 400 m3/day, the design total sludge age is infinite, the organic residual sludge discharge is nearly zero discharge, the mixed liquid concentration (MLSS) is mg/L, and the sludge load is 0.02 0.10 kg COD/(kg MLSS·day).
The ironcarbon-based material consisted of 40%50% elemental iron powder (300 mesh), 35%42% activated carbon powder (200 mesh), 6%8% metal catalyst (made of various metals), 5%8% adhesive, and foaming agent, etc. The materials were mixed evenly to prepare 1 2 cm balls, which were dried at 105 C for about 2 h in a drying oven, preheated at 600 C for half an hour in a muffle furnace, and heated at C for 3 h. After annealing and cooling, the balls were crushed and sifted to retain particles below 150 mesh. The time between production and use should not be too long and should be suitable for real-time production before use to ensure the activity of iron powder and avoid excessive oxidation.
The wastewater treatment efficiency of the new technology was determined by detecting the water quality indexes (CODCr, NH4+, NO3, NO22-, TP, and TN) in and out of the MBR reactor and comparing with the corresponding indexes of the original MBR reactor without ICMC-AS. CODCr was determined by potassium dichromate method, NH4+ was determined by sodium chlorite spectrophotometry, NO3 was determined by phenol disulfonic acid spectrophotometry, NO22 was determined by N-(1-naphthol)-ethylenediamine spectrophotometry, and TP was determined by potassium persulfate oxidation and ultraviolet spectrophotometry. TN is the sum of the values of NH4+, NO3, and NO22.
Carbonnitrogen reaction rate was determined and the reaction characteristics of the combined process were defined by detecting the concentration changes of COD, NH4+-N, NO3-N, and NO2-N during the operation of the MBR reactor (sampling every 30 min). The carbonnitrogen reaction rate was calculated by the Origin software.
Energy saving and carbon emission were estimated from three aspects: power consumption, water consumption, and drug consumption. Power consumption was converted according to the removal rate of the major pollutant (TN) and the increase rate. Water consumption only included the backwashing water. Other supporting water was relatively small, and water condition changed greatly; therefore, it was not measured. Carbon emissions were calculated on the basis of CO2.
The data shown in Figure 2 1) show that the COD of the influent municipal sewage varies at 112328 mg/L without regularity, and a large change in COD value will have a load impact on the water treatment system (Vleeschauwer et al., ). Studies have shown that such a load impact will often have a great impact on the water treatment system (Yadu et al., ). Experimental data show that the sewage treatment system formed a larger organic shock load, the stable effluent COD value was between 19 and 43 mg/L, and the water COD and effluent COD values had a significant positive correlation. However, the ratio changed, which allowed the sewage treatment system to have a good performance and strong load impact resistance. Compared with the original MBR system without ICMC-AS, the COD removal rate of the combined system increased from 80% to 92%.
FIGURE 2
FIGURE 2. Changes in water quality indicators in the combined sewage treatment system. 1) Changes in COD concentration. 2) Changes in TN and NH4+-N concentrations. 3) Changes in TP concentration.
As shown in Figure 2 2), the NH4+-N value measured at the inlet in the small test fluctuated greatly between 16 and 42 mg/L, and the TN value was between 2 and 55 mg/L, resulting in the large load impacts of NH4+-N and TN on the sewage treatment system. The load impacts of NH4+-N and TN loads have great influence on water treatment system (Meng et al., ). The NH4+-N and TN values measured at the outlet were maintained at about 23 mg/L, indicating that the sewage treatment system has a strong ability to resist the load impacts of NH4+-N and TN. In addition, the NH4+-N and TN removal rates were about 93.5% and 94%, respectively, which are not much different from the removal rates in the laboratory. This finding indicates that the removal capacities for NH4+ and TN in the sewage treatment system were strong, and the current concentrations of NH4+ and TN did not reach the treatment limits. Additionally, the results show that the sewage treatment system has strong adaptability and adjustment ability and can maintain efficient nitrogen pollutant removal ability under a large load shock. Compared with the original MBR system without ICMC-AS, the NH4+-N and TN removal rates increased from 40% and 30% to 93% and 93.5%, respectively, in the combined system.
As shown in Figure 2 3), the sewage treatment system has a good removal effect. TP values oscillated between 2 and 6 mg/L and were maintained at 0.3 mg/L after being treated by the sewage treatment system. This result indicates that the system had a stable treatment capacity for the TP of municipal sewage between 2 and 6 mg/L (most municipal sewage is within this range), and its removal rate was 92.58% on average. Compared with the original MBR system without ICMC-AS, the TP removal rate of the combined system increased from 10% to 92%.
