Phosphorus recovery from wastewater by struvite crystallization：Property of aggregates

Struvite crystallization is a promising method to remove and recover phosphorus from wastewater to ease both the scarcity of phosphorus rock resources and water eutrophication worldwide. To date, although various kinds of reactor systems have been developed, supporting methods are required to control the struvite fines flushing out of the reactors. As an intrinsic property, aggregation is normally disregarded in the struvite crystallization process, although it is the key factor in final particle size and therefore guarantees phosphorus recovery efficiency. The present study developed a method to analyze the characteristics of struvite aggregates using fractal geometry, and the influence of operational parameters on struvite aggregation was evaluated. Due to its typical orthorhombic molecular structure, struvite particles are prone to crystallize into needle or rod shapes, and aggregate at the corners or edges of crystals. The determined fractal dimension(Dpf) of struvite aggregates was 1.52–1.31, with the corresponding range of equivalent diameter(d0.5) at 295.9–85.4 μm. Aggregates formed in relatively low phosphorus concentrations(3.0–5.0 mmol/L) and mildly alkaline conditions(pH 9.0–9.5) displayed relatively compact structures, large aggregate sizes and high aggregation strength. Increasing pH values led to continuous decrease of aggregate sizes, while the variation of Dpfwas insignificant. As to the aggregate evolution, fast growth in a short time followed by a long steady stage was observed.     

Direct numerical simulation of the motion of circular pollutant particles in Newtonian fluid

An improved implementation of distributed multiplier/fictitious domain method is presented for the direct numerical simulation of particulate flow. The key improvement is to replace a finite-element triangulation for the velocity and a “twice-coarser“ triangulation for the pressure with a rectangular discretization for the velocity and pressure. For code validation, the sedimentation of a single particle in a twodimensional channel was simulated. The results showed that the simulation is independent of the mesh size as well as the time step. The comparison between experimental data and this simulation showed that our code can give a more accurate simulation on the motion of particlesthan previous DLM code. The code was then applied to simulate the sedimentation of 600 particles in a rectangular box. The falling course ispresented and discussed. At the same time, this simulation also demonstrates that the method presented in this paper can be used for solving the initial problems involving a lager number of particles exaclly with computing durations kept at acceptable levels.     

Effect of Ca:Mg ratio and high ammoniacal nitrogen on characteristics of struvite precipitated from waste activated sludge digester effluent

This study revealed the relationship between the presence of calcium impurities and ammoniacal nitrogen concentration upon crystallization of struvite. The research hypothesis was that the presence of both calcium and high concentrations of ammoniacal nitrogen(328–1000 mg/L) in waste activated sludge may influence the struvite quality and acid stability. Hence, we studied the impact of Ca:Mg ratio upon morphology, particle size, purity and dissolution of struvite, in the presence of varying levels of excess ammoniacal nitrogen. X-ray diffraction revealed that up to 31.4%amorphous material was made which was assigned to hydroxyapatite. Increasing the ammoniacal nitrogen concentration and elevation of the Mg:Ca ratio maximized the presence of struvite. Struvite particle size was also increased by ammoniacal nitrogen as was twinning of the crystals. Tests with dilute solutions of organic acid revealed the sensitivity of struvite dissolution to the physical characteristics of the struvite. Smaller particles(21.2 μm) dissolved at higher rates than larger particles(35.86 μm). However,struvite dissolved rapidly as the p H was further reduced irrespective of the physical characteristics. Therefore, addition of struvite to low p H soils was not viewed as beneficial in terms of controlled nutrient release. Overall, this study revealed that waste activated sludge effluent with high ammoniacal nitrogen was prospective for synthesis of high quality struvite material.     

