Bioresource Technology 98 (2007) 15291534

Removal of ammonia as struvite from anaerobic digester euents

and recycling of magnesium and phosphate
Mustafa Turker a, Ipek C
elen
b

b,*

a
Pak-Food Industries, P.O. Box 149, 41001 Izmit, Kocaeli, Turkey
Department of Environmental Engineering, Gebze Institute of Technology, Gebze, Kocaeli, Turkey

Received 13 July 2004; received in revised form 1 September 2005; accepted 15 June 2006
Available online 2 November 2006

Abstract
A second order kinetic model was developed to predict the rate and extent of NH
4 removal as struvite from anaerobic digester eu2+
ents. Alternative to this, NH
and PO3
4 can be recovered from struvite and the remaining Mg
4 can be recycled back to the wastewater
2+
3

to x more NH4 . The NH4 solution was retained and the remaining Mg and PO4 were returned back to be mixed with wastewater. In
2+
and PO3
a ve-step process, NH
4 at
4 recovery was initially 92% and progressively decreased to 77% in the fth stage, due to loss of Mg
each step in the supernatant. Finally, economic analysis of recycling nutrients was performed and compared to the one step process. The
cost of NH
4 recovery was calculated as $0.36/kg NH4-N which is lower than $7.7/kg NH4-N the cost of one step process without considering the market value of struvite obtained in one step process.
 2006 Elsevier Ltd. All rights reserved.
Keywords: Struvite precipitation; Ammonia removal; Kinetics; Recyling; Economics

1. Introduction
Nitrogen compounds, especially NH
4 , may be present
in domestic and some industrial wastewaters at levels that
may deteriorate the quality of receiving waters. Increasing
awareness of environmental issues in recent years has
resulted in a number of technologies being applied for
the removal of nitrogen from wastewaters. Some technologies, such as nitrication/denitrication and breakpoint
chlorination, convert ammonia to di-nitrogen gas. However an approach based on resource recovery is preferable
and may contribute positively to an overall nitrogen balance as well as to the economics of wastewater treatment
leading to sustainable technologies. In our previous work
we have studied the optimisation of ammonia recovery as

Corresponding author. Present address: Biosystems Engineering and

Environmental Science Department, The University of Tennessee, Knoxville, USA. Tel.: +1 865 974 2152.
E-mail address: icelen@utk.edu (I. C
elen).
0960-8524/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2006.06.026

struvite from anaerobic digester euents according to following reaction (C

elen and Turker, 2001):
3
Mg2 NH
4 PO4 6H2 O ! MgNH4 PO4 6H2 O

The kinetics of homogeneous chemical reactions can be

written with respect to one species as (Smith, 1970):


dC
n
kC
dt

where C is the concentration of reactant, k is the rate constant, and n is the order of reaction. If the equation is integrated for the rst, second, and third order, it yields the
following integrated equations respectively:
lnC lnC0  kt for 1st order
1
1

kt for 2nd order

C C0
1
1

kt for 3rd order

2
2
2C
2C0

3
4
5

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M. Turker, I. Celen / Bioresource Technology 98 (2007) 15291534

When the left hand side of Eqs. (3)(5) are plotted against
time t, one gets straight line for correct reaction order.
2. Methods
2.1. Analytical methods
The wastewater used in this work to recover ammonia is
the euent of anaerobic digester treating molasses based
industrial wastewater, the chemical composition of which
is given in Table 1. All struvite precipitation experiments
were carried out in magnetically stirred (Ikamag, Model
REC g, Germany) batch reactor equipped with temperature control unit using 200 mL of the euent. The reactions were performed in triplicate for raw wastewater and
in duplicate for kinetic data. Also, the precipitation reactions were performed in triplicate for recycled and nonrecycled nutrients. Since the anaerobic digester euent
temperature was 37 C, all precipitation experiments were
performed at that temperature. A thermostatic controller
was used to control the temperature of the reactor (Haakel,
Model 001.3568 Germany) The pH measurements were
made with pH meter (Metrohm, Model E588, Switzerland)
and pH was adjusted either with HCl or NaOH solutions.
The chemicals used were commercial grade, and their contents were determined before the experiments. All analyses
were carried out according to Standarts Methods for the
Examination of Water and Wastewater (1989). After each
experiment, the supernatants and the precipitates were ana3
lysed for Mg2+, NH
4 and PO4 to check the consistency
of experimental results. A mass balance conrmed that
3
the Mg2+, NH
present in the waste was
4 , and PO4
accounted for and exists in either in the supernatant or
the recovered precipitate.
2.2. Experiments for the kinetics of struvite formation
Kinetic studies related to struvite formation were performed with 200 ml wastewater at 37 C. The experiments
were performed in duplicate and took place at room temperature. The wastewater was thoroughly mixed using a
magnetic stir plate. pH was increased to 8.5 with NaOH
3
and Mg2 : NH
molar ratio was adjusted to
4 : PO4
1:1:1. Initially phosphoric acid (H3PO4) was used as a
PO3
4 source and a predetermined amount of NaOH were
added for pH adjustment. Since the reaction was very fast,
Table 1
The approximate composition of raw wastewater
Parameter

