Advanced treatment of coking wastewater by coagulation and zero-valent iron processes

Advanced treatment of coking wastewater was investigated experimentally with coagulation and zero-valent iron (ZVI) processes. Particular attention was paid to the effect of dosage and pH on the removal of chemical oxygen demand (COD) in the two processes. The results showed that ZVI was more effective than coagulation for advanced treatment of coking wastewater. The jar tests revealed that maximal COD removal efficiency of 27.5-31.8% could be achieved under the optimal condition of coagulation, i.e. 400mg/L of Fe(2)(SO(4))3 as coagulant at pH 3.0-5.0. On the other hand, the COD removal efficiency could be up to 43.6% under the idealized condition of ZVI upon 10 g/L active carbon and 30 g/L iron being dosed at pH 4.0. The mechanisms for COD removal in ZVI were dominated by coagulation, precipitation and oxidation-reduction. ZVI would also enhance the biodegradability of effluent by increasing BOD5/COD from 0.07 to 0.53. Moreover, some ester compounds could be produced in the reaction. Although ZVI was found more efficient than coagulation in eliminating low molecular weight (<2000 Da) compounds in the wastewater, there were still a few residual contaminants which could hardly be eliminated by either of the process.     

Zero-valent iron pretreatment for detoxifying iodine in liquid crystal display (LCD) manufacturing wastewater

This study investigated reductive transformation of iodine by zero-valent iron (ZVI), and the subsequent detoxification of iodine-laden wastewater. ZVI completely reduced aqueous iodine to non-toxic iodide. Respirometric bioassay illustrated that the presence of iodine increase the lag phase before the onset of oxygen consumption. The length of lag phase was proportional to increasing iodine dosage. The reduction products of iodine by ZVI did not exhibit any inhibitory effect on the biodegradation. The cumulative biological oxidation associated with iodine toxicity was closely fitted to Gompertz model. When iodine-laden wastewater was continuously fed to a bench-scale activated sludge unit, chemical oxygen demand (COD) removal efficiencies decreased from above 90% to below 80% along with a marked decrease in biomass concentration. On the other hand, the COD removal efficiency and biomass concentration remained constant in the integrated ZVI-activated sludge system. Respirometric bioassay with real iodine-laden LCD manufacturing wastewater demonstrated that ZVI was effective for detoxifying iodine and consequently enhancing biodegradability of wastewater. This result suggested that ZVI pretreatment may be a feasible option for the removal of iodine in LCD processing wastewater, instead of more costly processes such as adsorption and chemical oxidation, which are commonly in the iodine-laden LCD wastewater treatment facility.     

Performance evaluation of single-sludge reactor system treating high-strength nitrogen wastewater

In the single-sludge reactor system treating high-strength nitrogen wastewater (similar to anaerobically pretreated piggery wastewater), the NH4(+)-N removal efficiencies (98-82%) are higher than total nitrogen removal efficiencies (71-43%). The mixed liquor recycle ratio only imposes a slight effect on total nitrogen removal efficiency. The alkalinity change data could be used for monitoring and control of the reactor system. To evaluate the performance of the single-sludge reactor system, a simplified nitrification-denitrification model (with nitrification capacity, denitrification capacity, and denitrification potential concepts) and a graphically analytical technique are proposed. It turns out that ammonia nitrification and total nitrogen removal efficiencies are strongly dependent on the process load and reactor configuration, and an optimal operating condition requires a proper match between nitrification and denitrification.     

