Ammonium nitrogen removal from slurry-type swine wastewater by pretreatment using struvite crystallization for nitrogen control of anaerobic digestion.

Precipitation of ammonium together with phosphate and magnesium is a possible alternative for lowering the nitrogen content of wastewater. In this study we examine the removal of ammonium nitrogen and phosphorus from slurry-type swine wastewater containing high concentrations of nutrients by the addition of phosphoric acid along with either calcium oxide or magnesium oxide, which leads to the crystallization of insoluble salts such as hydroxyapatite and struvite. The struvite crystallization method showed a high capacity for the removal of nitrogen when magnesium oxide and phosphoric acid were used as the magnesium and phosphate sources, respectively. When it was applied to swine wastewater containing a high concentration of nitrogen, the injection molar ratio of Mg2+:NH4+:PO4(3-) that gave maximum ammonium nitrogen removal was 3.0:1.0:1.5.     

Evaluation and thermodynamic calculation of ureolytic magnesium ammonium phosphate precipitation from UASB effluent at pilot scale

The removal of phosphate as magnesium ammonium phosphate (MAP, struvite) has gained a lot of attention. A novel approach using ureolytic MAP crystallization (pH increase by means of bacterial ureases) has been tested on the anaerobic effluent of a potato processing company in a pilot plant and compared with NuReSys(?) technology (pH increase by means of NaOH). The pilot plant showed a high phosphate removal efficiency of 83 ± 7%, resulting in a final effluent concentration of 13 ± 7 mg · L(-1) PO(4)-P. Calculating the evolution of the saturation index (SI) as a function of the remaining concentrations of Mg(2+), PO(4)-P and NH(4)(+) during precipitation in a batch reactor, resulted in a good estimation of the effluent PO(4)-P concentration of the pilot plant, operating under continuous mode. X-ray diffraction (XRD) analyses confirmed the presence of struvite in the small single crystals observed during experiments. The operational cost for the ureolytic MAP crystallization treating high phosphate concentrations (e.g. 100 mg · L(-1) PO(4)-P) was calculated as 3.9 € kg(-1) P(removed). This work shows that the ureolytic MAP crystallization, in combination with an autotrophic nitrogen removal process, is competitive with the NuReSys(?) technology in terms of operational cost and removal efficiency but further research is necessary to obtain larger crystals.     

Predicting struvite formation for phosphorus recovery from human urine using an equilibrium model.

Interest in phosphorus recovery from urine diverted from faeces has been growing recently. Phosphorus in urine can be precipitated out as struvite (MgNH4PO4 x 6H2O) with addition of magnesium salt under alkaline conditions. Struvite formation, however, should be more well understood for its practical application. We predicted the struvite formation with a development of a new equilibrium model. The model considered the formation of eight different kinds of precipitates, including struvite, with effects of ionic strength and temperature. In addition, experiments on struvite formation in urine were conducted for the model validation. The model prediction of struvite formation had good agreement with the experimental results. The optimum pH to form struvite was predicted to be 9.4-9.7. In order to precipitate 99% of phosphate in urine with 1.5 fold Mg concentration to PO4-P, the pH value was necessary to be more than 8.1 based on the model prediction.     

Recovering phosphorus as struvite from the digested swine wastewater with bittern as a magnesium source

Recovering nitrogen and phosphorus through struvite (MgNH4PO4 6H2O) crystallization from swine wastewater has gained increasing interest. However, swine wastewater contains complex compositions, which may hinder the formation of struvite crystal and affect the purity of the precipitates by forming other insoluble minerals. In this work, experiments were carried out to evaluate struvite precipitation in the anaerobically digested swine wastewater, with dosing bittern as a low-cost magnesium source. Exceeded 90% phosphate removal and 23-29% ammonium reduction were obtained. FTIR, XRD and mass balance analysis were combined to analyze the species of precipitated minerals. Results showed that the precipitates were struvite, mixed with amorphous calcium phosphate (ACP) and brucite. The presence of Ca2+ diminished the percentage of struvite and gave rise to ACP formation. Controlling pH below 9.5 and bittern dosage above 1% (w/w) could inhibit ACP precipitation and harvest a highly pure struvite crystal product.     