Recovery of Cu(Ⅱ) from aqueous solution by induced crystallization in a long-term operation

The feasibility of copper recovery by induced crystallization in a long period(174 days) was investigated in a seeded fluidized bed reactor(FBR). The process was divided into 3 periods according to different influent conditions, and the period III was separated into III-a and IIIb due to the adjustment of the molar ratio of CO_3~(2-)concentration to copper concentration([CT]/[Cu~(2+)]). The removal efficiency could exceed 95% and the average effluent copper concentration decreased to 3.0 mg/L. The mean particle size of seed grains with copper crystals coating on, raised to 0.36 mm from initial 0.18 mm. During period III-a, the supersaturation exceeded 2.88 × 104, the removal efficiency decreased to 60%–80% and the particle size dropped to 0.30 mm, due to the generation of fines by homogeneous crystallization and seeds breaking. And the morphology of the crystals on the seed grains changed from rod-like to spherical which lead to the particle size decreasing. In period III-b,the supersaturation was modified by adjusting the molar ratio of [CT]/[Cu2+] to 1.2 from 2.The efficiency was back to 95% and the mean particle size grew to 0.36 mm at the end of IIIb, the crystals coating on the seeds turned back to rod-like products of good stability. This study illustrated that the copper salt crystal could keep on growing on the seed grains for over 150 days, the feasibility and controllability of copper recovery by induced crystallization process in FBR were satisfactory, even under the dramatic changes in influent conditions.     

Porous media grain size distribution and hydrodynamic forces effects on transport and deposition of suspended particles

The effects of porous media grain size distribution on the transport and deposition of polydisperse suspended particles under different flow velocities were investigated. Selected Kaolinite particles(2–30 μm) and Fluorescein(dissolved tracer) were injected in the porous media by step input injection technique. Three sands filled columns were used: Fine sand,Coarse sand, and a third sand(Mixture) obtained by mixing the two last sands in equal weight proportion. The porous media performance on the particle removal was evaluated by analysing particles breakthrough curves, hydro-dispersive parameters determined using the analytical solution of convection–dispersion equation with a first order deposition kinetics, particles deposition profiles, and particle-size distribution of the recovered and the deposited particles. The deposition kinetics and the longitudinal hydrodynamic dispersion coefficients are controlled by the porous media grain size distribution. Mixture sand is more dispersive than Fine and Coarse sands. More the uniformity coefficient of the porous medium is large, higher is the filtration efficiency. At low velocities, porous media capture all sizes of suspended particles injected with larger ones mainly captured at the entrance.A high flow velocity carries the particles deeper into the porous media, producing more gradual changes in the deposition profile. The median diameter of the deposited particles at different depth increases with flow velocity. The large grain size distribution leads to build narrow pores enhancing the deposition of the particles by straining.     

Production and application of anaerobic granular sludge produced by landfill

Sludge granulation is considered to be the most critical parameter governing successful operation of an upflow anaerobic sludge blanket and expanded granular sludge bed(EGSB)reactors.Pre-granulated seeding sludge could greatly reduce the required start- up time.Two lab-scale and a pilot-scale EGSB reactors were operated to treat Shaoxing Wastewater Treatment Plant(SWWTP) containing wastewater from real engineering printing and dyeing with high pH and sulfate concentration.The microbiological structure and the particle size distribution in aerobic excess sludge,sanitary landfill sludge digested for one year,and the granular sludge of EGSB reactor after 400 d of operation were analyzed through scanning electron microscopy (SEM) and sieves.The lab-scale EGSB reactor seeded with anaerobic sludge after digestion for one year in landfill showed obviously better total chemical oxygen demand (TCOD)removal efficiency than one seeded with aerobic excess sludge after cation polyacrylamide flocculation-concentration and dehydration.The TCOD removed was 470.8 mg/L in pilot scale EGSB reactor at short hydraulic retention time of 15 h.SEM of sludge granules showed that the microbiological structure of the sludge from different sources showed some differences.SEM demonstrated that Methanobacterium sp.was present in the granules of pilot-scale EGSB and the granular sludge produced by landfill contained a mixture of anaerobic/anoxic organisms in abundance.The particle size distribution in EGSB demonstrated that using anaerobic granular sludge produced by sanitary landfill as the seeding granular sludge was feasible.     

