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Effects of pH, molar ratios and pre-treatment on phosphorus recovery through struvite crystallization from effluent of anaerobically digested swine wastewater

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Struvite precipitation has been proven to be an effective method in removing and recovering ammonia nitrogen (N) and phosphate phosphorus (P) from wastewater. In this study, effects of pH, molar ratios and pre-treatment of effluent of anaerobically digested swine wastewater were investigated to improve struvite crystallization. The magnesium : ammonium : phosphate ratio of 1.2 : 1.0 : 1.0 was found to be optimal, yet the molar ratio in the wastewater was 1 : 74.9 : 1.8. From the analysis, the optimum pH was between 8.0 and 9.0 for maximal phosphate P release and from 8.0 to 10.0 for maximal ammonia N and phosphate P removal from real wastewater. Analysis from Visual MINTEQ predicted the pH range of 7-11 for ammonia N and phosphate P removal and recovery as struvite. For pre-treatment, microwave pre-treatment was ineffective for phosphate P release but ultrasound pre-treatment showed up to 77.4% phosphate P release at 1,000 kJ/L of energy dose. Precipitates analysis showed that phosphorus and magnesium in the collected precipitate had almost same values as theoretical values, but the ammonia content was less than the theoretical value.
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1. Introduction
Recently livestock wastewater treatment and recycling in South
Korea have become a big issue as animal wastewater generation
has reached to about 46,000 Mm3/y. Also, the wastewater from
the pig farming industry poses serious social and economic prob-
lems due to the negative effect on the environment with respect
to treatment and recycling of swine wastewater [1-2]. The treatment
and recovery of nutrient from the waste stream is important, since
swine wastewater contains high concentrations of nitrogen and
phosphorus that cause eutrophication in water bodies. Recently,
the depletion of phosphorus resources has been a big issue, which
has been discussed on a global basis [3], although it is estimated
that 7,000 billion kg of phosphate rock still exists [2].
Phosphorus as well as nitrogen in swine wastewater after anaero-
bic digestion has been widely used as a liquid fertilizer in Korea.
However, the quick-release fertilizer application is a principal
source of nitrogen and phosphorus pollution in the farming field,
causing water pollution. Alternative methods, however, such as
crystallization and adsorption processes have been developed to
recover nutrients to high quality [4-6]. Among these techniques,
the crystallization process of the magnesium ammonium phosphate
(MAP, also known as struvite) is considered to be one of the better
techniques, as struvite crystallization is cost-effective and yields
high-quality nutrients, used as valuable slow-release fertilizers [7-9].
Struvite (MgNH4PO46H2O) is a crystalline substance consisting
of magnesium, ammonium, and phosphate ions in equal molar
concentrations. Struvite crystal is commonly formed as scale after
anaerobic digestion on pipe walls and reactor vessels. The chemical
equation for struvite crystal formation is as follows [10]:




(1)
Environ. Eng. Res. 2017; 22(1): 12-18
pISSN 1226-1025
https://doi.org/10.4491/eer.2016.037
eISSN 2005-968X
Effects of pH, molar ratios and pre-treatment on phosphorus
recovery through struvite crystallization from effluent of
anaerobically digested swine wastewater
Daegi Kim1, Kyung Jin Min2,3, Kwanyong Lee4, Min Sung Yu2, Ki Young Park2
1Institute for Advanced Engineering, Gyeonggi-do 17180, Republic of Korea
2Department of Civil and Environmental System Engineering, Konkuk University, Seoul 05029, Republic of Korea
3AinChemTech Co., Ltd and EPS Solution Co., Ltd, Gyunggi-do 05029, Republic of Korea
4Korea Institute of Civil Engineering and Building Technology, Gyeonggi-do 10223, Republic of Korea
ABSTRACT
Struvite precipitation has been proven to be an effective method in removing and recovering ammonia nitrogen (N) and phosphate phosphorus
(P) from wastewater. In this study, effects of pH, molar ratios and pre-treatment of effluent of anaerobically digested swine wastewater were
investigated to improve struvite crystallization. The magnesium : ammonium : phosphate ratio of 1.2 : 1.0 : 1.0 was found to be optimal, yet
the molar ratio in the wastewater was 1 : 74.9 : 1.8. From the analysis, the optimum pH was between 8.0 and 9.0 for maximal phosphate
P release and from 8.0 to 10.0 for maximal ammonia N and phosphate P removal from real wastewater. Analysis from Visual MINTEQ predicted
the pH range of 7-11 for ammonia N and phosphate P removal and recovery as struvite. For pre-treatment, microwave pre-treatment was
ineffective for phosphate P release but ultrasound pre-treatment showed up to 77.4% phosphate P release at 1,000 kJ/L of energy dose. Precipitates
analysis showed that phosphorus and magnesium in the collected precipitate had almost same values as theoretical values, but the ammonia
content was less than the theoretical value.