Adsorption of organic pollutants from coking and papermaking wastewaters by bottom ash

Bottom ash, a power plant waste, was used to remove the organic pollutants in coking wastewater and papermaking wastewater. Particular attention was paid on the effect of bottom ash particle size and dosage on the removal of chemical oxygen demand (COD). UV-vis spectra, fluorescence excitation-emission matrix (FEEM) spectra, Fourier transform infrared (FTIR) spectra, and scanning electron microscopic (SEM) photographs were investigated to characterize the wastewaters and bottom ash. The results show that the COD removal efficiencies increase with decreasing particle sizes of bottom ash, and the COD removal efficiency for coking wastewater is much higher than that for papermaking wastewater due to its high percentage of particle organic carbon (POC). Different trends of COD removal efficiency with bottom ash dosage are also observed for coking and papermaking wastewaters because of their various POC concentrations. Significant variations are observed in the FEEM spectra of wastewaters after treatment by bottom ash. New excitation-emission peaks are found in FEEM spectra, and the fluorescence intensities of the peaks decrease. A new transmittance band in the region of 1400-1420 cm(-1) is observed in FTIR spectra of bottom ash after adsorption. The SEM photographs reveal that the surface of bottom ash particles varies evidently after adsorption.     

An integrated technique using zero-valent iron and UV/H2O2 sequential process for complete decolorization and mineralization of C.I. Acid Black 24 wastewater

The zero-valent iron (ZVI) reduction succeeds for decolorization, while UV/H(2)O(2) oxidation process results into mineralization, so that this study proposed an integrated technique by reduction coupling with oxidation process in order to acquire simultaneously complete both decolorization and mineralization of C.I. Acid Black 24. From the experimental data, the zero-valent iron addition alone can decolorize the dye wastewater yet it demanded longer time than ZVI coupled with UV/H(2)O(2) processes (Red-Ox). Moreover, it resulted into only about 30% removal of the total organic carbon (TOC), which was capable to be effectively mineralized by UV/H(2)O(2) process. The proposed sequential ZVI-UV/H(2)O(2) integration system cannot only effectively remove color and TOC in AB 24 wastewater simultaneously but also save irradiation power and time demand. Furthermore, the decolorization rate constants were about 3.77-4.0 times magnitude comparing with that by UV/H(2)O(2) process alone.     

Treatment of groundwater polluted by arsenic compounds by zero valent iron

Batch experiments were carried out to study the kinetics and efficiency of inorganic arsenic removal by zero valent iron (ZVI) powder, and as well as the effects of pH, anions, and humic material (HM) on this process. Moreover, column experiment was conducted for 31 days to treat arsenate solution of 500 microg As/L using waste iron chippings as filling. Batch experiments showed that both arsenate and arsenite compounds could be removed efficiently from simulated groundwater by ZVI under aerobic and relative anaerobic conditions. Aerobic condition was favorable to arsenic removal especially for arsenate, while arsenite could be removed more rapidly than arsenate in relative anaerobic condition. Oxidation of arsenite to arsenate by iron species in aerobic environment was observed, which is thought to be an important pathway of arsenite removal. In an unsealed system, the removal efficiency of both arsenate and arsenite decreased at higher pH value. In a sealed system, acidic and alkaline condition seemed to be favorable for arsenate and arsenite removal, respectively. Phosphate and low concentration sulfate caused a decrease in arsenate removal, while high concentration sulfate as well as nitrate caused slight increase in arsenate removal. Presence of HM in solution slightly inhibited arsenic removal. Arsenic removal efficiency in column study was influenced by flow rate and work period of the column. More than 98% of arsenate could be removed stably with a hydraulic resident time of 2 h at last, and the effluent meet the drinking water standard.     

Evaluation of potential integration of entrapped mixed microbial cell and membrane bioreactor processes for biological wastewater treatment/reuse

