Bioresource Technology 172 (2014) 253259

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Recovery and removal of ammonianitrogen and phosphate from swine

wastewater by internal recycling of struvite chlorination product
Haiming Huang , Yang Jiang, Li Ding
Hebei Key Laboratory of Applied Chemistry, School of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, PR China

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Recovery of phosphate was

signicantly inuenced by the

solution pH.
 Purity of struvite was mainly
determined by the solution pH and
Mg:P molar ratio.
 Nitrogen in struvite could be
completely oxidized to N2 gas by
NaClO.
 High NH4-N removal was achieved
using the chlorination decomposition
product.
 84.5% of NH4-N can be removed from
the swine wastewater by the
proposed process.

a r t i c l e

i n f o

Article history:
Received 19 July 2014
Received in revised form 31 August 2014
Accepted 4 September 2014
Available online 16 September 2014
Keywords:
Ammonianitrogen
Phosphate
Struvite
Chlorination
Recycling

a b s t r a c t
The recovery of the total orthophosphate (PT) and removal of the total ammonianitrogen (TAN) from
swine wastewater were investigated through a combined technology of using bittern as the magnesium
source in struvite precipitation along with internal recycling of the chlorination product of the recovered
struvite. Results revealed that the PT recovery efciency and the struvite purity was mainly depended on
the wastewater pH and the Mg:PT molar ratio. Co-precipitations of Mg3(PO4)2, MgKPO4, Ca3(PO4)2, and
Mg(OH)2 (pH > 9) were conrmed to be responsible for the decrease in the purity of struvite. The decomposition of recovered struvite by sodium hypochlorite (NaClO) was feasible. The TAN concentration of the
swine wastewater was decreased to 63 mg/L by internal recycling of the chlorination decomposition
product for seven cycles. An economic evaluation showed that 37% of the treatment cost of the proposed
process could be saved as compared with struvite precipitation using pure chemicals.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Nitrogen (N) and phosphorus (P) are the indispensable
elements for all living organisms. They play an irreplaceable role
in the breeding, growth, and development of organisms. Nitrogen
is abundant in the nature, and its resource is sufcient and hence
not a cause for concern. However, the resource amount of P is
rather limited; it has been estimated that the phosphate rock
Corresponding author. Tel.: +86 335 8387 741; fax: +86 335 8061 569.
E-mail address: huanghaiming52hu@163.com (H. Huang).
http://dx.doi.org/10.1016/j.biortech.2014.09.024
0960-8524/ 2014 Elsevier Ltd. All rights reserved.

reserves in the world that can be mined in the form of P2O5 is

7  109 metric tons (MT) (Shu et al., 2006). Phosphate rock (apatite) is mainly used as a raw material in fertilizer manufacturing.
With the increasing world population, the demand for P fertilizer
has been estimated to increase from 34.3  106 MT in 2000 to
47.6  106 in 2020 and to 83.7  106 in 2050 (Tilman et al.,
2001). Given the current rate of consumption, it can be predicted
that the P resource in the world would last for a maximum of
200 years more. Therefore, it is of great importance to recover
the used P from the society for sustainable development of P
resource.

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H. Huang et al. / Bioresource Technology 172 (2014) 253259