Keywords: Ammonia and phosphate recovery, Magnesium ammonium phosphate, Pre-treatment, Struvite, Ultrasonic treatment
This is an Open Access article distributed under the terms
of the Creative Commons Attribution Non-Commercial License
(http://creativecommons.org/licenses/by-nc/3.0/) which per-
mits unrestricted non-commercial use, distribution, and reproduction in any
medium, provided the original work is properly cited.
Copyright © 2017 Korean Society of Environmental Engineers
Received February 29, 2016 Accept ed September 6, 2016
Corresponding author
Email: kypark@konkuk.ac.kr
Tel: +82-2-450-3736 Fax: +82-2-450-3726
Environmental Engineering Research 22(1) 12-18
13
Struvite precipitation from wastewater is influenced by a large
number of parameters such as pH of the reaction, molar ratio,
interfering ions in the feed, reaction time, types of chemicals added,
types of the reactor used and temperature. From these, the reaction
pH and molar ratios of reactants, namely magnesium : ammonium
: phosphate molar ratios, are the main factors for struvite
precipitation.
The pH of the reaction plays a significant role during struvite
precipitation process, and not only affects the amount of struvite
precipitation, but also its purity. Increasing the pH and the reactant
concentration can reach solution saturation but increasing the
pH of the solution is more feasible and allows for more varied
applications [11]. Struvite can be precipitated at a wide pH range
(from 7.0 to 11.5), but the suitable pH range is from 8.0 to 9.5.
Struvite precipitation is a physico-chemical process that can occur
over a range of pH values bounded by the speciation of struvite
components so that the concentrations of magnesium, ammonium
and phosphate ions can be affected by the pH of the solution
[12]. A variety of magnesium and phosphate complex ions patterns
in the reactor solution, including MgOH+, Mg(OH)3-, MgH2PO4+,
MgHPO4, H3PO4, H2PO4-, HPO4-2, MgPO4- can be formed when
the pH of solution is varied [13].
The pH of the solution in the struvite precipitation reactor
influences struvite solubility. With increasing the pH, the struvite
solubility decreases, but the solubility begins to increase when
the pH rises above pH 9; this is because the ammonium ion concen-
tration decreases and the phosphate ion concentration increases
[12, 14]. As various factors such as reaction pH, ionic strength
and temperature affect struvite solubility, which in turn determines
the supersaturation ratio [15]. It is the excess supersaturation in
the liquid that is the major parameter in predicting struvite precip-
itation potential [16]; therefore, it is important to use chemical
equilibrium-based models to calculate and predict the practical
conditions for struvite formation. There is a geochemical equili-
brium speciation model MINTEQ that could be used to model
struvite formation [17]. For calculating metal speciation, solubility
equilibria, sorption, etc., for natural waters, visual MINTEQ is
available as a freeware chemical equilibrium model.