Concentration in water (mg l1) and standard deviation

NH
4
Mg2+
PO3
4
Ca2+
K+
COD

1400(2.5)
21.4(3)
24(5)
21.2(2)
2150(14)
3240(15)

pH was not adjusted during the course of the reaction. The

reaction started immediately after adding MgCl2 6H2O as
a Mg2+ source; and 5, 10, 20 and 30 s later samples were
taken and immediately ltered to determine the concentration of Mg2+ in the supernatant. The Mg2+ concentration
was used to follow the course of the reaction since it
requires a small amount (10 ml) of sample for analysis.
2.3. Experiments for the volatilization of ammonia from
precipitate
Three experiments were performed for the volatilization
of NH3 from precipitate; with and without the addition of
NaOH to the precipitate in a 110 C oven and stripping of
NH3 from precipitate by distillation. In the rst experiment, struvite was formed from the 200 ml wastewater
3
when Mg2 : NH
molar ratio was 1:1:1 at pH
4 : PO4
8.5. Ammonia was released into absorption water by adding NaOH and heating the solid struvite 3 h in a 110 C
oven. The molar ratio of NaOH:NH
4 was 1:1 in order to
neutralize NH
4 -NH3. The second method for the vaporization of NH3 from precipitant was distillation method.
While performing the experiments, NaOH was used to
increase pH because at high pH NH3 could be captured
in boric acid. In the last experiment, NaOH added precipitate was boiled for 15 min. The molar ratio of NaOH:NH
4
was 1:1.
2.4. Experiments for the feasibility of ammonia recovery
from precipitated struvite
3
Mg2 : NH
molar ratio and pH of the initial
4 : PO4
reaction were 1.2:1:1.2 and 8.5, respectively. After the precipitation experiment, NaOH was added to the struvite
precipitate (NaOH : NH
4 ratio equal to 1:1), the mixture
was boiled and ammonia (NH3) was stripped to the atmosphere. The resulting material (recovered Mg2+ and PO3
4 )
was added to a subsequent batch reaction. This process was
repeated four more times. After each experiment the super3
natant was analysed for Mg2+, NH
4 , and PO4 . At the
end, the precipitate was solubilized by adding concentrated
HCl and analysed for Mg2+ and PO3
4 in order to perform
economical analysis of the process.

3. Results and discussion

3.1. The composition of wastewater
The euent contains approximately 1400 mg l1 ammo1
1
nium NH
phosphate PO3
4 , 2 mg l
4 and 21.4 mg l
2+
3
2+
magnesium (Mg ). Since PO4 and Mg concentrations
were in negligible amounts, laboratory experiments were
2+
conducted using PO3
sources to force the pre4 and Mg

cipitation of NH4 as struvite and reduce the concentration

of NH
4 in the anaerobic digester euent. In an attempt to
optimize environmental conditions, C
elen and Turker
(2001) conducted experiments to identify the how much

M. Turker, I. Celen / Bioresource Technology 98 (2007) 15291534

0

2+

ln[Mg ]

2+
PO3
sources were added. Therefore, these ions
4 and Mg
were added in equimolar quantities in struvite precipitation
studies due to equimolar presence of ions in the precipitate.