The challenge of biological wastewater treatment process is the design and operation of effective retention of mixed microbial cells within the reactor. Entrapped mixed microbial cell (EMMC) technology is designed to entrap the mixed microbial cells in polymeric carriers; membrane bioreactor (MBR) process utilizes membrane sheets/fibers to effectively retain the biomass in the reactor. These two biotechnologies are considered potential alternatives for conventional biological treatment/reuse because of their capability of retaining high concentration of biomass in the reactor, or in other words increasing the solid retention time (SRT). The simultaneous removal of organics and nitrogen were investigated using a modified EMMC system design. The modified EMMC system demonstrated higher organic and nitrogen removal performance due to high SRT. Compared to single-stage MBR process operated at similar conditions, the modified EMMC system was able to achieve slightly lower organic removal, comparable nitrification, and higher total nitrogen removal. One limitation in applying an EMMC only treatment process regime for potential reuse of treated wastewater is that such an operation requires the removal of pathogens and large particles if disinfection and solid/liquid separation were not followed. The major challenge of MBR process to overcome is membrane fouling, and the high energy consumption associated with fouling control. The intrinsic features of EMMC process including high SRT, low, and stabilized effluent suspended biomass concentration may significantly reduce the chance and extent of membrane fouling; while the membrane filtration can further polish the effluent quality from EMMC process. Therefore, integrating MBR and EMMC is strongly recommended because it may be a ??break-through?? for solving the membrane fouling problem and in improving effluent quality for potential reuse.     

A pilot scale bioreactor using EMMC for carbon and nitrogen removal

A pilot scale (100 l reactor) of an entrapped mixed microbial cell (EMMC) process was fabricated and tested for simultaneous removal of carbon and nitrogen. Process performance, operational stability, and maintenance requirements were all determined. Two sources of actual agricultural processing wastewater containing a high concentration of chemical oxygen demand (COD) (about 800–1,000 mg/l) and domestic sewage containing a low concentration of COD (about 150–200 mg/l) were investigated in this study. Various HRT (hydraulic retention time) and aeration schedules were operated. It was found that soluble COD (SCOD) and soluble total nitrogen (STN) could be removed in the range of 40–70% and 20–90%, respectively, for domestic sewage depending on the operational conditions provided. For agricultural processing wastewater, removal efficiencies of SCOD and STN are 89–91% and 60–75%, respectively, depending on the HRTs and aeration schedules applied. Economic evaluation for the application of domestic sewage was conducted. It was found that at an HRT of 6 h with 24 h of aeration it costs U.S.$1.75 for the treatment of 1,000 gal/day (3.8 m³/day). It is apparent that the EMMC process is technically feasible for simultaneous removal of carbon and nitrogen under the operation of an alternated schedule of the aeration in one single bioreactor. Ultimately, it can replace or upgrade the existing conventional wastewater treatment plant by combining the secondary and tertiary wastewater treatment plant in one bioreactor and provides simple maintenance and operation. This will also assist in providing the high quality of treated effluent meeting current and future environmental regulation for reuse. Electronic Publication     

膨胀石墨负载零价铁的合成及其对水中Pb(II)去除效果与机制

以网络状孔型结构发达的膨胀石墨(EG)为载体, 采用化学沉积法制备负载零价铁(ZVI)的膨胀石墨(EG-ZVI)。利用SEM、XRD、FT-IR及XPS等对负载及反应前后的EG-ZVI进行表征, 探索了EG-ZVI对铅离子(Pb(II))的处理效果并对其反应产物及机理进行了分析。结果表明: 亚微米级ZVI成功负载到EG表面; 相比ZVI, EG-ZVI对Pb(II)的去除能力提升明显; EG-ZVI去除Pb(II)主要是吸附和还原作用的共同结果, 该过程符合一级动力学模型, 且控制步骤为化学反应过程。其还原过程是由负载在EG表面的ZVI腐蚀提供电子还原Pb(II)生成铅单质, 并进一步生成铅氧化物与氢氧化物; EG-ZVI能弥补ZVI在反应过程中生成惰性层导致去除效率低的不足, 使其在Pb(II)废水的实际修复中具有较高的应用前景。     

Butane extraction of model organic pollutants from water

In this study, n-butane (n-C(4)H(10)), a by-product of the oil refining process, was used as the extractant to remove various model organic pollutants including halogenated hydrocarbons, phenols and aromatic compounds from aqueous matrices. The presence of salt, inorganic acid and dissolved organic materials in the aqueous matrix were found to have little influence on the removal efficiency. High removal efficiencies are readily achievable for a great number of organic pollutants. The removal efficiencies for hydrophobic pollutants were greater than 90% for a single stripping stage for pollutants with a distribution constants (K(D)) greater than 45 and for a n-butane to aqueous phase ratio of 1-5. Results were also reported for the removal of residual butane in treated effluent by combinations of depressurization, air stripping and elevating operating temperature.     