As shown in Figure 3 1), COD was removed by rapid consumption within the first 120 min, and the value decreased from 400 mg/L to 100 mg/L. NH4+-N decreased from 20 mg/L to 2.32 mg/L within 270 min, and NH4+-N decreased more slowly at 40 60 and 90 120 min. The DO values in these two periods oscillated between 0.2 and 0.3 mg/L, indicating that the biochemical reaction of the system was very violent between 0 and 120 min, which made the DO values hover between 0.2 and 0.3 mg/L and inhibited NH4+-N decomposition. However, NO3-N concentration decreased from 5 mg/L to 2.81 mg/L between 0 and 40 min, increased from 2.58 mg/L to 2.89 mg/L between 40 and 180 min, and gradually decreased to 0.65 mg/L between 180 and 360 min. This finding is because the concentration change of NO3-N is affected by nitrification and denitrification reactions, as well as the biochemical reactions of other elements (such as the biochemical absorption of iron and carbon) (Xing et al., ). Therefore, during the first 040 min, NO3-N gradually entered the adsorption plane of various reactions and participated in various reactions. Therefore, its value was rapidly reduced to 2.81 mg/L. When these participating reactions reached saturation or equilibrium state, it reflects the comparison between the rates of nitrification reaction (NO3-N generation) and denitrification reaction (NO3-N transformation and removal) (Deng et al., b). When the rates of nitrification and denitrification reactions reach equilibrium, the value of NO3-N will keep oscillating within a certain numerical range. However, when the denitrification reaction is larger than the nitrification reaction, the value of NO3-N will gradually decrease. In this case, NO2-N is usually seen as an intermediate product in the conversion of NH4+-N to NO3-N (Deng et al., b). NO2-N accumulated gradually from 0 mg/L to 2.21 mg/L at 060 min, decreased to 0.61 mg/L at 4090 min, accumulated gradually accumulated from 0.61 m/L to 1.57 mg/L at 90240 min, and then decreased to 0.35 mg/L at 240360 min. In the whole process, the value of NO2-N experienced two accumulation processes. More complex changes occurred. This change law does not accord with the characteristics of synchronous nitrification and denitrification or short-cut nitrification (Jiaohui et al., ; Wang et al., ; Tong et al., a; Tong et al., b). Therefore, based on the analysis of the change values of TN and DO, COD, NH4+-N, NO3-N, NO2-N, and DO are co-changing according to a certain correlation. DO showed periodic oscillations and repeated changes during the operation of the system. The changes in DO can be divided into three stages. In the first stage, the operation time of the treatment system was between 0 and 120 min, and the DO value in this period changed between 0.1 and 0.4 mg/L. In the second stage, the operation time of the treatment system was between 120 and 270 min, and the DO value in this period varied between 1.0 and 1.4 mg/L. In the third stage, the operation time of the treatment system was between 270 and 360 min, and the DO value in this period varied between 1.8 and 2.3 mg/L.
FIGURE 3
FIGURE 3. Process changes of COD, NH4+-N, NO3-N, NO2-N, and TN in the operating cycle. 1) Process changes of COD, NH4+-N, NO3-N, NO2-N, and TN in the operating cycle. 2) Process changes of COD, NH4+-N, NO3-N, and TN removal rates in the operating cycle.
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As shown in Figure 3 2), the change rate of the NO3-N process value was close to that of COD at 040 min, indicating that the process of NO3-N reaction during this period was equally dramatic. On the one hand, the reason is that many biochemical reactions of microorganisms in the system require the participation of NO3-N. On the other hand, heterotrophic denitrification bacteria at this stage have sufficient organic carbon sources and a large amount of oxygen to efficiently carry out heterotrophic denitrification and consume NO3-N. At 40180 min, the NO3-N process value hardly changed and was in a relative equilibrium state because of the lack of relative oxygen and the indominance of the number of relative denitrifiers in the whole system. However, from the analysis of TN removal rate, the overall TN removal rate was maintained at a relatively high growth level. Moreover, the change rates of the decomposition and process values of NH4+-N were also maintained at relatively high levels, which indicates that the nitrification and denitrification reactions were maintained at a relatively high dynamic balance. At 180360 min, the change rate of the NO3-N process value was relatively large, and the COD value dropped to 57 mg/L, which made the organic carbon source become relatively short, and the NO3-N reaction process was transferred into the ICMC-AS. At this time, the organic carbon source materials (such as extracellular polymers, etc.) stored in ICMC-AS can be combined with the sufficient aerobic environment outside ICMC-AS to carry out heterotrophic denitrification, and the electron supply of ICMC-AS can be combined with the anoxic, facultative, and aerobic regions of MBR to carry out different degrees of autotrophic denitrification (Adav and Lee ; Pellicer-Nacher et al., ). Thus, an efficient denitrification reaction with a change rate similar to the process value of NH4+-N can be achieved.