Swine wastewater is a wastewater type that contains abundant

N and P, which are major pollutant source to water bodies if discharged without adequate treatment. Pollution problems related
to the N and P discharge of swine wastewater commonly include
eutrophication and dissolved oxygen depletion in water bodies as
well as toxicity to the aquatic life and increase in the chloride dose
for drink water disinfection due to the presence of ammonia (Dong
and Reddy, 2012; Huang et al., 2010). In order to avoid the appearance of these problems, more stringent water quality standards
have been established to decrease the levels of P and N entering
surface water resources (Adnan et al., 2003). Therefore, the recovery of P from swine wastewater is not only an available means to
realize sustainable development of P resource but also an essential
measure for maintaining the water environment quality. For P
recovery, various physicalchemical and biological methods such
as metal ion (e.g., Al, Fe, and Ca) precipitation (Xu et al., 2014),
adsorption (Alshameri et al., 2014), biological nutrient removal
process (Bassin et al., 2012), and struvite (magnesium ammonium
phosphate, MAP) crystallization (Huang et al., 2014) have been
reported. Among these processes, struvite crystallization is a
promising and feasible method to recover nutrients from swine
wastewater as the total ammonianitrogen (TAN) and the total
orthophosphate (PT) content can rapidly react with magnesium
(Mg) to form white struvite crystal, the solubility of which is only
0.023 mg per 100 g water (Li et al., 1999).
Swine wastewater generally contains several hundreds milligram per liter of TAN, less than 200 mg/L of PT, and small amount
of Mg (Liu et al., 2011). To obtain a high recovery efciency of PT,
addition of external Mg source is required in the process of struvite
crystallization. Pure Mg salts such as magnesium chloride (MgCl2)
and magnesium sulfate (MgSO4) are often selected as the Mg
source of struvite crystallization, but owing to their high cost price,
their use tends to increase the recovery cost of PT. Therefore, using
low-grade Mg-containing materials such as brucite mineral
(Huang et al., 2012), magnesite pyrolysate (Chen et al., 2009), magnesite mineral (Gunay et al., 2008), and seawater (Liu et al., 2013)
as alternatives of Mg is a good strategy to decrease the recovery
cost. Bittern is the remaining mother liquid in the process of seawater salt manufacturing and contains mostly MgCl2, MgSO4,
sodium chloride, and small amounts of other inorganic compounds
(Lee et al., 2003). With an increase in the degree of seawater
enrichment, the maximum Mg2+ content in bittern is near
60,000 mg/L. In a previous study (Lee et al., 2003), bittern has
proved to be an effective Mg source for struvite crystallization.
Although, in the process of PT recovery by struvite crystallization, some proportion of the TAN in swine wastewater can be
removed, but the removed amount is small as the amount of
TAN in swine wastewater is much more than that of PT. High
contents of TAN remaining in the swine wastewater may inhibit
the activity of microorganisms in the biological treatment system,
thereby lowering the treatment efciency of wastewater (Vadivelu
et al., 2007). Therefore, there is a need to decrease the TAN concentration of swine wastewater before biological processing. Generally, under this condition, additional phosphate has to be added
to the wastewater if high removal of TAN is desired. Nevertheless,
this operation would signicantly increase the treatment cost. To
overcome this issue, recycling of struvite pyrogenation product is
often considered to be an alternative process (Sugiyama et al.,
2005; Trker and elen, 2007). However, with an increase in the
recycling time, the removal ratio of TAN by this process decreased
progressively due to the accumulation of byproducts such as
Mg2P2O7 and Mg3(PO4)2 during struvite pyrogenation and the loss
of phosphate and Mg in during pyrolysate reuse (Huang et al.,
2011; Trker and elen, 2007).
In this study, in order to simultaneously recover PT and remove
TAN from swine wastewater, a novel treatment process that