For the anaerobically digested effluent of swine wastewater
from livestock, there is generally less magnesium and phosphate
ions compared with ammonium ion. It is then necessary to add
a source of magnesium and phosphate ions to enhance the struvite
crystallization process. The concentration of phosphate ion is ex-
pected to increase through solubilization of total phosphorus. The
first step, thus, is to enable phosphate P release from solid phases
to increase the recovery of phosphorus by the struvite crystal-
lization process. The general methods to facilitate phosphate P
release are physical and chemical techniques [18-20]. Among these
techniques, alkaline-ultrasonic pre-treatment is preferred as it also
disintegrates the solid from swine wastewater and enhances the
anaerobic digestion process [21-22].
The objectives of this study were to investigate the effect of
pH and molar ratios for magnesium, ammonium, and phosphate
ions on ammonia N and phosphate P removal and recovery. Also
alkaline-ultrasonic pre-treatment was applied to the struvite crys-
tallization process to enhance nutrient recovery.
2. Materials and Methods
2.1. Materials
The anaerobically digested effluent of swine wastewater used
in the study was from the P-city swine wastewater treatment
plant in Korea. The effluent of swine wastewater was concentrated
at 4°C for 24 h and its main characteristics are shown in Table
1. Based on the initial composition of the effluent solution, magne-
sium and phosphate ions concentrations were very low, and
they needed to be increased to reach the desired molar ratios
for magnesium, ammonium, and phosphate ions. For both syn-
thetic and real wastewater, the concentrations of magnesium,
ammonium and phosphate ions were adjusted to the required
molar concentration using MgCl26H2O, NH4Cl and KH2PO4 sol-
utions, respectively. All reagents were of analytical grade. To
investigate the effect of reaction pH, 2 N HCl and 2 N NaOH
were used to adjust the pH, and the pH was monitored with
a pH meter. In addition, the pH influenced the phosphorus frac-
tions [22-23].
Table 1. Characteristics of the Effluent from the Anaerobically Digested
Swine Wastewater
Concentration
pH 8.17
T-N (mg/L) 2,350
NH3-N (mg/L) 1,775
T-P (mg/L) 612
PO4-P (mg/L) 221
2.2. Crystallizations Experiments
A lab-scale airlift reactor with a working volume of 5 L was used
for struvite crystallization. The schematic diagram of the ex-
perimental apparatus for struvite crystallization is shown in Fig.
1. The reactor operated with a 10 min hydraulic retention time
for the mixing zone and 3 h for the whole reactor. The obtained
struvite cake from the process was dried at room temperature
to form a powder.
Fig. 1. Experimental equipment for struvite crystallization.
D. Kim et al.
14
2.3. Pre-treatment for Phosphate P Release
Ultrasonic pre-treatment was performed for phosphate P release
with STH-750S ultrasound (Sonitopia, Korea) with operating fre-
quency of 20 kH and maximal power of 750 watt. Microwave
pre-treatment device had a microwave frequency of 2,450 MHz
with maximal power of 600 watt. During pre-treatment, the sup-
plied energy density ranged from 100 to 20,000 kJ/L. The energy
density of pre-treatment device can be defined with following
Eq. (2) (the energy density conditions of pre-treatment are shown
in Table 2):
  


 ×
(2)
where Power is in watt, t (time) in s, and V (sample volume)
in L.
Table 2. Energy Density Used in Pre-treatment
Energy density (kJ/L) Electricity (watt) Contact time (s)
100 33 300
200 67 300
500 167 300
1,000 333 300
2,000 667 300
5,000 750 667
10,000 750 1,334
20,000 750 2,667
2.4. Analysis and MINTEQ Model
The concentrations for total nitrogen (T-N), ammonia N, pre-treat-
ment for organic phosphate measurement were determined by
the following standard methods [24]. To study the release of phos-
phate ions concentration at different ultrasonic doses with ultra-
sonic disintegration, total phosphorus (T-P) and ortho-phosphate
P (PO43--P) levels in the effluent of the swine wastewater were
established by the Persulfate Digestion Method in HACH methods
10072. The phosphorous concentrations were determined by the
ascorbic acid method, using a UV-V is spectrophotometer at 800
nm (Smart Plus SP-1900PC, Woongki Science, Seoul, Korea). The
pH meter (Orionstar, Thermo Scientific, Waltham, MA, USA) was
calibrated after each experiment. The potential for struvite for-
mation as a function of pH was predicted by using chemical equili-
brium freeware Visual MINTEQ 3.0 developed by the U.S.