Struvite crystallization versus amorphous magnesium and calcium phosphate precipitation during the treatment of a saline industrial wastewater

Struvite crystallization (MgNH(4)PO(4)·6H(2)O, MAP) could be an alternative for the sustainable and economical recovery of phosphorus from concentrated wastewater streams. Struvite precipitation is recommended for those wastewaters which have high orthophosphate concentration. However the presence of a cheap magnesium source is required in order to make the process feasible. For those wastewater treatment plants (WWTP) located near the seashore magnesium could be economically obtained using seawater. However seawater contains calcium ions that could interfere in the process, by promoting the precipitation of amorphous magnesium and calcium phosphates. Precipitates composition was affected by the NH(4)(+)/PO(4)(3-) molar ratio used. Struvite or magnesium and calcium phosphates were obtained when NH(4)(+)/PO(4)(3-) was fixed at 4.7 or 1.0, respectively. This study demonstrates that by manipulating the NH(4)(+)/PO(4)(3-) it is possible to obtain pure struvite crystals, instead of precipitates of amorphous magnesium and calcium phosphates. This was easily performed by using either raw or secondary treated wastewater with different ammonium concentrations.     

菌藻混合固定化及其对污水的净化实验

对菌藻共固定化系统进行研究,初步确定菌藻共固定化中较佳的污泥包埋量。在同等条件下,固定化菌藻对氮磷的去除效果优于固定化细菌和固定化藻类的去除效果。对氨氮和磷酸盐磷去除能力的48 h实验结果表明,按去除率的大小排列为:固定化菌藻固定化小球藻固定化细菌,固定化菌藻对NH4+-N和PO43--P的去除率分别达到97.09%和88.69%,可见把细菌和藻类共同包埋于同一载体内,在同时去除污水中的氮磷和有机物方面有着更大的优势。     

Effects of various process parameters on struvite precipitation kinetics and subsequent determination of rate constants.

In this paper, struvite (MgNH(4)PO(4).6H(2)O) precipitation kinetics were studied with different operating conditions (varying supersaturation, pH, Mg:P ratio, degree of mixing and seeding conditions) and relevant rate constants were determined by fitting a slightly modified first-order kinetic model to the experimental data obtained. The rate of change of ortho-P concentration in the bulk solutions increases with increasing supersaturation ratio. The estimated rate constants are 2.034, 1.716 and 0.690 hr(-1) for the supersaturation ratio of 9.64, 4.83, and 2.44, respectively. Kinetic parameters were also evaluated for the Mg:P ratio between the ranges of 1.0 and 1.6, indicating higher phosphorus removal efficiency with increasing Mg:P ratio. The rate constants were found to be 0.942, 2.034 and 2.712 hr(-1) for Mg:P ratios of 1.0, 1.3 and 1.6, respectively. The experimental observations for kinetic study of struvite precipitation with different stirrer speeds clearly show that the mixing intensity used had little effect on the intrinsic rate constants. K values found to be 2.034 and 1.902 h(-1) for 100 and 70 rpm, respectively. Seeding, with 250-500 microm of seed crystals during the struvite precipitation kinetics test, was found to have very little effect on the ortho-P removal.     

Zeta potential measurement on the surface of blue-green algae particles for micro-bubble process.

Any kind of blue-green alga produces metabolites of musty substances and toxins. Therefore, it is necessary to remove the blue-green algae, and processing also including nutrient removal is desired for the water quality improvement of eutrophic lakes. The purpose of this study has been to investigate the possibility of a flotation system using a hybrid technique (chemical compounds and electrostatic bridge) applied to raw water containing phytoplankton with high pH of water, and to examine the zeta potential value of phytoplankton surface and the removal efficiency for phytoplankton, ammonia, nitrogen, and phosphoric acid.The results were as follows: firstly, zeta potential of M. aeruginosa particles was observed to achieve charge neutralization on their surface by adhesion of magnesium hydroxide precipitation with increasing pH. Secondly, maximum removal efficiency concerning chlorophyll-a was observed as 84%, and this efficiency was obtained in the condition of pH > 10, and magnesium hydroxide precipitation was observed. Thirdly, in the pH condition that the maximum removal efficiency of chlorophyll-a was obtained, the removal efficiency and the amount of decrease of NH(4)-N and PO(4)-P before and after the change of pH values were observed as 6.7% (0.04 mg-P/L) and 63.6% (0.07 mg-N/L), respectively.     

Development of a process for the recovery of phosphorus resource from digested sludge by crystallization technology.