included the recovery of PT and the reuse of recovered struvite

was proposed. In this process, bittern as the external Mg source
in struvite precipitation was added to the swine wastewater for
the recovery of PT. The recovered struvite was decomposed by
sodium hypochlorite (NaClO), and its product was continuously
reused for the removal of TAN from the supernatant after PT recovery. The effects of pH and Mg dose on the recovery efciency of PT
and the purity of struvite were rst explored. Subsequently, the
inuences of pH and Cl/N weight ratio on the chlorination decomposition efciency of struvite were investigated. Finally, multiple
recycling of the chlorinated product was performed and an economic evaluation of the proposed process was performed.
2. Methods
2.1. Materials
Swine wastewater used during this study was collected from a
pig farm located in Beijing. Before use, the swine wastewater was
ltered through lter paper to remove the suspended solids and
then stored in a 30-L plastic bucket at 5 1 C. The chemical
characteristics of the ltered wastewater are given in Table 1.
The bittern used in the experiments was collected from a solar salt
eld in Tianjin, and its main components are listed in Table 1.
2.2. Experimental methods
The ow chart of the proposed process is shown in Fig. 1. As
seen in Fig. 1, the ow chart was divided into three stages: phosphate recovery, struvite decomposition, and product multiple recycling. (a) Swine wastewater was poured into the phosphate
recovery reactor (PRR), and the phosphate in the wastewater was
recovered with bittern as Mg source of struvite crystallization,
followed by the addition of the recovered struvite and the
supernatant into the struvite decomposition reactor (SDR) and
multiple-recycle reactor (MRT), respectively. (b) The recovered
struvite was decomposed using NaClO as an oxidant, and the resulting decomposition product was added to the MRT for the removal
of the remaining TAN in the supernatant. (c) The struvite formed in
MRT was returned to SDR and step (b) was repeated. (d) After
several repetitions of steps (b) and (c), the supernatant after
solidliquid separation was discharged to the next treatment
process and the formed struvite was recovered.
Here, batch experiments were conducted to optimize the operating conditions of each stage. The specic experiment procedures
were as follows:
1. PT recovery: For the rst-stage recovery of phosphate, 1000 mL
of swine wastewater was added into the PRR (a 1500-mL jar
with an airtight lid). Subsequently, bittern was added to the
swine wastewater at different Mg/PT molar ratios, and the
Table 1
Compositions of ltered swine wastewater and bittern used in this study.
Swine wastewater
Parameter

Bittern
Value and S.D. Parameter

pH
7.5 0.2
Alkalinity (as CaCO3) (mg/L) 2939 193
COD (mg/L)
3298 276
TAN (mg/L)
406 28
PT (mg/L)
128 13
K+ (mg/L)
338 21
Ca2+ (mg/L)
58 9
Mg2+ (mg/L)
28 5
3+
Fe (mg/L)
1.2 0.3
Zn2+ (mg/L)
0.6 0.2
3+
Al (mg/L)
0.5 0.1

Value and S.D.

Ca2+ (mg/L)
90 20
Mg2+ (mg/L) 44,000 2100
+
K (mg/L)
12,300 600
Na+ (mg/L)
58,000 1800
Cl (mg/L)
202,000 13,000
SO2
60,000 3000
4 (mg/L)
Br (mg/L)
5300 400

H. Huang et al. / Bioresource Technology 172 (2014) 253259

255

Fig. 1. The ow chart of the designed struvite recovery and multiple-recycle process.

mixture was agitated by a magnetic stirrer at pH of 810.5.

After 30 min of the reaction, the mixture was allowed to settle
for another 30 min. The supernatant was ltered through a
0.45-lm membrane lter for component analysis. The recovered struvite was washed with deionized water thrice and then
dried in an oven at 35 C for 48 h. The dried precipitates were
dissolved in 0.5% nitric acid solution and analyzed for the purity
of struvite and the contents of various elements.
2. Struvite decomposition: The precipitates obtained under the
above-mentioned optimal conditions were added to the SDR
(a 50-mL jar) to decompose struvite via chlorination reaction.
The subsequent experiment procedures were as follows: Firstly,
10 mL of deionized water was added to the SDR. Then, NaClO
solution was added to the solidliquid system at the designed
chlorine/nitrogen (Cl/N) weight ratio and the mixture was stirred at 200 rpm. The pH was adjusted with 1.5 M NaOH or 1.5 M
HCl as required (59). The reaction lasted for 10 min and then
1 mL of 1 M sodium hyposulte solution was added into the
reaction mixture to stop the reaction. Finally, the solution pH
after reaction was adjusted to 3 with 0.5% nitric acid to completely dissolve the solid matter, and 5 mL of the resulting solution was assessed by component analysis. In addition, to
investigate the TAN removal performance of the decomposition
product obtained under the optimal conditions, it was reused to
remove TAN from synthetic wastewater, which was prepared
by dissolving NH4Cl of analytical grade into pure water (TAN
concentration, 406 mg/L) at the TAN:PT ratio of 1:1 and at a
given experimental pH of 810.5. The experimental procedures
were similar to those detailed in step (1).
3. Product multiple recycling: Based on the results of the steps (1)
and (2), the entire decomposition product of the precipitates
obtained from 1000 mL swine wastewater was added to the
supernatant (approximately 1000 mL). Then, the recovered
struvite precipitate was recycled, [i.e., steps (2) and (3) were
repeated]. After treatment in MRT, the nal struvite precipitate
was recovered and the treated swine wastewater was discharged into the subsequent treatment vessel. The efuent
and the recovered struvite were analyzed according to the
above-mentioned methods.