Environmental Protection Agency. Using the composition of the
anaerobically digested effluent of swine wastewater from P-city
as input, the model’s.
3. Results and Discussion
3.1. Effect of MAP Molar Ratios on Struvite Formation
In this research, the effects of Mg2+ : NH4+ : PO43- molar ratios
on struvite crystallization using synthetic swine anaerobic digester
wastewater were analyzed based on indications from previous
work [25-27]. At the start of the experiment, using a 0.1 NaOH
solution, the initial pH of the digester effluent sample was adjusted
to 9.0. Table 2 shows the effect of molar ratios on ammonia and
phosphate ions removal. Molar ratio of Mg2+ : NH4+ : PO43- for
the effective removal seemed to be 1.2 : 1.0 : 1.1.
Nelson et al. reported that adding magnesium ions did not
play an important role in phosphorus removal [11]. Therefore,
external addition of magnesium and phosphate should be con-
trolled to ensure the feasibility of struvite precipitation from
wastewater. Rahman et al. had a wide range of PO43- and Mg2+
ratios tested for struvite precipitation, but in most cases, the effec-
tive ratio was 1 : 1 or 1 : 1.2 [28]. Most research to date has
reported that the optimum molar ratio of Mg2+ : NH4+ : PO43-
for struvite precipitation is between 1.0 : 1.0 : 1.0 and 1.6 : 1.0 :
1.0 [28], although phosphate removal is not affected when Mg2+
: NH4+ : PO43- molar ratio is more than 1.3 : 1.0 : 1.0 at pH 9.0
in a full-scale plant [26].
There was a significant difference between ion removals in
real and synthetic effluents of swine wastewater anaerobic digester.
Ammonia N removal efficiency from synthetic wastewater was
over 90%, while real wastewater had lower than 50% ammonia
N removal. Addition of magnesium ion facilitated ammonia N
removal up to ratio of 1.2 and then it negatively influenced it.
However, more ammonia N was removed than would be predicted
based on the magnesium removal and the chemical formula for
struvite as shown in Fig. 2.
Table 3. Molar Ratios of Mg2+ : NH4+
: PO43- for Ammonia and Phosphate
Removal
NH4+Mg2+ PO43- NH4+ removal (%) PO43- Removal (%)
1.0
1
186.9 97.1
1.1 88.7 88.2
1.2 88.4 83.4
1.3 90.4 76.4
1.5 91.2 70.3
283.8 61.1
1.1
188.8 99.2
1.1 92.7 96.9
1.2 93.6 89.4
1.2
187.5 99.8
1.1 94.5 98.9
1.2 95.8 95.9
1.3
187.4 99.4
1.3 98.6 98.2
1.5 97.6 41.8
295.4 78.3
1.5
192.3 99.9
1.3 98.4 99.3
1.5 98.3 95.3
297.7 93.9
2
189.9 99.5
1.3 98.1 99.4
1.5 98.7 99.4
299.0 95.0
Environmental Engineering Research 22(1) 12-18
15
Fig. 2. Nitrogen and phosphorus removal according to PO43- : Mg2+
ratio for the effluent of swine wastewater anaerobic digester at pH 9.
Initial levels of magnesium, ammonium and phosphate ions
in the effluent of swine wastewater anaerobic digester were 32,
1,775, and 221 mg/L (molar ratio 1 : 74.9 : 1.8), respectively. The
ammonium ion concentration was much higher than magnesium
and phosphate ions concentrations. Therefore, magnesium and
phosphate ions sources had to be adjusted to completely remove
the ammonium ion. The experimental design allowed observing
the effects of magnesium and phosphate ions source dosage on
ammonia N and phosphate P removal as struvite. Experiments
were carried out with 10 min in the mixing zone and 3 h for
the whole reactor retention time and a pH of 9.0 according to
previous results.