Removal and recovery of phosphorus from sewage in form of MAP (magnesium ammonium phosphate) have attracted attention from the viewpoint of eutrophication prevention and phosphorus resource recovery as well as scaling prevention inside digestion tanks. In this work, phosphorus recovery demonstration tests were conducted in a 50 m3/d facility having a complete mixing type reactor and a liquid cyclone. Digested sludge, having 690 mg/L T-P and 268 mg/L PO4-P, was used as test material. The T-P and PO4-P of treated sludge were 464 mg/L and 20 mg/L achieving a T-P recovery efficiency of 33% and a PO4-P crystallization ratio of 93%. The reacted phosphorus did not become fine crystals and the recovered MAP particles were found to be valuable as a fertilizer. A case study in applying this phosphorus recovery process for treatment of sludge from an anaerobic-aerobic process of a 21,000 m3/d sewage system, showed that 30% of phosphorus concentration can be reduced in the final effluent, recovering 315 kg/d as MAP.     

Removal of ammonium from aqueous solutions using the residue obtained from struvite pyrogenation

This paper reports the results of laboratory studies on the removal of ammonium from aqueous solutions using struvite pyrogenation residues. A series of experiments were conducted to examine the effects of the pyrogenation temperature (90-210 °C) and time (0.5-4 h) on the ammonium release of struvite. In addition, the pyrolysate of struvite produced at different pyrogenation temperatures and times was recycled for ammonium removal from aqueous solutions. The experimental results indicated that the ammonium release ratio of struvite increased with an increase in the pyrogenation temperature and time, and the struvite pyrolysate used as magnesium and phosphate source for ammonium removal was produced at the optimal condition of pyrogenation temperature of 150 °C for 1 h. Furthermore, experimental results showed that the optimum pH and pyrolysate dosage for ammonium removal from 100 ml synthetic wastewater (1,350 mg ammonium/L) were at pH 9 and 2.4 g of struvite pyrolysate, respectively, and initial ammonium concentration played a significant role in the ammonium removal by the struvite pyrolysate. In order to further reduce the cost of struvite precipitation, the struvite pyrolysate was repeatedly used for four cycles. The results of economic analysis showed that recycling struvite for three process cycles should be reasonable for ammonium removal, with ammonium removal efficiencies of over 50% and a reduction of 40% in the removal cost per kg NH(4)(+).     

Solutions to a combined problem of excessive hydrogen sulfide in biogas and struvite scaling.

The Woodman Point Wastewater Treatment Plant (WWTP) in Western Australia has experienced two separate problems causing avoidable maintenance costs: the build-up of massive struvite (MgNH4PO4. 6H2O) scaling downstream of the anaerobic digester and the formation of hydrogen sulfide (H2S) levels in the digester gas to levels that compromised gas engine operation and caused high operating costs on the gas scrubber. As both problems hang together with a chemical imbalance in the anaerobic digester, we decided to investigate whether both problems could be (feasibly and economically) addressed by a common solution (such as dosing of iron solutions to precipitate both sulfide and phosphate), or by using separate approaches. Laboratory results showed that, the hydrogen sulfide emission in digesters could be effectively and economically controlled by the addition of iron dosing. Slightly higher than the theoretical value of 1.5 mol of FeCl3 was required to precipitate 1 mol of dissolved sulfide inside the digester. Due to the high concentration of PO4(3-) in the digested sludge liquor, significantly higher iron is required for struvite precipitation. Iron dosing did not appear an economic solution for struvite control via iron phosphate formation. By taking advantage of the natural tendency of struvite formation in the digester liquid, it is possible to reduce the risk of struvite precipitation in and around the sludge-dewatering centrifuge by increasing the pH to precipitate struvite out before passing through the centrifuge. However, as the Mg2+/PO4(3-) molar ratio in digested sludge was low, by increasing the pH alone (using NaOH) the precipitation of PO4(3-) was limited by the amount of cations (Ca2+ and Mg2+) available in the sludge. Although this would reduce struvite precipitation in the centrifuge, it could not significantly reduce PO4(3-) recycling back to the plant. For long-term operation, maximum PO4(3-) reduction should be the ultimate aim to minimise PO4(3-) accumulation in the plant. Magnesium hydroxide liquid (MHL) was found to be the most cost-effective chemical to achieve this goal. It enhanced struvite precipitation from both, digested sludge and centrate to the point where more than 95% PO4(3-) reduction in the digested sludge was achieved.     

Analysis of phosphorus removal and anaerobic selector performance in a full-scale activated sludge process in Singapore.