Evaporation and air-stripping to assess and reduce ethanolamines toxicity in oily wastewater

Toxicity from industrial oily wastewater remains a problem even after conventional activated sludge treatment process, because of the persistence of some toxicant compounds. This work verified the removal efficiency of organic and inorganic pollutants and the effects of evaporation and air-stripping techniques on oily wastewater toxicity reduction. In a lab-scale plant, a vacuum evaporation procedure at three different temperatures and an air-stripping stage were tested on oily wastewater. Toxicity reduction/removal was observed at each treatment step via Microtox bioassay. A case study monitoring real scale evaporation was also done in a full-size wastewater treatment plant (WWTP). To implement part of a general project of toxicity reduction evaluation, additional investigations took into account the monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) role in toxicity definition after the evaporation phase, both as pure substances and mixtures. Only MEA and TEA appeared to contribute towards effluent toxicity.     

Confirming Pseudomonas putida as a reliable bioassay for demonstrating biocompatibility enhancement by solar photo-oxidative processes of a biorecalcitrant effluent

The performance of a sequencing batch reactor (SBR) seeded with aerobic granular sludge was studied. The lab-scale SBR treating domestic wastewater operated at a volumetric loading rate (VLR) of 0.75-3.41 kg COD/(m(3)d). The granule stability was related to the organic loading, and high loading would be favorable for granule stability. Analysis of typical cycle showed that granular sludge had good ability to simultaneously remove nitrogen and phosphorus. Most organic substances were removed at the anaerobic stage. At the aerobic stage, simultaneous nitrification and denitrification (SND) happened with phosphorus absorption. The SBR had good removal performance for organic matter and phosphate. However, the total nitrogen (TN) removal performance was ordinary, with average removal efficiency of about 52%. Batch experiments indicated that increases of influent C/N ratio and a large percentage of granule in the sludge were conducive for SND in SBR.     

Reduction of chromate from electroplating wastewater from pH 1 to 2 using fluidized zero valent iron process

Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO(4)(2-)) to trivalent chromium (Cr(3+)) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1-2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation of Cr(OH)(3(s)) to save the coagulant cost. (3) Higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. For influent chromate concentration of 418 mg/L as Cr(6+), pH 2 and ZVI dosage of 3g (41 g/L), chromate removal was only 29% with hydraulic detention time (HRT) of 1.2 min, but was increased to 99.9% by either increasing HRT to 5.6 min or adjusting pH to 1.5. For iron species at pH 2 and HRT of 1.2 min, Fe(3+) was more thermodynamically stable since oxidizing agent chromate was present. However, if pH was adjusted to 1.5 or 1, where chromate was completely removed, high Fe(2+) but very low Fe(3+) was present. It can be explained that ZVI reacted with chromate to produce Fe(2+) first and the presence of chromate would keep converting Fe(2+) to Fe(3+). Therefore, Fe(2+) is an indicator for complete reduction from Cr(VI) to Cr(III). X-ray diffraction (XRD) was conducted to exam the remained species at pH 2. ZVI, iron oxide and iron sulfide were observed, indicating the formation of iron oxide or iron sulfide could stop the chromate reduction reaction.     

Study of the aerobic biodegradation of coke wastewater in a two and three-step activated sludge process