2.3. Analytical methods

In this study, water samples were analyzed according to the
standard methods detailed elsewhere (APHA, 1998). The pH of
solution was measured using a pH meter (pHS-3C; China). The concentrations of the TAN and PT in the reaction solution were determined using the Nesslers reagent spectrophotometric method and
MoSb anti-spectrophotometric method (752 N-spectrophotometer; China), respectively. Metal ions such as K+, Ca2+, Na+, and
Mg2+ were quantied by using an atomic adsorption photometer
(AA-6800; Shimadzu, Japan). Anions in bittern such as Cl, SO2
4 ,
and Br were quantied by using the Dionex Series 4500i Ion Chromatograph. The collected solids in the experiments was washed
with deionized water thrice and then dried in an oven at 35 C
for 48 h. The dried solids were characterized under a scanning electron microscope (SEM; SUPRA 55 SAPPHIRE; Germany) and X-ray
diffraction analyzer (XRD; DMAX-RB; Rigaku, Japan). All tests were
performed in triplicate, and their average data was reported.

3. Results and discussion

3.1. Recovery of phosphate
The crystallization of struvite occurs only when the ionic activity products of Mg2+, NH+4, and PO3
4 exceeds the thermodynamic
solubility product of struvite (Wang et al., 2006). However, the species of the three constitutional ions were signicantly inuenced
by the solution pH. Therefore, to effectively recover the TAN and
PT from swine wastewater by struvite crystallization, control of
the solution pH is the key factor. In addition, increasing the ionic
activity product through increase in the Mg2+ concentration is also
an effective method. The changes in the removal efciencies of TAN
and PT as well as the purity of struvite with the solution pH and
Mg:PT molar ratio are shown in Fig. 2.
As shown in Fig. 2a, at the pH range of 89.5, the removal efciency of PT signicantly increased with an increase in the pH and
Mg:PT molar ratio. Nevertheless, at pH > 9.5, further increases of
pH and Mg:PT molar ratio incurred a slight decrease in the removal

H. Huang et al. / Bioresource Technology 172 (2014) 253259

90
Mg:PT=1:1
Mg:PT=1.2:1
Mg:PT=1.4:1

80
70
15

10
5
0
80

4.5

Ca

Mg

40
K

TOC

35

4.0
3.5

30

3.0

25

2.5

20

2.0

15

1.5
10

1.0

0.5

0.0

Mass concentration (mg/g)

100

Molar concentration (mmol/g)

Struvite purity (%) TAN removal rate (%)

PT removal rate (%)

256

8.0

8.5

9.0

9.5

10.0

10.5

pH

60
Fig. 3. The analysis of the elements of the precipitates obtained at different pHs and
its TOC value (Mg:PT = 1.2:1).

40
20
8.0

8.5

9.0

9.5

10.0

10.5

pH
Fig. 2. The changes in the removal efciencies of the TAN and PT and the purity of
struvite with pH and Mg:PT molar ratio.

efciency of PT. It was observed from Fig. 2b that an increase in the

amount of added Mg2+ has a negligible effect on the removal of
TAN. At a given Mg:PT ratio, the TAN removal efciency rst
increased at a pH 89 and then decreased at pH 9.510.5. At pH
9 and Mg:PT molar ratio of 1.2:1, the removal efciencies of the
TAN and PT were 12.9% and 98%, respectively. The changes in the
purity of struvite in the obtained precipitates with pH and Mg:PT
ratio are shown in Fig. 2c. From this gure, it can be observed that
the purity of struvite slightly decreased in the pH range of 89, but
sharply decreased in the pH range of 910.5. Furthermore, at
pH > 9, an increase in the Mg:PT molar ratio further decreased
the purity of struvite.
Although struvite is constituted by Mg2+, NH+4, and PO3
in
4
equal molar ratio, its formation reaction proceeds by the Eq. (1)
given below (Wu and Zhou, 2012).