As shown in Figure 4, the reaction rate constants of each substance were obtained by fitting the COD, NH4+-N, NO3-N, and TN removal efficiencies. Among them, the KCOD (0120 min) was 0.647 ± 0.017, which is the maximum reaction rate constant of each substance, and the minimum value of KTN was 0.258 ± 0.083. If only the conversion of NH4+-N into NO3-N under aerobic condition was considered, the converted KNO3N will be about 0.416 ± 0.044, but the actual conversion to NO3-N is not only the ammonification reaction of NH4+-N. The actual value of KNO3N will be higher than 0.416. Ammonification reaction is the main way to convert NH4+-N to NO3-N; thus, other transformation ways are greatly affected by the reaction conditions. Here, we only calculated the NH4+-N ammonification reaction after weighted estimation. According to the size of the reaction rate constant, the reaction rates were in the order: KCOD (0.647 ± 0.017) > KNO3N (0.416 ± 0.044) > KNH4+N (0.275 ± 0.014) > KTN (0.258 ± 0.083). Therefore, the combined application system is a wastewater treatment system with high nitrogen removal efficiency dominated by COD removal. The removal rates of various pollutants were in the order of: COD > NO3-N > NH4+-N > TN.
FIGURE 4
FIGURE 4. Carbon and nitrogen removal rates of the combined sewage treatment system. 1) TN rate fitting; 2) COD rate fitting; 3) NH4+-N rate fitting; 4) NO3-N rate fitting.
Membrane contamination is inevitable during the operation of the combined system. The system stops the sewage treatment operation and starts the membrane cleaning operation when the membrane pressure difference reaches 50 kPa. The membrane cleaning system adopts full automatic control. The membrane pressure difference of the original MBR system reached 50 kPa between 5 and 7 days, whereas that of the combined system reached 50 kPa between 7 and 10 days. This finding indicates that the combined system effectively mitigated the membrane contamination. Compared with the original MBR system, the sludge settling performance of the combined system was remarkably improved, and the settling performance of the combined system can reach the settling effect of the original system (30 min) in 5 min.
The sewage treatment scale of the railway station is 3,000 t/day, including six lifting pumps with a total operating power of 9 kW and six MBR wastewater processors with a total operating power of 99 kW. This scale translates into a daily power consumption of 1,903.2 kWh. According to the TN removal rate, which increased by three times conversion, a total of .8 kW h/day energy saving was achieved, and the annual electricity saving was 463,112 kWh. The amount of membrane-cleaning water was 159.6 t/time, and the drug dosage was 1.92 t/day. The average membrane-cleaning volume was reduced from 61 times per year to 43 times, with a reduction of 18 times, saving 2,872.8 t of water and 34.54 t of drug consumption. According to CO2 conversion, the annual reduction in electricity was 463,112 kWh, which corresponds to the carbon emission reduction of 363,542.92 kg CO2e; the water saved was 2,872.8 t, which corresponds to the carbon emission reduction of 482.63 kg CO2e; and the reduction in pharmaceutical dosage was 34.54 t, which corresponds to the comprehensive carbon emission reduction of 24,178 kg CO2e. Therefore, the annual carbon reduction of the combined system is at least 388,203.55 kg CO2e.
The results showed that ICMS-AS + MBR has a strong ability to resist the impacts of COD, NH4+-N, and TP hydraulic loads. The COD, NH4+-N, and TP values of raw water vary irregularly at 112.0328.0 , 16.042.0 , and 2.06.0 mg/L, respectively, whereas the COD, TN, and TP values of the combined system were all stable in the ranges of 19.243.3 , 2.13.4 , and 0.30.4 mg/L, respectively. This finding indicates that the combined system has good resistance to hydraulic load impact and has stable effluent quality. Compared with the original MBR system without ICMC-AS, the COD, TN, and TP removal efficiencies of the combined system increased from 80%, 30%, and 10% to 92%, 93.5%, and 92%, respectively.
The study of the operation efficiency and parameters of the combined system and the in-depth analysis of the reaction process and reaction rate of the ironcarbon microelectrolysis wastewater treatment system revealed that the combined system is a wastewater treatment system dominated by COD removal with high nitrogen removal efficiency. The removal rate constants of various pollutants were in the order: KCOD (0.647 ± 0.017) > KNO3N (0.416 ± 0.044) > KNH4+N (0.275 ± 0.014) > KTN (0.258 ± 0.083).
Compared with the original MBR system, the combined system had a considerably improved sludge settling performance and can reach the settling effect of the original system (30 min) in 5 min. This performance effectively mitigated membrane contamination in the combined system.
The above results indicate that adding ironcarbon microelectrolysis activated sludge to the MBR processor for combined wastewater treatment can enhance the efficiency of wastewater treatment and obtain better energy-saving and emission-reducing effects. This combined application provides an effective way for the transformation and upgrading of small- and medium-scale water treatment systems.
The original contributions presented in the study are included in the article/supplementary material, further inquiries can be directed to the corresponding authors.
All authors listed have made a substantial, direct, and intellectual contribution to the work and approved it for publication.
This work was funded by the Science and Technology Research Project of the Education Department of Jiangxi Province, China (No. GJJ).
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
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