3.2. Kinetics of struvite formation

3.3. Single step precipitation

In order to assess the economic viability of the process
in comparison to existing nitrogen removal technologies,
the cost of ammonia recovery as struvite was studied based
on the experimental results presented here. In this assessment, investment cost was not taken into account and only
Table 2
Kinetic data (average of two sets of experimental data)
Time
(s)

Mg2+ (mg/l)
and standard
deviation

Mg2+
(M)

Remaining
Mg2+ in
supernatant
(%)

ln
[Mg2+]

1/
[Mg2+]

1/
2[Mg2+]2

0
5
10
20
30

1855.8(12.9)
558.9(7)
340.2(10)
218.7(12)
145.8(3.5)

0.076
0.023
0.014
0.009
0.006

100
30
18.3
12.1
7.8

2.6
3.8
4.3
4.7
5.12

13.1
42.6
71.4
107.5
166.7

85.4
905.4
2551
5781
13888.9

-2
y = -0.075x - 3.102
2

R = 0.8462

-4

-6
0

10

20
Time (second)

30

40

Fig. 1. Time versus ln[Mg2+] for 1st order reaction.

150

2+

1/[Mg ]

200

100

y = 4.9334x + 16.115
2

50

R = 0.9925

0
0

10

20
Time (second)

30

40

Fig. 2. Time versus 1/[Mg2+] for 2nd order reaction.

2+ 2

18000

1/2 [Mg ]

The time course of the reaction is given in Table 2 as the

average of two sets of experimental data. The reaction was
completed in about 30 s. Integrated forms of the rst, second, and third order reaction models were tted to the
experimental data. These are presented in Figs. 13. The
constants of the kinetic model thus obtained are presented
in Table 3. The rst order approach did not give satisfactory t to the experimental data with the poor R-square
value of 0.84, whereas the third order gave reasonable t
with the R-square value of 0.92. The best t was obtained
with the second order rate approach with the R-square
value of 0.99. The initial concentration of Mg2+ was better
predicted by 2nd order model. The reaction of struvite formation was considered to be homogeneous and crystal formation was not taken into account. This assumption is true
in the nucleation period of the reaction (see Fig. 4).
In the literature, there are a few reports dealing with
struvite kinetics. Gunn (1976) claimed that the order of
struvite formation is 2.3. Ohlinger et al. (2000) reported
that struvite crystallisation obeyed rst order kinetics with
rate constant 4.2 h1. Nelson et al. (2003) also reported
rst order kinetics with the rate constants 3.7 (at pH 8.4),
7.9 (at pH 8.7) and 12.3 h1 (at pH 9.0), in similar range
as Ohlinger et al. (2000). However, we have observed much
faster precipitation kinetics completed in less than a minute. The dierence between our results and the others
might be due to the fact that we have studied nucleation
process whereas Ohlinger et al. (2000) and Nelson et al.
(2003) have investigated crystal growth, both processes
are governed by dierent mechanisms resulting in dierent
kinetic expressions.

1531

13000
8000

y = 449.26x - 1198
2

R = 0.9298

3000
-2000
0

10

20
Time (second)

30

40

Fig. 3. Time versus 1/2[Mg2+]2 for 3rd order reaction.

Table 3
Estimation of kinetic parameters in kinetic model
Order

R2

Predicted
C0 (mg/l)

Experimental
C0 (mg/l)

1st
2nd
3rd

0.8462
0.9925
0.9298

270 h1
17.76 103 l/mol h
1.6 106 l2/mol2 h

1090
1506
486

1792
1792
1792

the cost of chemicals including NaOH and steam were considered (Table 4). The commercial value of struvite was
also not considered. However, the market prices of the
chemicals used in the calculations are given in Table 4.
The results of the economic analysis for the experimental results presented are given in Table 5, with the contribution of each chemical to overall cost of struvite. The cost of
ammonia removal is a function of the removal ratio and
the cost of chemicals added per kg ammonia present in
the euent. The relative cost of MgCl2, as a Mg2+ source,
is the highest compared to those of H3PO4 and NaOH,
amounting to approximately 5565% of the overall cost.

1532

M. Turker, I. Celen / Bioresource Technology 98 (2007) 15291534

15 kg MgCl2.6H2O ($4.66)
Supernatant

6.15 L H3PO4 ($2.92)

Wastewater
1 m3
NH4+ = 1366 mgl-1

16.95 kg MAP
($0.62/kg MAP)
($7.72/kg NH4+-N)

18.25 L Caustic ($0.64)

Fig. 4. The simplied diagram for the calculation of cost of struvite from
the experimental results.