The addition of magnesium and phosphate ions was required
to maximize ammonia recovery from the effluent of swine waste-
water anaerobic digester. The removal efficiency reached over
95%, and it was almost the same for the synthetic effluent.
Moreover, increasing added magnesium likely attributed to both
improvement of struvite precipitation and reduction of phosphate
P dose. Over dosing of magnesium could also contribute to de-
creased residual phosphorous concentration in the effluent and
phosphate recovery. However, if the concentration of magnesium
was increased up to a certain value, phosphorus removal would
not change [29].
Fig. 3. Addition of PO43- and Mg2+ to real wastewater for enhanced
recovery.
3.2. Effect of pH on Ammonia N and Phosphate P Removal
The ideal pH range for struvite precipitation could occur at a
wide pH range of 7.0 to 11.5. However, the suitable pH range
for struvite formation is 8 to 9.5 [30]; this is consistent with many
other reports [17, 29]. Interfering ions in solution also affect the
pH range for struvite precipitation and nutrient removal. To inves-
tigate the effect of pH on ammonia N and phosphate P removal
and recovery from the effluent of swine wastewater anaerobic
digester, the residual concentrations of ammonia N and phosphate
P were examined after each experiment. Removal of ammonia
N and phosphate P was calculated based on the change between
the initial concentration and the residual concentration.
Experiments were carried out under the same reactor conditions
at the pH range of 6.0 to 12.0 and an equal ratio (Mg2+ : NH4+ :
PO43- = 1.0 : 1.0 : 1.0).
Based on the batch experiment, the optimum pH for struvite
precipitation was investigated. Fig. 4 and Fig. 5 display the removal
efficiencies, depending on the pH, for ammonia N and phosphate
P in synthetic and real wastewaters, respectively. For synthetic
wastewater, as shown in Fig. 4, both ammonia N and phosphate
P removal efficiencies depended on the reaction pH, and the max-
imum ammonia N and phosphate P removal occurred at pH 9.0
and 11.0, respectively. For real wastewater, from Fig. 5, the optimal
Fig. 4. Ammonia N and P phosphate removal according to pH for
synthetic wastewater.
Fig. 5. Ammonia N and phosphate P removal according to pH for
real wastewater.
D. Kim et al.
16
range of phosphate P was reduced to between pH 8 and pH 10.
The maximum removal efficiency of phosphate P achieved were
over 95% in both wastewater types, while the maximum ammonia
N removal efficiency was very low in real wastewater due to the
high initial concentration of ammonia N. Thus, the pH of 8.0-10.0
can be considered as the optimum pH range for both ammonia
N and phosphate P removal from the effluent of swine wastewater
anaerobic digester.
Fig. 6 shows the optical microscope images of the struvite crystals
at various reaction pH values. This indicates larger struvite crystals
seen in higher pH values. Moreover, the increased size affected
struvite formation, and led to more precipitates forming at high
pH values. This could be explained in terms of more ammonia-based
precipitates forming compared to phosphate-based precipitates
at these conditions.
3.3. Pre-treatments Affecting Phosphate P Release
Acid-alkaline pre-treatments were applied for phosphate P release
from the effluent of swine wastewater anaerobic digester of P-city.
In this experiment, the initial pH was 7.2 and the pH was changed
with HCl and NaOH for the test pH range of 2.0-12.0. Acid-alkaline
pre-treatments were carried out under the same conditions so
that the ammonia N and phosphate P removals could be tested
in terms of the pH conditions of the wastewater. As shown in
Fig. 7, both T-P and phosphate P concentrations increased with
Fig. 7. Change of phosphorus concentration according to pH.
the increasing reaction pH, while poly-P concentration was slightly
decreased with the increasing pH. Fig. 8 shows the change of
phosphorus fraction according to pH. Maximum phosphate P re-
lease was observed at pH between 8.0-9.0.