This paper analyses the performance of the anaerobic selector (A/O process) in a full-scale activated sludge process receiving mostly industrial sewage discharge (> 60%) in Singapore. In addition to the sludge settleability, enhanced biological phosphorus removal (EBPR) was studied. The sludge volume index (SVI) reduced from 200 to 80 ml g(-1) and foaming was suppressed significantly, indicating the effectiveness of the anaerobic selector in improving sludge settleability. The phosphorus removal efficiency was 66%, and 7.5 mg HAc-COD was consumed per mg PO4(3-) -P removed. In the anaerobic compartment, 31% of the SCOD and 73% of the acetic acid in the settled sewage were removed with PO4(3-) -P release of 14.1 mg PO4(3-)-P l(-1). The linear correlation between PO4(3-) -P release in the anaerobic compartment and PO4(3-) -P uptake in the aerobic compartment indicates that there is about 0.8 mg PO4(3-) -P release in the anaerobic compartment per mg PO34(3-) -P uptake in the aerobic compartment. The fates of volatile fatty acids (VFAs) and its short chain acids (SCAs) in the process were studied and discussed.     

CASS工艺生物脱氮除磷效果分析

对CASS工艺脱氮除磷效果进行了试验研究,重点研究了温度和回流比对脱氮效果的影响,曝气量对除磷效果的影响。研究结果表明,水温在30℃时系统脱氮效果最好,此时NH3-N去除率在80%左右,TN去除率在70%左右;污泥回流比为25%、50%、100%和200%时,TN去除率分别为50%、58%、62%和70%,增加回流比可以提高脱氮效率;好氧区DO维持在2mg/L和4 mg/L时,TP去除率分别为82%和37%。     

污水处理厂回流液中回收磷酸铵镁的试验研究

用污水处理厂回流液进行磷酸铵镁(MAP)沉淀试验,研究化学沉淀法回收MAP的适宜条件.结果表明,pH为8～11时生成沉淀的主要成分为MAP;当pH为10,药剂配比n(NH+4)∶n(Mg2+)∶n(PO43-)控制在1∶1∶1和1∶1.4∶1时得到的晶体纯度高,前者形成的沉淀量为5.3 g/L,氨氮去除率为90.86%;后者形成的沉淀量为5.74 g/L,氨氮去除率为95.84%.分析表明从回流液中回收MAP可以大幅降低处理成本以及系统的氮磷负荷,还可解决MAP结垢问题,实现资源的再生.     

Treatment of slaughterhouse plant wastewater by using a membrane bioreactor

The use of a membrane bioreactor (MBR) for removal of organic substances and nutrients from slaughterhouse plant wastewater was investigated. The chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) concentrations of slaughterhouse wastewater were found to be approximately 571 mg O2/L, 102.5 mg/L, and 16.25 mg PO4-P/L, respectively. A submerged type membrane was used in the bioreactor. The removal efficiencies for COD, total organic carbon (TOC), TP and TN were found to be 97, 96, 65, 44% respectively. The COD value of wastewater was decreased to 16 mg/L (COD discharge standard for slaughterhouse plant wastewaters is 160 mg/L). TOC was decreased to 9 mg/L (TOC discharge standard for slaughterhouse plant wastewaters is 20 mg/L). Ammonium, and nitrate nitrogen concentrations of treated effluent were 0.100 mg NH4-N/L, and 80.521 mg NO3-N/L, respectively. Slaughterhouse wastewater was successfully treated with the MBR process.     

温度和基质对人工湿地脱氮除磷效果的影响

构建由潜流人工湿地和表流人工湿地串联而成的复合人工湿地系统,研究了复合人工湿地脱氮除磷效果以及温度和基质对人工湿地脱氮除磷效果的影响。结果表明,复合人工湿地TP、氨氮平均去除率为33.64%、57.24%;水温降低会导致人工湿地氮磷去除率下降;基质为粗砂的潜流人工湿地脱氮除磷能力大于基质为砾石的潜流人工湿地。     