Table 4
The market prices of the chemicals used in the experiments
Chemical

Price ($/kg)

H3PO4 (75%)
MgCl2 6H2O
MgO (85%)
NaOH (100%)
NH
4

0.40
0.31
0.44
0.12
0.23

Table 5
Economic analysis of the process
Product

Price ($)/m3 wastewater

Consumed MgCl2 6H2O

Consumed 75% H3PO4
Consumed NaOH
Consumed energy
Recovered ammonium

0.00015
0.00021
0.00026
0.00012
0.00029

Total ($)
Total ($/kg NH
4)

0.00045
0.36 $/kg NH
4

However the cost of the ammonia recovery per kg ammonia xed as struvite depends on the type and stoichiometric
ratio of chemicals used. When MgO is used as a Mg2+
source, the major cost is that of H3PO4 since MgO is relatively cheap compared to MgCl2. However, the cost of the
process per kg ammonia removed as struvite does not
change much since the recovery of ammonia is relatively
low in comparison to the use of MgCl2. In order to reduce
the overall cost of the process, cheaper caustic sources such
as Ca(OH)2 can be used for pH adjustment. In this case,
calcium may compete for phosphate which may reduce
the availability of phosphate for struvite formation
(Stumm and Morgan, 1996).
The economic analysis based on the experimental results
presented in the single step precipitation work compares
well to the cost reported by other researchers. The ammonium recovery cost was calculated to be $7.7/kg NH
4 in
the one step process (Table 6) (C
elen and Turker, 2001).
Siegrist et al. (1994) considered electricity and maintenance
in addition to chemical cost of the process and came up
with $9.1011.38/kg NH
4 -N. Andrade and Schuling
(1999) reported the cost between $4.559.92/kg NH
4- N
at high ammonium concentrations. Siegrist (1996) calcu-

Table 6
Economic analysis of subsequent precipitations using recycled and nonrecycled nutrients

(NH3)initial (mg)
(Mg)initial (mg)
(PO4)initial (mg)
(Mg)added (mg)
(PO4)added (mg)
(Mg)nal precipitate (mg)
(PO4)nal precipitate (mg)
Cost ($/kg NH
4)

NH3 removal using

recycled nutrients

NH3 removal using

non-recycled nutrients

291
Negligible
Negligible
515
1888
458
1367
0.36

273.2
Negligible
Negligible
2187.5
8555
2102.5
7795
7.7

lated the cost of the process $9.72/kg NH

4 -N. In all these
works, including ours, the commercial value of struvite was
not taken into account. Webb et al., 1995) reported the cost
of chemicals as $14.9/kg NH3-N. Struvite market is still not
well established. There is an active interest to produce struvite on commercial scale in Japan. Ueno and Fuji (2001)
have reported the selling price of struvite approximately
245 Euro/ton or $4.50/kg NH
4 -N. As a result, local availability and price of chemicals and use and selling price of
struvite will determine whether this process can potentially
compete with alternative nitrogen removal and recovery
technologies currently available in the market.
Janus and van der Roest (1997) have compared economics of currently available potential biological and physical/
chemical treatment options for nitrogen-rich reject water.
They are biolm air-lift suspension reactor, conventional
nitrication and denitrication combined with membrane
bioreactor, bioreactor without sludge retention, ammonia
stripping by both air and steam and magnesium phosphate
precipitation with optional recycle. They reported that lowest cost was obtained with bioreactor without sludge retention between $3 and $5.5/kg NH
4 -N. The cost of other
methods varied between $5 and $9/kg NH
4 -N depending
on ammonia concentration present in the wastewater.
3.4. Multistep precipitation using recycled magnesium and
phosphate
The objectives of this work were NH3 removal from
wastewater, evaluation of subsequent precipitation reactions for NH3 removal using recycled nutrients (Mg2+
and PO3
4 ), and comparison of the above approach versus
NH3 removal using non-recycled nutrients. Some researchers recycle magnesium and phosphate as a precipitation
agent. Schulze-Rettmer et al. (2001) disintegrated precipitated struvite into ammonia, magnesium and phosphate
by injection of hot steam and air. Then they stripped the
ammonia and condensed it in water. The residual magnesium phosphate was used as a precipitating agent.
The vaporization of NH3 from precipitant with and
without the addition of NaOH to the precipitant in a
110 C oven and vaporization (stripping) of NH3 from precipitant by distillation is shown in Fig. 5. Ammonia