A pilot-scale study of cryolite precipitation from high fluoride-containing wastewater in a reaction-separation integrated reactor

Fluoride removal by traditional precipitation generates huge amounts of a water-rich sludge with low quality, which has no commercial or industrial value. The present study evaluated the feasibility of recovering fluoride as low water content cryolite from industrial fluoride-containing wastewater. A novel pilot-scale reaction-separation integrated reactor was designed. The results showed that the seed retention time in the reactor was prolonged to strengthen the induced crystallization process. The particle size of cryolite increased with increasing seed retention time, which decreased the water content. The recovery rate of cryolite was above 75% under an influent fluoride concentration of 3500 mg/L, a reaction temperature of 50℃, and an influent flow of 40 L/hr. The cryolite products that precipitated from the reactor were small in volume, large in particle size, low in water content, high in crystal purity, and recyclable.     

Computer simulation of the coagulation of suspended solids — The applicability of the Müller–Smoluchowski theory

The results of studies carried out using a computer programme simulating the coagulation of suspensions containing spherical sol particles and spherical coagulant particles are reported.The influence of the degree of dispersion of the system on the coagulation reaction kinetics was investigated. The obtained results of kinetic studies were tested in the light of classical Müller–Smoluchowski equations. The influence of the physical properties of the coagulant,such as size, density and mass, on the coagulation rate was tested. It was found that within the range described in this paper, the rate of the simulated coagulation process fulfils both the kinetic equation of a first-order reaction, and the kinetic equation of a second-order reaction.Within the tested range, a significant influence of the mass and size of the coagulant on the coagulation rate was ascertained. The kinetic Müller–Smoluchowski dependence is fulfilled in a broader range of the degree of dispersion, when the coagulant particle mass and the sol particle mass are equal. When the particle mass increases with an increase in the particle radius, the coagulation rate increases faster that it would result from the Müller's dependence.     

Aerobic granules cultivated and operated in continuous-flow bioreactor under particle-size selective pressure

A novel method based on the selective pressure of particle size （particle-size cultivation method, PSCM） was developed for the cultivation and operation of aerobic granular sludge in a continuous-flow reactor, and compared with the conventional method based on the selective pressure of settling velocity （settling-velocity cultivation method, SVCM）. Results indicated that aerobic granules could be cultivated in continuous operation mode by this developed method within 14 days. Although in the granulation process, under particle-size selective pressure, mixed liquor suspended solids （MLSS） in the reactor fluctuated greatly and filamentous bacteria dominated the sludge system during the initial operation days, no obvious difference in profile was found between the aerobic granules cultivated by PSCM and SVCM. Moreover, aerobic granules cultivated by PSCM presented larger diameter, lower water content and higher specific rates of nitrification, denitrifieation and phosphorus removal, but lower settling velocity. Under long term operation of more than 30 days, aerobic granules in the continuous-flow reactor could remain stable and obtain good chemical oxygen demand （COD）, NH4^＋-N, total nitrogen （TN） and total phosphorus （TP） removal. The results indicate that PSCM was dependent on the cultivation and maintenance of the stability of aerobic granules in continuous-flow bioreactors.     

Sulfide oxidation in fluidized bed bioreactor using nylon support material

A continuous fluidized bed bioreactor (FBBR) with nylon support particles was used to treat synthetic sulfide wastewater at different hydraulic retention time of 25, 50 and 75 min and upflow velocity of 14, 17 and 20 m/hr. The effects of upflow velocity, hydraulic retention time and reactor operation time on sulfide oxidation rate were studied using statistical model. Mixed culture obtained from the activated sludge, taken from tannery effluent treatment plant, was used as a source for microorganisms. The diameter and density of the nylon particles were 2-3 mm and 1140 kg/m³, respectively. Experiments were carried out in the reactor at a temperature of (30 ± 2)℃, at a fixed bed height of 16 cm after the formation of biofilm on the surface of support particles. Biofilm thickness reached (42 ± 3) μupm after 15 days from reactor start-up. The sulfide oxidation, sulfate and sulfur formation is examined at all hydraulic retention times and upflow velocities. The results indicated that almost 90%-92% sulfide oxidation was achieved at all hydraulic retention times. Statistical model could explain 94% of the variability and analysis of variance showed that upflow velocity and hydraulic retention time slightly affected the sulfide oxidation rate. The highest sulfide oxidation of 92% with 70% sulfur was obtained at hydraulic retention time of 75 min and upflow velocity of 14 m/hr.     