Experiences on dual media filtration of WWTP effluent

This research is legislation driven by the European Water Framework Directive (WFD) and the Dutch Fourth Memorandum on Water Management. The objective of this research is to achieve the removal of total nitrogen and total phosphorus by Dual Media Filtration. The target value during this research for total nitrogen is 2.2 mg/L and for total phosphorus 0.15 mg/L. The results show that for NOx-N concentrations in the WWTP effluent up to 10 mg/L, a stable operation of the process can be reached with removal rates of 80% to 90%. The maximum nitrogen removal rate was 3.5 kg N/(m3.d). Above 10 mg/L a risk of filter bed clogging occurred. When the orthophosphorus concentration in the WWTP effluent exceeds the maximum of 0.3 mg/L, the total phosphorus concentration in the filtrate water will exceed the target value of 0.15 mg P-total/L. Temperature has a large impact in the phosphorus removal; the optimum temperature range is within 13 degrees C-18 degrees C. In conclusion, Dual Media Filtration is capable of producing reusable water with total phosphorus concentrations of <0.15 mg/L, under the condition that the wastewater treatment plant produces WWTP effluent with steady concentrations for orthophosphorus (<0.3 mg PO4-P/L). To reach total nitrogen concentrations in the filtrate water of <2.2 mg/L a NOx-N removal efficiency of nearly 100% is required.     

Phosphorus recovery from wastewater through struvite formation in fluidized bed reactors: a sustainable approach.

Recovery of phosphate as struvite (MgNH4PO4.6H2O), before it forms and accumulates on wastewater treatment equipment, solves wastewater treatment problems and also provides environmentally sustainable, renewable nutrient source for the agriculture sector. A pilot-scale fluidized bed reactor was used to recover phosphate through crystallization of struvite, from anaerobic digester centrate at the Lulu Island Wastewater Treatment Plant, Richmond, British Columbia, Canada. The desired degree of phosphate removal was achieved by maintaining operating pH (8.0-8.2), and recycle ratio 5-9, to control the supersaturation conditions inside the reactor. The performance of the system was found to be optimal when in-reactor supersaturation ratio was 2-6. Among several other operating parameters, apparent upflow velocity and magnesium to phosphate molar ratio were also found important to maintain system performance, both in terms of efficiency of phosphate removal and recovery as struvite pellets. A narrow window of upflow velocity (400-410 cm/min) was found to be effective in removing 75-85% phosphate. TOC level inside the rector was found to affect the performance to some extent. The precipitation potential of struvite could be successfully predicted using a thermodynamic solubility product value of 10(-13.36) and its temperature dependence in PHREEQC.     

Impacts of nutrients and related environmental factors on distribution and size structure of Noctiluca scintillans populations of the eutrophic Tha Chin estuary, Thailand

This study aimed to analyze the impacts of nutrients and related aquatic factors on changes in the Noctiluca population of the Tha Chin estuary, a nutrient-rich estuary located in the inner Gulf of Thailand. Field surveys were carried out at 30 stations during November 2009 to August 2010. The results indicated high levels of dissolved inorganic nitrogen (DIN; 13.89-46.99 μmol/L) and PO(4)(3-)-P (0.20-3.05 μmol/L) where the Noctiluca red tide occurred, particularly during the high-loading period. Dense populations were usually found in the outer part of the estuary with comparatively high salinity (25-29 psu). The highest Noctiluca density was 72,333 cells L(-1) and the cell diameters ranged between 360 and 460 μm. Proportions of small-sized cells (P(s); less than 300 μm) varied over time. In this study, P(s) showed a positive correlation with levels of PO(4)(3-)-P, while the total population density was significantly affected by levels of NH(4)(+)-N and DIN (p < 0.05). Overall, PO(4)(3-)-P influenced the development of the Noctiluca red tide, with the limitation of PO(4)(3-)-P levels to below 1 μmol/L suggested for controlling Noctiluca red tide outbreaks at their origin. To support environmental conservation and maintain sustainable production in the estuary, the levels of PO(4)(3-)-P should be considered for the further effective development of water quality standards in estuarine zones.     

Effects of organic and inorganic acids on phosphorus release from municipal sludge.

This paper reports on the effects of inorganic acids (sulphuric acid, hydrochloric acid, nitric acid) and organic acids (citric acid, oxalic acids) for phosphorus recovery from sludge and struvite precipitation results. It was observed that both inorganic acid and organic acids were effective at phosphorus release. The studies on precipitation of released phosphorus from sludge as magnesium ammonium phosphate (struvite) were also done using nitric and oxalic acids. Phosphorus and heavy metals of leachate were analyzed before and after precipitation. It was observed that heavy metal concentrations in the extracted samples decrease after precipitation. Precipitation was accomplished by using extract derived with nitric acid; however, in oxalic acid applications, it was not achieved. When the chemical constituents of the dried material were examined oxygen, sodium and nitrogen were found to be the major elements.