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.     

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.     

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)(+).     

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.     

A study of NH3-N and P refixation by struvite formation in hybrid anaerobic reactor.

This research is concerned with the removal of ammonia nitrogen and phosphorus in foodwaste by crystallization. Reductions have been achieved by struvite formation after the addition of magnesium ions (Mg2+). Magnesium ions used in this study were from magnesium salts of MgCl2. The results of our analysis using scanning electron microscopy and energy dispersive X-ray analysis showed that the amount of struvite in precipitated sludge grew enough to be seen with the naked eye (600-700 microm). EDX analysis also showed that the main components of the struvite were magnesium and phosphorus. NH3-N removal efficiency using MgCl2 was 67% while PO4-P removal efficiency was 73%. It was confirmed that nitrogen and phosphorus could be stabilized and removal simultaneously through anaerobic digestion by Mg, NH3 and PO4-P, which were necessary for struvite formation.     

Phosphorus recovery as struvite from eutropic waters by XDA-7 resin

Phosphorus releases into aquatic environment and its subsequent contribution to eutrophication have resulted in a widespread global pollution issue. However, phosphorus is a non-renewable source. The potential supplies of phosphorus are decreasing worldwide. Therefore, removal and recovery of phosphorus from the eutropic waters is important, emergent and necessary. In this research, experiments for recovering phosphate from eutropic waters by anion exchange combined with struvite precipitation were conducted. The results indicated that the prepared XDA-7 resin was an effective adsorbent for phosphate. The adsorption isotherm of XDA-7 resin was found to be a modified Freundlich type. The maximum phosphate adsorption (20.9 mg/g) occurred in the pH range of 6.0-8.0. Phosphate adsorbed on the XDA-7 resin was effectively desorbed with 8% NaCl solution, and the resin was able to be regenerated with 3% NaClO and 4% NaOH solutions. Phosphate desorbed from the resin was recovered as magnesium ammonium phosphate (struvite). The obtained struvite was analyzed by acid dissolution method, scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). The struvite precipitate was found to be 75.8% in purity, a high-value fertilizer.     

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.     

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.     

External carbon feeding strategy for enhancing nitrogen removal in SBR.

Effective method for feeding an external carbon source (ECS) in SBR was investigated to enhance denitrification based on modifying the anoxic/aerobic sub-cycle for swine wastewater treatment. The wastewater discharged from the scraper-type barns contains relatively low readily biodegradable organic. Therefore NOx-N was accumulated during repeating sub-cycle in SBR operation. When acetic acid was fed as ECS during the final sub-cycle, the maximum nitrogen removal rate was 0.22 kg N/m3/d. This was due to both less denitrification rate during the sub-cycle period and inhibition of denitrification by pH drop during the final cycle. The pH drop was caused by a large amount of ECS feeding to remove high concentration of NOx-N in the final period. To overcome these limitations and achieve higher nitrogen removal rate, the intermittent ECS feeding method with raw wastewater at every anoxic period was developed. Using the modifying ECS feeding method, the removal rate was increased to 0.45 kg N/m3/d without NOx-N accumulation.     

Onsite wastewater nitrogen reduction with expanded media and elemental sulfur biofiltration

A passive biofiltration process has been developed to enhance nitrogen removal from onsite sanitation water. The system employs an initial unsaturated vertical flow biofilter with expanded clay media (nitrification), followed in series by a horizontal saturated biofilter for denitrification containing elemental sulfur media as electron donor. A small-scale prototype was operated continuously over eight months on primary wastewater effluent with total nitrogen (TN) of 72.2 mg/L. The average hydraulic loading to the unsaturated biofilter surface was 11.9 cm/day, applied at a 30 min dosing cycle. Average effluent TN was 2.6 mg/L and average TN reduction efficiency was 96.2%. Effluent nitrogen was 1.7 mg/L as organic N, 0.93 mg/L as ammonium (NH(4)-N), and 0.03 as oxidized (NO(3) + NO(2)) N. There was no surface clogging of unsaturated media, nitrate breakthrough, or replenishment of sulfur media over eight months. Visual and microscopic examinations revealed substantially open pores with limited material accumulation on the upper surface of the unsaturated media. Material accumulation was observed at the inlet zone of the denitrification biofilter, and sulfur media exhibited surface cavities consistent with oxidative dissolution. Two-stage biofiltration is a simple and resilient system for achieving high nitrogen reductions in onsite wastewater.     