Removal of heavy metals and arsenic from a co-contaminated soil by sieving combined with washing process

Batch experiments were conducted with a heavy metals and arsenic co-contaminated soil from an abandoned mine to evaluate the feasibility of a remediation technology that combines sieving with soil washing.Leaching of the arsenic and heavy metals from the different particle size fractions was found to decrease in the order: 0.1,2–0.1,and 2 mm.With increased contact time,the concentration of heavy metals in the leachate was significantly decreased for small particles,probably because of adsorption by the clay soil component.For the different particle sizes,the removal efficiencies for Pb and Cd were75%–87%,and 61%–77% for Zn and Cu,although the extent of removal was decreased for As and Cr at 45%.The highest efficiency by washing for Pb,Cd,Zn,and As was from the soil particles 2 mm,although good metal removal efficiencies were also achieved in the small particle size fractions.Through SEM-EDS observations and correlation analysis,the leaching regularity of the heavy metals and arsenic was found to be closely related to Fe,Mn,and Ca contents of the soil fractions.The remediation of heavy metal-contaminated soil by sieving combined with soil washing was proven to be efficient,and practical remediation parameters were also recommended.     

Effects of temperature and composite alumina on pyrolysis of sewage sludge

An interactive dual-circulating fluidized bed system has been proposed in which the pyrolysis of sewage sludge(SS) and incineration of biomass proceed simultaneously, and alumina is used as the bed material and heat carrier. The alumina coated with biomass ash would mix with sewage sludge in the pyrolysis reactor of this device. It is important to know the influence of composite alumina(CA) on the pyrolysis progress. Sewage sludge was pyrolyzed in a fixed bed reactor from 400 to 600°C using CA as catalyst. The effects of temperature and CA additive ratio on the products were investigated. The product yields and component distribution of non-condensable gas were more sensitive to the change of temperature, and the maximum liquid yield of 48.44 wt.% and maximum Useable Energy of Liquid of 3871 k J/kg sludge were observed at 500°C with 1/5 CA/SS(mass ratio). The gas chromatography–mass spectrometry results showed that the increase of temperature enhanced devolatilization of organic matter and promoted cyclization and aromatization of aliphatics. The presence of CA could strengthen secondary cracking and interaction among primary products from different organic compounds, such as acid–amine condensation,and reduce the content of oxygenated compounds. When the CA additive amount exceeded a certain proportion, the aromatization was clearly strengthened. The effects of CA on decomposition of fatty acids and formation of aromatics were similar to that of temperature. This means that the reaction temperature could be lowered by introducing CA, which has a positive effect on reducing energy consumption.     

Phosphate recovery from anaerobic digester effluents using CaMg(OH)4

Dolomite lime(DL)(CaMg(OH)_4) was used as an economical source of Mg~(2+)for the removal and recovery of phosphate from an anaerobic digester effluent of a municipal wastewater treatment plant(MWWTP) wastewater. Batch precipitation results determined that phosphate was effectively reduced from 87 to less than 4 mg-P/L when the effluent water was mixed with 0.3 g/L of DL. The competitive precipitation mechanisms of different solids in the treatment system consisting of Ca~(2+)–Mg~(2+)–NH_4~+–PO_4~(3-)CO_3~(2-)were determined by comparing model predictions with experimental results. Thermodynamic model calculations indicated that hydroxyapatite(Ca_(10)(PO_4)_6(OH)_2), Ca_4H(PO_4)_3?3H_2O, Ca_3(PO_4)_2(beta), and Ca_3(PO_4)_2(am2)were more stable than struvite(MgNH_4PO_3?6H_2O) and calcite(CaCO_3). However, X-ray diffraction(XRD) analysis determined the formation of struvite and calcite minerals in the treated effluent. Kinetic experimental results showed that most of the phosphate was removed from synthetic effluent containing NH_4~+within 2 hr, while only 20% of the PO_4~(3-)was removed in the absence of NH_4~+after 24 hr of treatment. The formation of struvite in the DL-treated effluent was due to the rapid precipitation rate of the mineral. The final pH of the DL-treated effluent significantly influenced the mass ratio of struvite to calcite in the precipitates. Because more calcite was formed when the p H increased from 8.4 to 9.6, a p H range of 8.0–8.5 should be used to produce solid with high PO_4~(3-)content. This study demonstrated that DL could be used for effective removal of phosphate from the effluent and that resultant precipitates contained high content of phosphate and ammonium.     