Mg2 NH4 HPO2

4 6H2 O ! MgNH4 PO4  6H2 O # H

At solution pH < 8, although the majority of the TAN in solution

was presented in the form of NH+4 species, high concentration of H+
may inhibit the formation of struvite [according to Eq. (1)], resulting in low removal efciencies of the TAN and PT. When the pH
increased from 8 to 9, although the ratio of NH+4 species in the
TAN rapidly decreased from >90% to about 55% (Li et al., 2012),
the concentration of HPO2
rapidly increased along with a
4
decrease in the H+ concentration. This event could promote the
proceeding of the precipitation reaction, resulting in an increase
in the removal efciencies of the TAN and PT. However, at
pH > 9, the conversion from NH+4 to NH3 may accelerate, and at
pH 10.5, 95% of NH+4 can be converted to NH3 (Li et al., 2012),
which cannot be precipitated by the formation of struvite. In
addition, some Mg2+ in the solution may react with PO3
and
4
OH to form amorphous Mg3(PO4)2 and Mg(OH)2 (Wu and Zhou,
2012). Consequently, the ionic activity product of the struvite constitutional ions decreased, leading to a decrease in the removal
efciency of the TAN. Nevertheless, the PT removal efciency
maintained a stable value owing to the formation of other amorphous solids such as Mg3(PO4)2 and Ca3(PO4)2. This event may be
responsible for the rapid decrease in the purity of struvite at the
pH of 910.5.

In order to further determine the relationship between purity of

struvite and pH, the components of the precipitates obtained at
different pHs and at the Mg:P molar ratio of 1.2:1 were analyzed.
The contents of K, Ca, N, Mg, P, and TOC are given in Fig. 3. As
observed in the gure, with an increase in the pH, the molar concentration of N in the precipitates progressively decreased,
whereas those of Mg and P gradually increased. Furthermore, it
seemed that the molar concentration of Mg obviously exceeded
that of P at pH > 9. The stoichiometric ratio of Mg2+, NH+4, and
PO3
4 in struvite is 1:1:1. The Mg:N (or P:N) molar ratio exceeding
this value in the obtained precipitates indicated formation of some
impurity during precipitation. In this work, it can be clearly
observed that the Mg:N (or P:N) molar ratio increased with
increasing pH from 8 to 10.5, which suggested that some Mgcontaining compounds were formed and their amount increased
with an increase in the pH. These Mg-containing compounds
may include Mg3(PO4)2, MgKPO46H2O, MgHPO43H2O, and
Mg(OH)2. Since the formation of MgHPO43H2O occurs signicantly
only at pH around 6 and at high concentrations of Mg and phosphate (Musvoto et al., 2000), it was not formed in this study. The
K+ present in the swine wastewater could compete with NH+4 to
form MgKPO46H2O (struvite-K), which is one of the struvite analogs (Wilsenach et al., 2007). The data shown in Fig. 3 revealed that
MgKPO46H2O formed at all the tested pH and that its amount
increased slightly with an increase of pH. Mg(OH)2 generally
begins to form at pH > 9, and its amount increases with an increase
in the pH (Wu and Zhou, 2012). This may explain why the Mg:P
molar ratio in the precipitates gradually increased at pH > 9.
Certainly, this may also be caused by the increase in the amount
of Mg3(PO4)2. Hence, it was conrmed that, at the pH range of
89, the possible byproducts containing Mg may include
Mg3(PO4)2 and MgKPO46H2O, and the other byproducts further
included Mg(OH)2 at pH > 9. Presence of high concentration of
Ca2+ in swine wastewater could react with PO3
4 to form Ca3(PO4)2.
As observed from Fig. 3, at the tested pHs, all of the obtained
precipitates contained Ca, and its content progressively increased
with an increase in the pH. In addition, the TOC values of the precipitates were measured. The results indicated that, at pH > 9.5, the
TOC value obviously increased, suggesting an increase in the
amount of organic matter in the precipitates, probably caused by
the adsorption of these amorphous compounds. Nonetheless, it
can be speculated that the organic matter content in the precipitates have a weak effect on the chlorination decomposition of
struvite.
Solution pH can inuence the ionic equilibrium system in swine
wastewater, which resulted in the changes of composition and