Treatment of strong nitrogen swine wastewater in a full-scale sequencing batch reactor.

Treatment of swine wastewater containing strong nitrogen was attempted in a full-scale SBR. The strongest swine wastewater was discharged from a slurry-type barn and called swine-slurry wastewater (SSW). Slightly weaker wastewater was produced from a scraper-type barn and called swine-urine wastewater (SUW). TCOD, NH4+-N and TSS in raw SSW were 23,000-72,000 mg/L, 3,500-6,000 mg/L and 17,000-50,000 mg/L, respectively. A whole cycle of SBR consists of 4 sub-cycles with anoxic period of 1 hr and aerobic period of 3 hr. The maximum loading rates of both digested-SSW and SUW were similar to 0.22 kg NH4+-N/m3/day whereas the maximum loading rates of raw SSW was up to 0.35 TN/m3/day on keeping the effluent quality of 60 TN mg/l. The VFAs portion of SCOD in raw SSW was about more than 60%. The VFAs in SUW and digested-SSW were about 22% and 15%, respectively. NH4+-N and PO4(3-)-P in SSW were removed efficiently compared to those in digested-SSW and DUW because SSW had high a C/N ratio and readily biodegradable organic. High concentration of organic was useful to enhance denitrification and P uptake. Also the amount of external carbon for denitrification was reduced to 5% and 10% of those for digested-SSW and SUW.     

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.     

Model experiments on improving nitrogen removal in laboratory scale subsurface constructed wetlands by enhancing the anaerobic ammonia oxidation.

Anaerobic ammonia oxidation (Anammox) has been identified as a new general process-strategy for nitrogen removal in wastewater treatment. In order to evaluate the role and effects of the Anammox process in wetlands, laboratory-scale model experiments were performed with planted fixed bed reactors. A reactor (planted with Juncus effusus) was fed with synthetic wastewater containing 150-200 mg L(-1) NH4+ and 75-480 mg L(-1) NO2(-). Under these operating conditions, the plants were affected by the high ammonia and nitrite concentrations and the nitrogen removal rate fell within the same range of 45-49 mg N d(-1) (equivalent to 0.64-0.70 g Nm(-2)d(-1)) as already reported by other authors. In order to stimulate the rate of nitrogen conversion, the planted reactor was inoculated with Anammox biomass. As a result, the rate of nitrogen removal was increased 4-5-fold and the toxic effects on the plants also disappeared. The results show that, in principle, subsurface flow wetlands can also function as an "Anammox bioreactor". However, the design of a complete process for the treatment of waters with a high ammonia load and, in particular, the realisation of simple technical solutions for partial nitrification have still to be developed.     

Using a compact combined constructed wetland system to treat agricultural wastewater with high nitrogen.

The objectives of this study were to find appropriate conditions for nitrogen removal by a compact combined constructed wetland system and to evaluate the removal rate constant in a tropical climate. This study will present suitable operating conditions for a combined system to treat pig farm wastewater containing high ammonia-nitrogen. Four laboratory-scale combined constructed wetland units (0.5 x 1.0 x 1.0 m3): vertical flow vegetated bed over horizontal flow sand bed, were operated under an average temperature of 24 degrees C. Pig farm wastewater with COD and NH4-N concentration of 1034 and 448 mg/L in average was fed to the system at different HLR from 2 to 8 cm/day. The performance of the system when operated with a vertical flow bed followed by a horizontal flow bed or vice versa did not show a significant difference but under high HLR, nitrogen removal efficiencies were clearly reduced. Nitrobacter and Nitrosomonas were found in a large number in vertical flow beds and the same for denitrifier bacteria in a horizontal flow beds. Removal rate constants for nitrification (kNH4+ -N) were 0.0413 m/d for H-Vmode and 0.0339 m/d for V-H mode. Removal rate constants for denitrification (kNOx-N) were 0.0979 m/d for H-Vmode and 0.0399 m/d for V-H mode, respectively.     