Modeling of air quality with a modified two-dimensional Eulerian model： A case study in the Pearl River Delta （PRD） region of China

A modified two-dimensional Eulerian air quality model was used to simulate both the gaseous and particulate pollutant concentrations during October 21-24, 2004 in the Pearl River Delta （PRD） region, China. The most significant improvement to the model is the added capability to predict the secondary organic aerosols （SOA） concentrations because of the inclusion of the SOA formation chemistry. The meteorological input data were prepared using the CALMET meteorological model. The concentrations of aerosol-bound species such as NO3^-, NH4^＋, SO4^2-, and SOA were calculated in the fine particle size range （〈2.5 μm）. The results of the two-dimensional model were compared to the measurements at the ground level during the PRD Intensive Monitoring Campaign （IMC）. Overall, there were good agreements between the measured and modeled concentrations of inorganic aerosol components and O3. Both the measured and the modeled results indicated that the maximum hourly O3 concentrations exceeded the China National Air Quality Standard. The predicted 24-h average SOA concentrations were in reasonable agreement with those predicted by the method of minimum OC/EC ratio.     

Hydrolyzed AI（Ⅲ） clusters： Speciation stability of nano-All3

Pure nano-Al13 and aggregates at various concentrations were prepared to examine the particle size e ect of coagulation with inorganic polymer flocculant. The property and stability of various species formed were characterized using Infrared, 27Al-NMR, photo correlation spectroscopy (PCS), and Ferron assay. Results showed that concentration and temperature exhibited di erent roles on the stability of Al13. The quantity of Alb species analyzed by ferron assay in the initial aging period corresponded well with that of Al13, which has been confirmed in a dimension range of 1–2 nm by PCS. Al13 solutions at high concentrations (0.5–2.11 mol/L) were observed to undergo further aggregation with aging. The aggregates with a wide particle size distribution would contribute to the disappeared/decreased Al13 basis on the 27Al-NMR spectrum, whereas a part of Al13 would still remain as Alb. At low concentrations, Al13 solution was quite stable at normal temperature, but lost its stability quickly when heating to 90°C.     

Destruction of methylphosphonic acid in a supercritical water oxidation bench-scale double wall reactor

The destruction of methylphosphonic acid (MPA), a final product by hydrolysis/neutralization of organophosphorus agents such as sarin and VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothionate), was investigated in a a bench-scale, continuous concentric vertical double wall reactor under supercritical water oxidation condition. The experiments were conducted at a temperature range of 450–600°C and a fixed pressure of 25 MPa. Hydrogen peroxide was used as an oxidant. The destruction e ciency (DE) was monitored by analyzing total organic carbon (TOC) and MPA concentrations using ion chromatography on the liquid e uent samples. The results showed that the DE of MPA up to 99.999% was achieved at a reaction temperature of 600°C, oxygen concentration of 113% storichiometric requirement, and reactor residence time of 8 sec. On the basis of the data derived from experiments, a global kinetic rate equation for the DE of MPA and DE of TOC were developed by nonlinear regression analysis. The model predictions agreed well with the experimental data.     