A laboratory-scale biological plant composed of two aerobic reactors operating at 35 degrees C was used to study the biodegradation of coke wastewater. The main pollutants to be removed are organic matter, especially phenols, thiocyanate and ammonium nitrogen. The concentrations of the main pollutants in the wastewater during the study ranged between 922 and 1,980 mg COD/L, 133 and 293 mg phenol/L, 176 and 362 mg SCN/L and 123 and 296 mg NH(4)(+)-N/L. The biodegradation of these pollutants was studied employing different hydraulic residence times (HRT) and final effluent recycling ratios in order to minimize inhibition phenomena attributable to the high concentrations of pollutants. During the optimisation of the operating conditions, the removal of COD, phenols and thiocyanate was carried out in the first reactor and the nitrification of ammonium took place in the second. The best results were obtained when operating at an HRT of 98 h in the first reactor and 86 h in the second reactor, employing a recycling ratio of 2. The maximum removal efficiencies obtained were 90.7, 98.9, 98.6 and 99.9% for COD, phenols, thiocyanate and NH(4)(+)-N, respectively. In order to remove nitrate, an additional reactor was also implemented to carry out the denitrification process, adding methanol as an external carbon source. Very high removal efficiencies (up to 99.2%) were achieved.     

Multivariate analysis of a biologically activated carbon (BAC) system and its efficiency for removing PAHs and aliphatic hydrocarbons from wastewater polluted with petroleum products

The efficiency of a biologically activated carbon system for treating wastewater polluted with petroleum products was examined and the effects of process parameters on its efficacy were evaluated. In each experiment 17 alkylated and 19 non-alkylated polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPHs, C₁₀–C₄₀) were extracted using semipermeable membrane devices from wastewater before and after treatment. The acquired data during experiments were analyzed using principal component analysis (PCA). The treatment system robustly removed dissolved PAHs across the studied ranges of the process parameters, providing overall removal efficiencies of 96.9–99.7% for the sum of 36 PAHs. However, the major contributor to their removal was sorption rather than biodegradation, and despite the general efficiency of the process there was up to a 9-fold range in the sums of quantified PAHs in the effluents between experiments. Combinations of long process contact time (24 h) with high temperature (24 °C) and moderate oxygen concentration (6–7 mg O₂ L⁻¹) resulted in good removal of bioavailable PAHs. The removal of TPHs was more dependent on biological activities during the wastewater treatment, and consequently more dependent on the process parameters. In addition, small but significant proportions of PAHs were volatilized and released during the wastewater treatment.     

HEAVY METALS REMOVAL IN A RAPID INFILTRATION SAND COLUMN

Sand filtration has been used as a cost-effective tertiary treatment process for sewage and wastewaters. However, little information is available on the performance of the process for heavy metals removal. In this project, the effect of a rapid infiltration sand filtration system on the removal of total organic carbon (TOC) phosphorus, Cd, Cu, Pb, and Zn from a mixed industrial and domestic wastewater was evaluated. To facilitate observation of the system behavior under varied conditions, the influent samples were also subjected to extreme pH values. Further studies were conducted to determine the effects of calcium carbonate addition for heavy metals precipitation prior to application onto the sand column. The results revealed that sand filtration was remarkably successful in removing phosphorus from wastewater under all conditions. The data further confirmed that in a sand filtration process, the mechanism of phosphorus removal was mainly due to chemical precipitation. Under neutral pH conditions, TOC, Cd, and Cu, were removed in the order of 20%, and Pb, and Zn were about 35-40% removed. Addition of a chemical precipitant such as calcium carbonate increased the pollutant removal to about 50%. At pH values below 2.4 and above 11.0, the TOC and all the metals showed an increase in concentration in passing through the sand column.     

用集成膜过程对含油废水进行资源化回收利用处理

采用电渗析与超滤、微滤相结合的集成膜过程对含油废水进行了资源化回收利用处理,并对该工艺中电渗析脱盐过程的各项运行参数与分离效果之间的关系进行了讨论.在此基础上,为进一步改善出水水质,还对不同材料的超滤、微滤膜去除废水CODCr的效果作了相应的实验比较.     