M. Turker, I. Celen / Bioresource Technology 98 (2007) 15291534

NH3 removal (%)

decreases from the precipitant amended with NaOH at the

110 C oven, were 47.7%, 70%, and 81% after 1, 2, and 3 h,
respectively. When the same experiment performed without
addition of NaOH to the precipitant at the 110 C oven,
ammonia decrease becomes less and takes more time. As
shown in Fig. 5, ammonia removal are 30%, 28%, 75%
after 1, 2, and 24 h respectively. However, after 0.25 h,
100% loss of ammonia from the precipitate was determined
when the distillation combined with NaOH were
performed.
Since the wastewater contains high ammonium concentration (approximately 1400 mg l1 NH
4 ) the concentrations of phosphate and magnesium are very low,
therefore they are added in equimolar quantities in struvite
precipitation studies. NH3 removal versus subsequent precipitations using recycled and non-recycled nutrients is
shown in Fig. 6. In a ve-step process, NH3 recovery was
initially 92% and progressively decreased to 77% in the fth
stage. NH3 removal decreased because a portion of the
added nutrients remained with the supernatant during each
subsequent reaction; this reduced the molar ratio required
for complete NH3 removal. Also, recycled magnesium
phosphate becomes more inactive because Mg3(PO4)2 or
Mg4P2O7 contents were increased (Schulze-Rettmer et al.,
2001). The nal reaction using recycled nutrients removed
20% less NH3 than reaction using non-recycled nutrients.

100
80
60
40
20
0
0.001

0.01

0.1

10

100

Time (hr)
NaOH amended precipitant at 110C
No NaOH amended precipitant at 110C

1533

3.5. Economic analysis of recycling

Economic analysis of the process was carried out and
compared to the process using non-recycled nutrients. In
this assessment, the cost of chemicals, Mg2+ source, PO3
4
source and caustic and steam used for distillation have
been considered in the calculations. As shown in Table 6,
NH3 recovery cost from the wastewater is $0.36/kg
NH
4 -N. Ueno and Fuji (2001) has reported the market
value of struvite $4.50/kg NH
4 -N. If this value is deduced
from $7.7/kg NH
4 -N which is the cost of single step precipitation process, we obtain $3.2/kg NH
4 -N as the net
cost of single step struvite precipitation which is signicantly higher than multi-step nutrient recycling process.
As a result, ammonia recovery based on the recycling of
nutrients looks attractive and can be used to remove
ammonia especially from high strength nitrogenous wastewaters as a pretreatment step.
4. Conclusions
It can be concluded from the present investigation that:
The rate of struvite precipitation is very fast and completed in less than a minute under the conditions studied
here. The rate of reaction is closer to the 2nd order. Multistep precipitation approach may provide a sustainable
method to remove NH3 from wastewaters containing primarily high NH3 levels. This method may be suitable for
high NH
4 containing wastewaters for recovering bulk of
ammonia. If the discharge standards are not met, remaining
ammonia may then be removed with conventional techniques in case single step struvite precipitation is not preferred considering the uncertainties involved in the nal
use of struvite as fertilizer. Distillation combined with caustic addition is the ecient method for vaporization of NH3
from precipitation compared to those tested here. Using
recycled nutrients for the precipitation process is as eective
and less costly than using non-recycled nutrients.

Distillation with NaOH amended precipitant

Acknowledgements

Fig. 5. The vaporization of NH3 from precipitant.

The authors would like to thank Mr. Celal Aksit, Pak

Food Industry for laboratory analysis.
Using Recycled Nutrients

Using Non-Recycled Nutrients

100
90
80
70
60
50
40
30
20
10
0

NH3 removal (%)

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3
Precipitation reaction

Fig. 6. NH3 removal versus subsequent precipitations using recycled and

non-recycled nutrients.

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elen, I., Turker, M., 2001. Recovery of ammonia from anaerobic digester
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