Physicochemical interaction and its influence on deep bed filtration process

The capillary model was used to analyze the hydraulic conditions in the deep bed filtration process. The physicochemical interaction forces between the filter media and suspended particles and their influence on deep bed filtration process were also studied theoretically. Through the comparison of the hydraulic and physicochemical forces, the key influencing factors on the filtration process were proposed and investigated. Pilot study of the microflocculation deep bed filtration was carried out in the No. 9 Potable Water Treatment Plant of Beijing, and the experimental results of hydraulic head loss, particle distribution and entrapment were presented. The theoretical prediction was reasonably consistent with the experimental results under different conditions, which indicated that the regulation and control of micro-flocculation and deep bed filtration could be realized by the evaluation of the physicochemical interactions. Further theoretical and experimental research should be carried out to investigate the interaction mechanism and its application in the deep bed filtration and other cases.     

Debromination of decabromodiphenyl ether by organo-montmorillonite-supported nanoscale zero-valent iron：Preparation, characterization and influence factors

An organo-montmorillonite-supported nanoscale zero-valent iron material(M-NZVI) was synthesized to degrade decabromodiphenyl ether(BDE-209). The results showed that nanoscale zero-valent iron had good dispersion on organo-montmorillonite and was present as a core-shell structure with a particle size range of nanoscale iron between 30–90 nm, characterized by XRD, SEM, TEM, XRF, ICP-AES, and XPS. The results of the degradation of BDE-209 by M-NZVI showed that the efficiency of M-NZVI in removing BDE-209 was much higher than that of NZVI. The efficiency of M-NZVI in removing BDE-209 decreased as the pH and the initial dissolved oxygen content of the reaction solution increased, but increased as the proportion of water in the reaction solution increased.     

Oxygen tolerance capacity of upflow anaerobic solid-state (UASS) with anaerobic filter (AF) system

In order to investigate the oxygen tolerance capacity of upflow anaerobic solid-state(UASS)with anaerobic filter(AF) system, the effect of microaeration on thermophilic anaerobic digestion of maize straw was investigated under batch conditions and in the UASS with AF system. Aeration intensities of 0–431 m L O2/gvswere conducted as pretreatment under batch conditions. Aeration pretreatment obviously enhanced anaerobic digestion and an aeration intensity of 431 m L O2/gvsincreased the methane yield by 82.2%. Aeration intensities of 0–355 m L O2/gvswere conducted in the process liquor circulation of the UASS with AF system. Dissolved oxygen(DO) of UASS and AF reactors kept around 1.39 ±0.27 and 0.99 ± 0.38 mg/L, respectively. p H was relatively stable around 7.11 ± 0.04. Volatile fatty acids and soluble chemical oxygen demand concentration in UASS reactor were higher than those in AF reactor. Methane yield of the whole system was almost stable at 85 ± 7 m L/gvs as aeration intensity increased step by step. The UASS with AF system showed good oxygen tolerance capacity.     

Effect of traffic restriction on atmospheric particle concentrations and their size distributions in urban Lanzhou, Northwestern China

During the 2012 Lanzhou International Marathon, the local government made a significant effort to improve traffic conditions and air quality by implementing traffic restriction measures. To evaluate the direct effect of these measures on urban air quality, especially particle concentrations and their size distributions, atmospheric particle size distributions(0.5–20 μm) obtained using an aerodynamic particle sizer(model 3321, TSI, USA) in June 2012 were analyzed. It was found that the particle number, surface area and volume concentrations for size range 0.5–10 μm were(15.0±2.1) cm-3,(11.8±2.6) μm2/cm3and(1.9±0.6) μm2/cm3, respectively, on the traffic-restricted day(Sunday), which is 63.2%, 53.0% and 47.2% lower than those on a normal Sunday. For number and surface area concentrations, the most affected size range was 0.5–0.7 and 0.5–0.8 μm, respectively, while for volume concentration, the most affected size ranges were 0.5–0.8, 1.7–2.0 and 5.0–5.4 μm. Number and volume concentrations of particles in size range 0.5–1.0 μm correlated well with the number of non-CNG(Compressed Natural Gas) powered vehicles, while their correlation with the number of CNG-powered vehicles was very low, suggesting that reasonable urban traffic controls along with vehicle technology improvements could play an important role in improving urban air quality.