Enhancement of electrokinetic remediation of hyper-Cr(VI) contaminated clay by zero-valent iron

This paper investigated the effectiveness of incorporating zero-valent iron (ZVI) into electrokinetic (EK) to remediate hyper-Cr(VI) contaminated clay (2497 mg/kg). A ZVI wall was installed in the center of the soil specimen and was filled with 1:1 (w/w) ratio of granular ZVI and sand. Results show that transport of H(+) is greatly retarded by the strong opposite migration of anionic chromate ions, whereupon a revered electroosmosis flow (EO) was resulted and alkaline zone across the specimen was developed promoting the release of Cr(VI) from the clay. Chromium removal was characterized by high Cr(VI) concentration occurred in the anolyte and the presence of Cr(III) precipitates in the catholyte. The Cr(VI) reduction efficiencies for the process without ZVI wall were 68.1 and 79.2% for 1 and 2V/cm, respectively. As ZVI wall was installed, the corresponding reduction efficiencies increased to 85.8 and 92.5%. The costs for energy and ZVI utilized in this process are US$ 41.0 and 57.5 per cubic meter for the system with electric gradient of 1 and 2V/cm, respectively. The role of ZVI wall effectively reducing Cr(VI) contamination and the operation simultaneous collection of Cr(VI) from the electrode reservoirs are two major advantages of this process.     

HEAVY METALS REMOVAL IN A RAPID INFILTRATION SAND COLUMN

ABSTRACT

Sand filtration has been used as a cost-effective tertiary treatment process for sewage and wastewaters. However, little information is available on the performance of the process for heavy metals removal. In this project, the effect of a rapid infiltration sand filtration system on the removal of total organic carbon (TOC) phosphorus, Cd, Cu, Pb, and Zn from a mixed industrial and domestic wastewater was evaluated. To facilitate observation of the system behavior under varied conditions, the influent samples were also subjected to extreme pH values. Further studies were conducted to determine the effects of calcium carbonate addition for heavy metals precipitation prior to application onto the sand column. The results revealed that sand filtration was remarkably successful in removing phosphorus from wastewater under all conditions. The data further confirmed that in a sand filtration process, the mechanism of phosphorus removal was mainly due to chemical precipitation. Under neutral pH conditions, TOC, Cd, and Cu, were removed in the order of 20%, and Pb, and Zn were about 35–40% removed. Addition of a chemical precipitant such as calcium carbonate increased the pollutant removal to about 50%. At pH values below 2.4 and above 11.0, the TOC and all the metals showed an increase in concentration in passing through the sand column.     

Improvement of COD and color removal from UASB treated poultry manure wastewater using Fenton's oxidation

The applicability of Fenton's oxidation as an advanced treatment for chemical oxygen demand (COD) and color removal from anaerobically treated poultry manure wastewater was investigated. The raw poultry manure wastewater, having a pH of 7.30 (+/-0.2) and a total COD of 12,100 (+/-910) mg/L was first treated in a 15.7 L of pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB reactor was operated for 72 days at mesophilic conditions (32+/-2 degrees C) in a temperature-controlled environment with three different hydraulic retention times (HRT) of 15.7, 12 and 8.0 days, and with organic loading rates (OLR) between 0.650 and 1.783 kg COD/(m3day). Under 8.0 days of HRT, the UASB process showed a remarkable performance on total COD removal with a treatment efficiency of 90.7% at the day of 63. The anaerobically treated poultry manure wastewater was further treated by Fenton's oxidation process using Fe2+ and H2O2 solutions. Batch tests were conducted on the UASB effluent samples to determine the optimum operating conditions including initial pH, effects of H2O2 and Fe2+ dosages, and the ratio of H2O2/Fe2+. Preliminary tests conducted with the dosages of 100 mg Fe2+/L and 200 mg H2O2/L showed that optimal initial pH was 3.0 for both COD and color removal from the UASB effluent. On the basis of preliminary test results, effects of increasing dosages of Fe2+ and H2O2 were investigated. Under the condition of 400 mg Fe2+/L and 200 mg H2O2/L, removal efficiencies of residual COD and color were 88.7% and 80.9%, respectively. Under the subsequent condition of 100 mg Fe2+/L and 1200 mg H2O2/L, 95% of residual COD and 95.7% of residual color were removed from the UASB effluent. Results of this experimental study obviously indicated that nearly 99.3% of COD of raw poultry manure wastewater could be effectively removed by a UASB process followed by Fenton's oxidation technology used as a post-treatment unit.