中水湿地去氮效果研究

以山东省平阴中水湿地为研究对象,通过对湿地水体、底泥的氨态氮(NH3-N)、硝态氮(NO3--N)沿程变化的分析,研究湿地对中水中氮(N)的去除效果。结果表明:湿地对水体中NH3-N的去除效果较好,而作为水体中N主要存在形式的NO3--N沿水流方向却呈增加趋势,微生物硝化作用强烈。底泥中总氮(TN)沿水流方向也呈增加趋势,累计效应比较明显。研究结果为湿地设计的进一步改进提供理论支持。     

Factors affecting nitrogen removal by nitritation/denitritation.

Nitrogen removal from wastewater with high nitrogen concentration and low COD/N ratio via nitrite is advantageous. The specific character of the sludge liquor enables the application of such a method. The factors affecting process efficiency were studied. From the factors followed pH, NH4+/NH3 and NO2-/HNO2 concentration and distribution seem to be most important, using sequencing batch reactor technology and treating wastewater with high NH4+ concentration (above 1 g/l). The efficient oxidation of N-NH4+ to nitrite was achieved at a minimal nitrate production. Primary sludge was used as an internal source of substrate for the denitritation because of the organic substrate deficiency of the sludge liquor. The denitritation can be controlled by dosing of the primary sludge and can be complete. There are two operational alternatives of sludge liquor pretreatment: without pH control--lower operational costs and N-removal up to 65% and with pH control--higher operational costs and N-removal close to complete.     

污水处理领域磷回收技术及其应用

介绍了国内外从污水中磷回收研究与应用现状,多以含磷丰富的污泥脱水上清液、厌氧污泥消化液以及富磷废水为磷源,鸟粪石、磷酸钙等沉淀是目前广泛采用的回收形式。简述污水处理领域的磷回收技术有沉淀法,结晶法,电渗析法、离子交换等。沉淀法中鸟粪石、磷酸钙等的研究相对较为成熟,应用较多。最后展望了我国污水处理领域磷回收前景,2005年我国污水中的磷量相当于2000年全国磷矿开采量的42.7%,具有广泛的回收前景和环境经济效益。     

鸟粪石法去除废水中氨氮的影响因素及应用

以鸟粪石沉淀的形式去除废水中的氨氮,操作简便,反应速度快,是一种较有效的方法。介绍了鸟粪石晶体的性质、反应机理,总结了鸟粪石法反应的主要影响因素及应用,对存在问题进行了分析,并在此基础上对该方法的未来趋势进行了展望。     

不同氮源对黄花鸢尾净化富营养化水体的影响

利用水生植物床系统研究了不同氮源(硝酸盐、亚硝酸盐、铵盐)对黄花鸢尾(Iris pseudoacorus)去除水体氮磷营养盐效率的影响,同时对植物的生长量、水体中叶绿素a含量、黄花鸢尾对氮磷的吸收利用以及氮循环细菌的分布和氧化亚氮的通量进行了综合研究。结果表明:黄花鸢尾对硝酸盐氮具有优先选择性,而对氨氮的去除效果较差。从植物总氮、总磷吸收量来看,3种氮源中硝酸盐氮>亚硝酸盐氮>氨氮;从氮循环菌分布和N2O释放量来看,硝酸盐氮>氨氮>亚硝酸盐氮。一定范围内,植物对营养盐的吸收随营养盐浓度增加而增加,但水体中营养盐浓度过高则会抑制植物的生长,浓度为80 mg/L的硝酸盐氮,亚硝酸盐氮和氨氮都对黄花鸢尾生长有抑制作用,尤其是高浓度氨氮溶液中,植物的湿重明显减少,因此,黄花鸢尾更适宜治理硝酸盐污染的水体。     

Effect of C/N ratio on nitrous oxide emission from swine wastewater treatment process.

To evaluate control parameters for nitrous oxide (N2O) emissions in the swine wastewater treatment process, the N2O emission was compared in the activated sludge from SBRs acclimated in different carbon/nitrogen (C/N) ratios. N2O emission from a denitrification phase was very strongly dependent on C/N ratio of swine wastewater, and the total N2O emission in the operating condition of BOD5/TN ratio of 2.6 was approximately 270 times greater than that in BOD5/TN ratio of 4.5. However, the effect of C/N ratio on N2O emission amount from nitrification was not significant in an oxic phase study. It is considered that stabilization of the C/N ratio through optimal solid-liquid separation of slurry or use of an external carbon source is indispensable for effective N2O emission control from nitrogen removal process of swine wastewater.