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H. Huang et al. / Bioresource Technology 172 (2014) 253259

The chlorination decomposition of the struvite obtained at

Mg:PT 1.2:1 and pH 9 was performed at the pH range of 59 and
Cl/N ratio of 6.5:1 to 9.5:1. The results shown in Fig. 4 indicate that
the decomposition efciencies of nitrogen in struvite were inuenced by the pH and Cl/N ratio. Under the same pH values, the N
decomposition efciencies signicantly increased with an increase
in the Cl/N ratio. For example, at pH 6.0, the N decomposition efciencies increased from 80% to 99% as the Cl/N ratio increased from
6.5 to 8.5; however, it remained unchanged when the Cl/N ratio
increased to 9.5. Under the same Cl/N conditions, the N decomposition efciencies increased at pH 56, reached a peak at pH 6, and
then slightly decreased at pH 79.
It is well known that the TAN in swine wastewater can be oxidized to nitrogen gas by breakpoint chlorination. In this study,
with the addition of NaClO to the struvite solidliquid system, it
can be converted to hypochlorous acid through adjustment of the
pH. In the chlorination process, the overall reaction occurring in
the solution system can be expressed as follows:

ClO H ! HOCl

MgNH4 PO4 H $ Mg2 NH4 HPO2

4

3


2NH4 3HOCl ! N2 3H2 O 5H 3Cl

As the chlorination reaction proceeded, the concentrations of

Mg2+ and HPO2
4 in solution system rapidly increased. Under this
pH condition, supersaturated Mg2+ and HPO2
in the solution
4
may form insoluble MgHPO43H2O and Mg3(PO4)2 (Mijangos
et al., 2004; Wu and Zhou, 2012). During the experiments,

Nitrogen removal ratio (%)

100

Cl/N=6.5:1
Cl/N=7.5:1

Cl/N=8.5:1
Cl/N=9.5:1

80
60
40
20
0
5

7
pH

90
80
70
60
50
40
8.0

8.5

9.0

9.5

10.0

10.5

pH

3.2. Chlorination decomposition of the recovered struvite

100

TAN removal ratio (%)

morphology of the precipitates. In order to further corroborate the

relation between the purity of struvite and pH, the precipitates
obtained at Mg:PT 1.2:1 and at pH 8.5, 9.5, and 10.5, respectively,
were characterized by SEM and XRD. The SEM image showed that
some regular prismatic crystal with a diameter of 2050 lm and
smooth surfaces were obtained at pH 8.5. When pH increased to
9.5, the size of the crystals decreased (1030 lm) and their surfaces became coarse. At pH 10.5, no obvious crystal was observed,
and amorphous compounds amounted for the majority of the precipitates. XRD patterns demonstrated that the intensity of characteristic peaks of struvite in the precipitates decreased with an
increase in the pH of 8.510.5, suggesting that the content of struvite in the precipitates reduced with an increase in the pH.

Fig. 4. The decomposition ratio of nitrogen in struvite at different pH and Cl/N

ratios.

Fig. 5. TAN removal ratio for recycling the struvite chlorinated product at different
pHs.