In this work, the effect of ultrasonic and microwave pre-treat-
ment was also studied for changes in phosphate P release from
the effluent of swine wastewater anaerobic digester. The range
of the supplied energy density was from 100 kW/L to 20,000 kW/L.
From this analysis, phosphate P levels increased by increasing
ultrasonic energy density (up until 1,000 kJ/L); however, microwave
Fig. 8. Change of phosphorus fraction according to pH.
Fig. 9. Phosphate P release from swine wastewater according to energy
density.
a b c
Fig. 6. Struvite crystals (1000X); a) pH 8, b) pH 8.5, c) pH 9.
Environmental Engineering Research 22(1) 12-18
17
pre-treatment did not lead to any increases. At 1,000 kJ/L of energy
dose by using ultrasound, the highest phosphate P release (at
77.4%) was observed (Fig. 9).
3.4. Composition of Recovered Struvite
Precipitates from the anaerobically digested effluent of swine waste-
water collected from the experimental reactor were analyzed for
the composition of struvite. The contents of phosphorus and magne-
sium were similar to theoretical values but the ammonia content
was less than the theoretical value. This observed low ammonia
content could likely be attributed to precipitation of other minerals,
such as potassium struvite (KMgPO46H2O) instead of magnesium
ammonium phosphate due to introduction of potassium (KH2PO4)
for phosphate P supply.
For samples from the effluent of swine wastewater anaerobic
digester of P-city, Visual MINTEQ 3.0 was applied to concentrations
of Mg2+, NH4+ and PO43- at the pH range of 6.0 to 13.0 at 25˚C
to investigate the effect of pH on the amount and purity of struvite
formation from ammonia N and phosphate P removal in the
wastewater. Fig. 10 shows the levels and types of supersaturated
solids modeled by Visual MINTEQ. From the analysis, struvite
would be precipitated in the pH range 6.5 to 12.5, and as the
ion activity product (IAP) exceeded the minimum equilibrium
constant of solubility [31], struvite crystals would be formed in
the pH 7.5 to 10.5.
Table 4. Composition of Recovered Struvite
 Theoretical Sewage (Ueno and Fujii, 2001) This study
Mg2+ 9.9 9.7 9.9
NH4+7.3 7.3 4.1
PO43- 38.7 39.5 39.6
Fig. 10. Solids formation predicted at the pH range 6.0 to 13.0.
4. Conclusions
In this study, a wide range of molar ratios and pH values were
tested to determine optimum struvite recovery in terms of
efficiency. Microwave and ultrasonic pre-treatments were also in-
vestigated for phosphate P release from solid phases for increased
recovery of phosphorus from wastewater. From this analysis, the
optimum molar ratio of Mg2+ : NH4+ : PO43- for the effective removal
was 1.2 : 1.0 : 1.1. For real wastewater, the optimal pH range
of phosphate P was found to be between 8 and 10. The pH range
of 8 to 9 was found to lead to maximum phosphate P release
and could be the optimum condition for phosphorus recovery.
Ultrasound pre-treatment had the highest phosphate P release
of 77.4% at 1,000 kJ/L of energy dose but the microwave pre-treat-
ment had no effect under the tested conditions. Contents of phos-
phorus and magnesium in the collected precipitate were similar
to theoretical values but the ammonia content was less than the
predicted value. The modeling by Visual MINTEQ pointed to
struvite as the dominant solid phase in the pH range 7 to 11.
Acknowledgements
This study was supported by the Korea Ministry of the Environment
(MOE) as an “Eco-Innovation Project” (Project No. 2014-000015-
0017) and the Waste to Energy and Recycling Human Resource
Development Project funded by the Korea Ministry of the
Environment.
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Using chemical equilibrium model to predict amendments re-
quired to precipitate phosphorus as struvite in liquid swine
manure. Water Res. 2007;41:1689-1696.