abundant white aggregations with large particles were formed at

the original solidliquid system. Furthermore, the precipitates
obtained at pH 6 and Cl/N ratio 8.5 was collected and characterized
by SEM and XRD. SEM image showed that the morphology of the
precipitates was rectangular block with a diameter of 520 lm.
XRD pattern indicated that the main composition of the solid product was MgHPO43H2O. Although the formation of MgHPO43H2O
and Mg3(PO4)2 occurred in the chlorination reaction, large amounts
of Mg2+ and phosphate anions still remained in the solution. Hence,
the total solid and liquid products after chlorination decomposition should be added into the wastewater for reuse.
Since the chlorination decomposition product contained a certain amount of Mg3(PO4)2, which has a weak effect on the removal
of TAN (Yu et al., 2012), the solution pH of the product had to be
adjusted to reduce the effect of Mg3(PO4)2. In this study, the pH
of the chlorination product solution was adjusted to 4 before recycling. The TAN removal efciencies of recycling the nal product
solution at the pH of 810.5 were determined (Fig. 5). As seen in
Fig. 5, it was observed that the TAN removal efciencies rapidly
increased from 73% to 88% when the pH of the wastewater solution
increased to 89 and then slightly decreased to 85% at pH 9.5. At
pH 10.5, the TAN removal efciency rapidly declined to 74%. The
results were similar to those of using pure Mg and phosphate salts
(Li and Zhao, 2003; Yetilmezsoy and Sapci-Zengin, 2009). Here, the
recycling of the decomposition product was mainly achieved by
the reaction in Eq. (1).
In the previous literatures, Zhang et al. (2009) reported that
approximately 83% of the TAN could be removed from the coking
wastewater when the product of struvite pyrolyzed with NaOH
was recycled at pH 9.5. He et al. (2007) recycled the NaOH decomposition product of struvite at pH 9 for the removal of TAN from
landll leachate to obtain a high degree of TAN removal. Yu et al.
(2013) found that the optimum pH for the recycling of the struvite
NaOH pyrolysate was 9.5, and the TAN removal ratio could be
maintained at >80%. Huang et al. (2011) reported that the maximum TAN removal ratio (82.5%) was achieved at the pH range of
88.5 when the struvite pyrolysate was recycled for the treatment
of swine wastewater. Comparing with the results reported by these
literatures, it was found that the TAN removal efciency for recycling the chlorination decomposition product clearly exceeded that
of using the struvite NaOH pyrolysate.
3.3. Mutiple-recycle of decomposition products
Under the above-mentioned optimal conditions, the mutiplerecycle of struvite decomposition product was performed (Fig. 6).
It can be noted from Fig. 6 that, with an increase in the number

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H. Huang et al. / Bioresource Technology 172 (2014) 253259

TAN
PT

60
50
40
30

20

3
2

10

1
0

Amount of TAN removed (mg/L)

Remaining concentration (mg/L)

70
300
250
200
150
100
50
5

Table 2
The market price of chemicals used and the economic analysis of the proposed
process as compared to the struvite precipitation with pure chemicals.
Chemical

Market
price
($/kg)

Cost of the
proposed process
($/m3
wastewater)

Cost of struvite
precipitation with pure
chemicals ($/m3
wastewater)

MgCl26H2O
Na2HPO412H2O
NaOH
NaClO (10%)
HCl (31%)

0.079
0.36
0.29
0.07
0.03

0.63
1.75
0.20

0.52
3.20
0.38

Total

2.58

4.10

0
1

2
3
4
5
6
7
Recycle times of decomposition product

Fig. 6. Changes in the TAN and PT by recycling of struvite chlorinated product with
different number of recycling times.

of times of recycling, the TAN concentration of swine wastewater

decreased gradually and the remaining PT concentration in the
solution remained constant at the range of 25 mg/L. When
the decomposition product was internally recycled seven times,
the TAN concentration reduced to 63 mg/L. From calculation, it
was derived that 84.5% of the TAN could be removed by the
proposed process. The amount of the TAN removed at different
recycling times was maintained at approximately 43 mg/L wastewater. This suggested that the TAN removal performance of the
struvite decomposition product did not reduce with an increase
in the number of recycle times. This may be due to the fact that
the amounts of active Mg and phosphate kept the same during
the mutiple-recycle. Trker and elen (2007) reported that when
the struvite pyrolysate was repeatedly reused ve times, the TAN
removal efciency progressively decreased from 92% in the rst
cycle to 77% in the fth cycle. Huang et al. (2011) found that the
TAN removal efciency was initially 80% and rapidly reduced to
67% in the fth cycle recycling of the struvite pyrolysate as the
Mg and phosphate sources in struvite precipitation. He et al.
(2007) recycled the pyrolysate of struvite and achieved the TAN
removal of >90% in the rst cycle; however, it rapidly decreased
to <65% in the sixth recycle. In these literatures, the decrease of
the TAN removal efciency may be due to the increase of the inactive Mg3(PO4)2 and Mg2P2O7 contents in recycled pyrolysate
(Schulze-Rettmer et al., 2001) and the losses of Mg2+ and PO3
4 in
the supernatant per recycle time. In addition, the accumulation
of some components such as potassium and calcium in the wastewater may also be an important factor toward inhibiting the
formation of struvite in later cycles (Huang et al., 2011). However,
in the proposed process, all these problems were not noted. When
the desired number of recycle times was completed, the nal
precipitate was collected and characterized by SEM and XRD.
SEM image (Fig. S1, see Appendix A) showed that the crystals were
rectangular in shape and accompanied with some folds on the surface and their sizes were irregular (1030 lm). XRD pattern
(Fig. S2, see Appendix A) revealed that the main component of
the precipitates was struvite. Moreover, the chemical composition
analysis of the precipitates demonstrated that the purity of struvite
was 90.3%, and the contents of K, Ca, Mg, N, and P in it were 0.10,
0.47, 3.98, 3.56, and 3.91 mmol/g, respectively. Therefore, the
precipitates could be recovered as released fertilizer in agriculture
(Antonini et al., 2012). In addition, the Na+ concentration of the
efuent after the treatment was measured to be around
4500 mg/L, which may have a moderate inuence on the subsequent biological treatment (Huang et al., 2014).

3.4. Economic evaluation

Economic evaluation of the proposed recovery and recycling
process of struvite was performed and compared to the struvite
precipitation using pure chemicals (MgCl26H2O and Na2HPO4
12H2O; Mg:N:P = 1:1:1). In this evaluation, to facilitate the calculation, only the cost of chemicals used in the treatment process was
considered, whereas the manpower, transportation and energy
costs and the market values of the recovered struvite were not
considered. Since the bittern used in the experiments was the
byproduct resulting from the process of manufacturing salt, its
price was very low. Additionally, the amount of bittern consumed
in the treatment was only 2.1 L/m3 swine wastewater, the cost of
bittern was also not considered in the calculation. The market costs
of various chemicals used and the calculated cost are listed under
Table 2. As shown in Table 2, the cost of the proposed process
(including the recovery of struvite and seven recycle times of
decomposition product) was incurred due to the costs of HCl,
NaOH, and NaClO consumed in the treatment process. The total
cost was calculated at 2.58 $/m3 swine wastewater. In comparison
to the costs of struvite precipitation with pure chemicals (4.10 $/m3
swine wastewater; Table 2), 37% of the cost could be reduced by the
proposed process.
In the published literatures, Huang et al. (2011) reported that
recycling of the struvite pyrolysate for three process cycles could
save 81% of the cost as compared with struvite precipitation with
pure chemicals. He et al. (2007) reduced approximately 44% of
the chemical costs when the pyrolysate of struvite was recycled
for three cycles. In the proposed process, although the level of cost
reduction was lower than that in the reported paper, there was no
secondary pollution of ammonia, which may be present in the process of struvite pyrogenation.
4. Conclusions
The solution pH and Mg:PT molar ratio were the important factors inuencing the recovery efciency of PT and the purity of the
recovered struvite. The recovered struvite could be effectively
decomposed by NaClO, and the N decomposition ratio in it was
near 100%. When the resulting chlorination product was reused
at pH 9, the removal ratio of TAN was maximum. The TAN removal
performance of the chlorination product was maintained during
multiple recycling. The economic analysis showed that the proposed process is feasible and less costly as compared with struvite
precipitation using pure chemicals.
Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (Grant No. 51408529), the Natural
Science Foundation of Hebei Province (Grant No. E2014203080)

H. Huang et al. / Bioresource Technology 172 (2014) 253259

and the Free Research Foundation for Young Teachers of Yanshan

University (13LGB023).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2014.
09.024.
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