... In addition, the pH also affects the formation of other precipitates relevant to the system under analysis, such as MgHPO 4 ·3H 2 O [17]. According to the literature and the experiments conducted in the present study ( Figure S1, Supplementary Materials), the highest removal efficiency (near 80%) was observed at a pH of 9. Therefore, this pH value was set to carry out the following tests [30,31]. ...
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Phosphorus (P) is a critical element for life, and wastewater treatment systems can be strategic points for its recovery, thereby avoiding eutrophication pollution in nature. The aim of this research was to investigate P recovery via struvite, namely in terms of the influence of operating parameters, coexisting interfering ions, and seeding. This paper focuses on synthetic solutions, although an assessment was performed on wastewater. The results of the assessment indicated that, in the synthetic solution, the minimum concentration for struvite precipitation is about 30 mg P/L, and that the Mg/P molar ratio of 1 promotes P removal efficiency with less contribution from other minerals. In order to assess the results in terms of real-world scenarios, the influence of coexisting ions (calcium and sodium) was investigated. Calcium was shown to have the greatest impact on the process, as 80% was removed for an initial concentration of 200 mg Ca/L. Indeed, these experiments generated an amorphous precipitate that did not contain struvite. The utilization of biomass ash (size < 63 µm) as seeding in crystallization increased the P removal efficiency compared to the sample without seed and helped to control the pH. The precipitation experiments with wastewater demonstrated good P removal efficiencies (over 90%) but indicated a reduction in the purity of the final product (struvite was a minor crystalline phase identified in XRD—15%wt).
... In phase 2, two conditions for struvite precipitation were tested: molar ratio 1 (MR1: NH 4 + excess; Mg:NH 4 :PO 4 = 1:1.5:1) and molar ratio 2 (MR2: Mg 2+ excess; Mg:NH 4 :PO 4 = 2:1:1), both of which have been considered optimum for struvite precipitation (Stratful et al. 2004;Quintana et al. 2005;Martí et al. 2010;Kim et al. 2017). ...
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This study investigates the effect of microwave treatment on the disintegration of municipal activated sludge. Sludge samples underwent heating at a targeted temperature of 90 °C for 35 min, with a 5-min retention time. Soluble chemical oxygen demand, sugars, proteins, nitrogen, and phosphorus exhibited notable increases compared to untreated samples. Results indicate a substantial (42–45%) rise in CH4 production during the anaerobic digestion process of the disintegrated sludge compared to the untreated counterpart CH4 production was estimated using a transference model, which showed the best fit compared to other models. Further experimentation involved testing digested sludge with excess soluble NH4–N and PO4–P for the recovery of struvite at a 1.50/1/1 (Mg/N/P) ratio. The findings reveal that up to 90.1% and 90.4% of PO4–P and NH4–N, respectively, can be efficiently removed from the solution. Despite the increased CH4 output, the energy recovered was insufficient to offset the electrical energy used by the microwave. There was a significant deterioration in sludge filter resistance due to the increase in fine particles and bound water after anaerobic digestion of the pretreated sludge.
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This report shows that silica sulfate is removing phosphate from wastewater very efficiently. Phosphorus removal and recovery from wastewater is a worldwide issue due to pollution of natural waters by phosphate and depletion of phosphate ores. Adsorption is a process that can remove phosphate at low concentrations. Adsorption also allows the recovery of phosphate for possible re-use. Here, we studied the adsorption of phosphate from wastewater using commercial Zr ferrite, Zr-MCM 41 and silica sulfate. We calculated equilibrium isotherms, kinetic models and thermodynamic effects under conditions similar to real wastewaters. We found that the equilibrium data for the adsorption of phosphate were best fitted to the Freundlich model. The results show that the maximum uptake of phosphate was 3.36 mg g−1 for Zr-MCM, 27.73 mg g−1 for Zr ferrite and 46.32 mg g−1 for silica sulfate. The kinetic results of the three adsorbents were satisfactorily predicted using a pseudo-second-order model. We found that silica sulfate provided excellent characteristics in terms of the maximum adsorption and rate constant for the adsorption of phosphate. The thermodynamic data showed that increasing the temperature enhanced the adsorption of phosphate onto silica sulfate. Our findings will help to define efficient methods to remove phosphate from wastewater.
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Struvite is a phosphate mineral that can form hard-scale deposits in the recycle components of livestock waste management systems that utilize recycled lagoon effluent to transport waste. Previous research of struvite formation in piping systems has been hindered by the presence of erroneous solubility constant values in the literature and the use of a set of less-than-comprehensive equilibrium equations. This article identifies the erroneous solubility product constant commonly found in text books and documents an apparently correct value. Previous work using a set of simplified equilibrium equations indicated that the pH for minimum solubility of struvite is 10.7. For the study described herein, a more comprehensive set of equilibrium model, indicated that the pH of minimum solubility is approximately 9.0. Information derived from this study can aid in the development of management practices which will either prevent struvite formation or remove struvite from the system with controlled precipitation
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Selective release characteristics of phosphorus and nitrogen from waste activated sludge (WAS) were investigated during combined thermal and alkali treatment. Alkali (0.001-1.0N NaOH) treatment and combined thermal-alkali treatment were applied to WAS for releasing total P(T-P) and total nitrogen(T-N). Combined thermal-alkali treatment released 94%, 76%, and 49% of T-P, T-N, and COD, respectively. Release rate was positively associated with NaOH concentration, while temperature gave insignificant effect. The ratio of T-N and COD to T-P that released with alkali treatment ranged 0.74-0.80 and 0.39-0.50, respectively, while combined thermal-alkali treatment gave 0.60-0.90 and 0.20-0.60, respectively. Selective release of T-P and T-N was negatively associated with NaOH. High NaOH concentration created cavities on the surface of WAS, and these cavities accelerated the release rate, but reduced selectivity. Selective release of P and N from sludge has a beneficial effect on nutrient recovery with crystallization processes and it can also enhance methane production. Copyright © 2015 Elsevier Ltd. All rights reserved.
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For phosphorus (P) recovery from waste activated sludge (WAS), the most important step is to release P into the solution, which is greatly dependent on the pH of the solution. The contributions of different P speciation to P release amount from WAS as well as P release kinetics were investigated at different pHs, with the Standards Measurements and Testing (SMT) protocol being used for P fractions tests. The results showed that the total P in the solid (TP(s)) release percentages were 36.2% and 12.4% at pH = 2.0 and pH = 11.0, respectively. P speciation and fractions study made clear that the released P comes mainly from dissolving of inorganic P (IP) under acid condition, but from non-apatite inorganic P (NAIP) and organic P (OP) under alkaline condition. Simulation study using Visual MINTEQ indicated that the P release amount came from the experimental results is unanimous.
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The aim of this study was to explore the feasibility of utilizing inorganic mesostructures for the removal of phosphorous in laboratory experiments. The emphasis of the experiments was on the comparison of the efficiency of phosphorous adsorption between mesostructures synthesized using two different inorganic materials. Powder X-ray diffraction, Fourier transformed infrared spectroscopy, and Brunauer-Emmett-Teller(BET) methods were used to characterize the inorganic mesostructures. The efficiencies of silica and titanium mesostructures for the removal of phosphorous from aqueous solutions were investigated on a batch scale. Equilibrium data were analyzed using the Langmuir isotherm. The maximum adsorption capacities of the mesostructured adsorbents were found to be 49.3 and 19.5 mg g-1 for the titanium and silica mesostructures, respectively. The adsorption kinetics was best described by a pseudo-third-order kinetic model. The results from this study indicated that the titanium mesostructure, because of low cost and high capability, has the potential to be utilized for the cost-effective removal of phosphorous from sewage or wastewater. (C) 2011 American Institute of Chemical Engineers Environ Prog, 2012